Aspen Polymers Vol1V7 1 Usr PDF
Aspen Polymers Vol1V7 1 Usr PDF
Aspen Polymers Vol1V7 1 Usr PDF
Aspen Polymers, Aspen Custom Modeler, Aspen Dynamics, Aspen Plus, Aspen Properties, aspenONE, the
aspen leaf logo and Plantelligence and Enterprise Optimization are trademarks or registered trademarks of Aspen
Technology, Inc., Burlington, MA.
All other brand and product names are trademarks or registered trademarks of their respective companies.
This document is intended as a guide to using AspenTech's software. This documentation contains AspenTech
proprietary and confidential information and may not be disclosed, used, or copied without the prior consent of
AspenTech or as set forth in the applicable license agreement. Users are solely responsible for the proper use of
the software and the application of the results obtained.
Although AspenTech has tested the software and reviewed the documentation, the sole warranty for the software
may be found in the applicable license agreement between AspenTech and the user. ASPENTECH MAKES NO
WARRANTY OR REPRESENTATION, EITHER EXPRESSED OR IMPLIED, WITH RESPECT TO THIS DOCUMENTATION,
ITS QUALITY, PERFORMANCE, MERCHANTABILITY, OR FITNESS FOR A PARTICULAR PURPOSE.
Contents iii
Segment Databank..............................................................................26
Polymer Databank ...............................................................................27
Segment Methodology ...................................................................................27
Specifying Components..................................................................................27
Selecting Databanks ............................................................................28
Defining Component Names and Types...................................................28
Specifying Segments ...........................................................................29
Specifying Polymers.............................................................................29
Specifying Oligomers ...........................................................................30
Specifying Site-Based Components ........................................................30
References ...................................................................................................31
6 End-Use Properties............................................................................................70
Polymer Properties ........................................................................................70
iv Contents
Prop-Set Properties .......................................................................................71
End-Use Properties........................................................................................72
Relationship to Molecular Structure ........................................................72
Method for Calculating End-Use Properties ........................................................73
Intrinsic Viscosity ................................................................................74
Zero-Shear Viscosity............................................................................74
Density of Copolymer...........................................................................75
Melt Index..........................................................................................75
Melt Index Ratio..................................................................................76
Calculating End-Use Properties........................................................................76
Selecting an End-Use Property ..............................................................76
Adding an End-Use Property Prop-Set ....................................................76
References ...................................................................................................76
Contents v
Specifying Built-In Reaction Rate Constants .......................................... 154
Assigning Rate Constants to Reactions ................................................. 154
Including User Reactions .................................................................... 154
Adding or Editing User Reactions ......................................................... 155
Specifying Rate Constants for User Reactions ........................................ 155
Assigning Rate Constants to User Reactions .......................................... 156
Selecting Report Options .................................................................... 156
Selecting the Reacting Phase .............................................................. 156
Specifying Units of Measurement for Pre-Exponential Factors................... 157
Including a User Kinetic Subroutine...................................................... 157
Including a User Rate Constant Subroutine ........................................... 157
Including a User Basis Subroutine........................................................ 157
References ................................................................................................. 158
vi Contents
Radical Balance................................................................................. 203
Kinetics of Emulsion Polymerization ..................................................... 207
Model Features and Assumptions................................................................... 211
Model Assumptions............................................................................ 211
Thermodynamics of Monomer Partitioning............................................. 211
Polymer Particle Size Distribution ........................................................ 212
Polymer Particle Properties Calculated ............................................................ 214
User Profiles ..................................................................................... 214
Specifying Emulsion Polymerization Kinetics....................................................215
Accessing the Emulsion Model ............................................................. 215
Specifying the Emulsion Model ............................................................ 215
Specifying Reacting Species ................................................................ 216
Listing Reactions ...............................................................................216
Adding Reactions............................................................................... 217
Editing Reactions............................................................................... 217
Assigning Rate Constants to Reactions ................................................. 217
Selecting Calculation Options .............................................................. 218
Adding Gel-Effect ..............................................................................218
Specifying Phase Partitioning .............................................................. 218
Specifying Particle Growth Parameters ................................................. 219
References ................................................................................................. 219
Contents vii
12 Ionic Polymerization Model ...........................................................................241
Summary of Applications.............................................................................. 241
Ionic Processes ...........................................................................................242
Reaction Kinetic Scheme .............................................................................. 242
Formation of Active Species ................................................................ 246
Chain Initiation ................................................................................. 247
Propagation ...................................................................................... 247
Association or Aggregation ................................................................. 248
Exchange ......................................................................................... 248
Equilibrium with Counter-Ion .............................................................. 248
Chain Transfer .................................................................................. 249
Chain Termination ............................................................................. 249
Coupling ..........................................................................................250
Model Features and Assumptions................................................................... 250
Phase Equilibria ................................................................................ 250
Rate Calculations .............................................................................. 250
Polymer Properties Calculated ....................................................................... 251
Specifying Ionic Polymerization Kinetics ......................................................... 252
Accessing the Ionic Model................................................................... 252
Specifying the Ionic Model .................................................................. 252
Specifying Reacting Species ................................................................ 252
Listing Reactions ...............................................................................253
Adding Reactions............................................................................... 253
Editing Reactions............................................................................... 253
Assigning Rate Constants to Reactions ................................................. 254
References ................................................................................................. 254
viii Contents
Including a User Rate Constant Subroutine ........................................... 280
Including a User Basis Subroutine........................................................ 281
References ................................................................................................. 281
14 Steady-State Flowsheeting............................................................................282
Polymer Manufacturing Flowsheets ................................................................ 282
Monomer Synthesis ........................................................................... 283
Polymerization .................................................................................. 284
Recovery / Separations ...................................................................... 284
Polymer Processing............................................................................ 284
Modeling Polymer Process Flowsheets ............................................................ 284
Steady-State Modeling Features .................................................................... 285
Unit Operations Modeling Features....................................................... 285
Plant Data Fitting Features ................................................................. 285
Process Model Application Tools........................................................... 285
References ................................................................................................. 285
Contents ix
Preliminary Parameter Fitting .............................................................. 334
Preliminary Model Development........................................................... 335
Trend Analysis .................................................................................. 335
Model Refinement .............................................................................336
Steps for Using the Data Regression Tool ....................................................... 336
Identifying Flowsheet Variables ........................................................... 338
Manipulating Variables Indirectly ......................................................... 339
Entering Point Data ........................................................................... 341
Entering Profile Data.......................................................................... 342
Entering Standard Deviations .............................................................. 343
Defining Data Regression Cases .......................................................... 343
Sequencing Data Regression Cases ...................................................... 344
Interpreting Data Regression Results ................................................... 344
Troubleshooting Convergence Problems................................................ 345
17 User Models...................................................................................................351
User Unit Operation Models .......................................................................... 351
User Unit Operation Models Structure................................................... 351
User Unit Operation Model Calculations................................................. 352
User Unit Operation Report Writing ...................................................... 357
User Kinetic Models .....................................................................................357
User Physical Property Models ....................................................................... 361
References ................................................................................................. 365
19 Run-Time Environment..................................................................................372
Aspen Polymers Architecture.........................................................................372
Installation Issues ....................................................................................... 373
Hardware Requirements ..................................................................... 373
Installation Procedure ........................................................................ 373
Configuration Tips .......................................................................................373
Startup Files .....................................................................................373
Simulation Templates ........................................................................ 373
User Fortran ...............................................................................................374
User Fortran Templates ...................................................................... 374
User Fortran Linking .......................................................................... 374
Troubleshooting Guide ................................................................................. 374
User Interface Problems ..................................................................... 374
Simulation Engine Run-Time Problems ................................................ 376
References ................................................................................................. 377
x Contents
A Component Databanks ....................................................................................378
Pure Component Databank ........................................................................... 378
POLYMER Databank .....................................................................................378
POLYMER Property Parameters ............................................................ 378
POLYMER Databank Components ......................................................... 379
SEGMENT Databank .................................................................................... 382
SEGMENT Property Parameters ........................................................... 382
SEGMENT Databank Components ........................................................ 383
Contents xi
NPHASE ...........................................................................................456
NSVAR.............................................................................................457
SSCOPY ........................................................................................... 457
Other Utilities ............................................................................................. 458
VOLL ............................................................................................... 458
Index ..................................................................................................................522
xii Contents
Introducing Aspen Polymers
Related Documentation
A volume devoted to simulation and application examples for Aspen Polymers
is provided as a complement to this User Guide. These examples are designed
to give you an overall understanding of the steps involved in using Aspen
Polymers to model specific systems. In addition to this document, a number
of other documents are provided to help you learn and use Aspen Polymers,
Aspen Plus, and Aspen Dynamics applications. The documentation set consists
of the following:
Installation Guides
Aspen Engineering Suite Installation Guide
Help
Aspen Polymers has a complete system of online help and context-sensitive
prompts. The help system contains both context-sensitive help and reference
information. For more information about using Aspen Polymers help, see the
Aspen Plus User Guide.
Third-Party
More detailed examples are available in Step-Growth Polymerization Process
Modeling and Product Design by Kevin Seavey and Y. A. Liu, ISBN: 978-0-
470-23823-3, Wiley, 2008.
Technical Support
AspenTech customers with a valid license and software maintenance
agreement can register to access the online AspenTech Support Center at:
http://support.aspentech.com
This Web support site allows you to:
Access current product documentation
Search for tech tips, solutions and frequently asked questions (FAQs)
Search for and download application examples
Search for and download service packs and product updates
Submit and track technical issues
Send suggestions
Report product defects
Polymer Molecular
Bonds
Polymer molecules involve the same chemical bonds and intermolecular
forces as other smaller chemical species. However, the interactions are
magnified due to the molecular size of the polymers. Also important in
polymer production are production rate optimization, waste minimization and
compliance to environmental constraints, yield increases and product quality.
In addition to these considerations, end-product processing characteristics
and properties must be taken into account in the production of polymers
(Dotson, 1996).
Polymerization
The polymerization step is usually the most important step in terms of the
economic viability of the manufacturing process. The desired outcome for this
step is a polymer product with specified properties such as:
Molecular weight distribution
Melt index
Composition
Crystallinity/density
Viscosity
Recovery / Separation
The recovery/separation step can be considered the step where the desired
polymer produced is further purified or isolated from by-products or residual
reactants. In this step, monomers and solvents are separated and purified for
recycle or resale. The important concerns for this step are heat and mass
transfer.
Polymer Processing
The last step, polymer processing, can also be considered a recovery step. In
this step, the polymer slurry is turned into solid pellets or chips. Heat of
vaporization is an important factor in this step (Grulke, 1994).
Summary
In summary, production rate optimization, waste minimization and
compliance to environmental constraints, yield increase, and product quality
are also important issues in the production of polymers. In addition, process
dynamics and stability constitute important factors primarily for reactors.
Component Characterization
Characterization of a polymer component poses some unique challenges. For
example, the polymer component is not a single species but a mixture of
many species. Properties such as molecular weight and copolymer
composition are not necessarily constant and may vary throughout the
flowsheet and with time. Aspen Polymers provides a flexible methodology for
characterizing polymer components (U.S. Patent No. 5,687,090).
Each polymer is considered to be made up of a series of segments. Segments
have a fixed structure. The changing nature of the polymer is accounted for
by the specification of the number and type of segments it contains at a given
processing step.
Each polymer component has associated attributes used to store information
on molecular structure and distributions, product properties, and particle size
when necessary. The polymer attributes are solved/integrated together with
the material and energy balances in the unit operation models.
Polymerization Kinetics
The polymerization step represents the most important stage in polymer
processes. In this step, kinetics play a crucial role. Aspen Polymers provides
built-in kinetic mechanisms for several chain-growth and step-growth type
polymerization processes. The mechanisms are based on well-established
sources from the open literature, and have been extensively used and
Modeling Data
A key factor in the development of a successful simulation model is the use of
accurate thermodynamic data for representing the physical properties of the
system, and of kinetic rate constant data which provide a good match against
observed trends.
In order to provide the physical property models with the parameters
necessary for property calculations, Aspen Polymers has property parameter
databanks available. These include:
Polymer databank containing parameters independent of chain length
Segment databank containing parameters to which composition and chain
length are applied for polymer property calculations
Functional group databank containing parameters for models using a
group contribution approach is also included
This User Guide contains several tabulated parameters which may be used as
starting values for specific property models. Property data packages are also
being compiled for some polymerization processes and will be made available
in future versions.
In addition to physical property data, Aspen Polymers provides users with
ways of estimating missing reaction rate constant data. For example, the data
regression tool can be used to fit rate constants against molecular weight
data.
Process Flowsheeting
Aspen Polymers provides unit operation models, flowsheeting options, and
analysis tools for a complete representation of a process.
Models for batch, semi-batch and continuous reactors with mixing extremes
of plug flow to backmix are available. In addition, other unit operation models
essential for flowsheet modeling are available such as:
Mixers
Flow splitters
Flash tanks
Devolatilization units
Flowsheet connectivity and sequencing is handled in a straightforward
manner.
Several analysis tools are available for applying the simulation models
developed. These include tools for:
Process optimization
Polymer Structure
Polymers can be defined as large molecules or macromolecules where a
smaller constituting structure repeats itself along a chain. For this reason,
polymers tend to exhibit different physical behavior than small molecules also
called monomers. Synthetic polymers are produced when monomers bond
together through polymerization and become the repeating structure or
segment within a chain. When two or more monomers bond together, a
polymer is formed. Small polymer chains containing 20 or less repeating units
are usually called oligomers.
The fact that identifiable segments are found repeatedly along a polymer
chain, provides convenient ways to categorize polymers. Polymers can be
classified based on segment composition or sequence:
Homopolymers - containing one type of repeating unit which can be
mapped into one segment
Characterization Approach
Aspen Polymers allows for the different types of chemical species that may be
found in a polymer system:
Monomers
Solvents
Catalysts
Oligomers
Polymers
Polymer segments are introduced to identify the chemical structure of the
polymer or oligomer repeat unit. In addition, they are used as building blocks
within polymerization reactions, and in the determination of thermodynamic
properties.
More than the chemical structure of the segments is needed in order to define
a polymer. Also needed is the segment composition of the chains. In addition,
properties related to size are needed: degree of polymerization or number of
segments.
Component Attributes
Within Aspen Polymers, component attributes are used to define these
structural characteristics. Component attributes are available to track
segment composition, degree of polymerization, molecular weight, etc.
Because the polymer is a mixture of chains, there is normally a distribution of
References
Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ:
Prentice Hall.
Munk, P. (1989). Introduction to Macromolecular Science. New York: John
Wiley and Sons.
Odian, G. (1991). Principles of Polymerization (3rd Ed.). New York: John
Wiley and Sons.
Rudin, A. (1982). The Elements of Polymer Science and Engineering. Orlando:
Academic Press.
Component Categories
When developing a simulation model in Aspen Polymers (formerly known as
Aspen Polymers Plus), users must assign components present in process flow
streams to one of the following categories:
Conventional
Polymer
Oligomer
Segment
Site-based
The following figure illustrates the different categories of components and
their input requirements:
3 Component Classification 21
Conventional Components
Standard conventional components are molecular components such as water.
These components have a fixed molecular structure and participate in phase
equilibrium. Components falling into this category include:
Monomers
Initiators
Chain transfer agents
Solvents
Catalysts
In order to fully specify conventional components, you need only specify pure
component data required for the phase equilibrium calculations. This data
may be entered or retrieved from component databanks.
Polymers
In Aspen Polymers, polymer components represent a distribution of polymeric
species. The average size and composition of the molecules in this distribution
22 3 Component Classification
can change throughout the simulation. Each polymer molecule is considered
to be made up of repeating units or segments. Typically, the segments
correspond to the monomers that are used to grow the polymer.
The structure of polymers depends on the number and type of segments they
contain and the arrangement of segments in linear, branched, or cross-linked
forms.
Component attributes are used to track polymer structural properties (U.S.
Patent No. 5,687,090) such as:
Segment composition
Copolymer composition and average sequence length
Degree of polymerization
Molecular weight
Branching
Moments of molecular weight distribution
Molecular architecture (physical arrangement of segments within the
polymer molecule)
Segments are specified independently from polymers. For each polymer, you
must select the types of component attributes to be included in the simulation
model. If the polymer is present in the process feed streams, you must
provide its properties by initializing the component attributes while specifying
input data for these feed streams.
For more information on component attribute specification, see Polymer
Structural Properties on page 32.
Oligomers
By convention, oligomers are defined as components with two or more
segments and a fixed molecular structure. They can be defined as volatile or
non-volatile. Typically, the oligomer feature is used to allow users to track the
loss of volatile short-chain polymers.
In order to specify oligomers, you must specify their composition in terms of
the number and type of segments they contain. Oligomers do not require
component attributes. For this reason, you may treat a polymer as an
oligomer in cases where you want to process the polymer within a unit
operation model which cannot handle polymer component attribute data.
When using oligomer components, you may specify addition properties
through the following unary property parameters:
Parameter Definition Default
3 Component Classification 23
Note: Not all kinetic models track oligomers as separate components. If a
model does not provide fields for specifying oligomers on its input forms, then
these components are not tracked.
Segments
Segments are the structural units of a polymer or oligomer and are specified
independently from these components. Their structure is fixed throughout a
simulation. Segments typically correspond to the monomers used to grow the
polymer. They are divided into types depending on their location on the
polymer chain:
Repeat units
End groups
Branch point (attached to three or four branches)
Site-Based
Site-based components pertain to multisite reaction kinetic models (Ziegler-
Natta and Ionic). Site-based components include Ziegler-Natta catalysts and
ionic initiators.
Ziegler-Natta Catalysts
Ziegler-Natta catalysts are often used to initiate polymer chain formation in
chain-growth polymerization reactions. Catalysts can be treated as standard
conventional components. Ziegler-Natta catalysts or metallocene catalysts
involve one or more polymerization site types which may be in an activated or
deactivated state.
In order to use Ziegler-Natta catalysts, you must specify the number of site
types and the catalyst properties to be tracked, that is, the site activity.
Catalyst properties are defined as component attributes. You must initialize
the catalyst properties while specifying input data for the streams containing
the catalysts.
For more information on component attribute specification, see Polymer
Structural Properties on page 32.
Ionic Initiators
Ionic initiators are used in anionic and cationic polymerization. The ionic
initiators can be treated as standard conventional components. The
propagating species in ionic polymerization can be:
Free-ions
Ion-pairs
Dormant esters
24 3 Component Classification
In Aspen Polymers, these different species are modeled as different sites of
an ionic initiator. Three different site-based attributes are tracked for an ionic
initiator. For more information, see Ionic Initiator Attributes on page 44.
Component Databanks
The thermodynamic and transport property models needed to perform the
physical property and phase equilibrium calculations during a simulation
require pure component property data. These include:
Molecular weight
Heat capacity
Heat of formation
Heat of vaporization
Vapor pressure
Density
Enter that information while selecting and specifying physical property
models. Normally, you would make use of the pure component databanks and
retrieve data from them for each of the components present in the simulation
model:
Data for conventional components are retrieved from the Pure Component
databank
Data for free-radical initiators are retrieved from the INITIATOR databank
Data for polymers are retrieved from the POLYMER databank
Data for oligomers are retrieved either from the pure component databank
or from the POLYMER databank
Data for segments are retrieved from the SEGMENT databank
Data for PC-SAFT are retrieved from the PC-SAFT databank
Data for POLYPCSF are retrieved from the POLYPCSF databank
Descriptions of the databanks, and the parameters they contain are given in
Appendix A.
Note: Catalysts are often solid components and may not be found in the
PURE11 databank. Normally, you do not need a rigorous representation of
these components.
3 Component Classification 25
An acceptable approach is to assign a monomer alias to the catalyst and then
provide the correct molecular weight and certain parameters which will
prevent the catalyst from vaporizing. If an activity coefficient model is being
used for phase equilibrium representation, the catalysts can be assumed to be
non-volatile by specifying -40 as the first Antoine parameter (PLXANT(1) = -
40).
PC-SAFT Databank
The PC-SAFT databank contains pure and binary parameters used with the
PC-SAFT property method. The parameters are taken from the literature,
including many normal compounds, polar compounds and associating
compounds.
POLYPCSF Databank
The POLYPCSF databank contains pure and binary parameters used with the
POLYPCSF property method. The parameters are taken from the literature,
including many normal compounds, but excluding polar compounds and
associating compounds.
INITIATO Databank
The INITIATO databank contains data for initiator components. Rate
constants in this databank are derived from half-life data in vendor
datasheets published on public web sites. These datasheets generally contain
data at several temperatures, allowing the activation energy and prefactor to
be determined. These rate constants depend on the reaction environment,
and may vary between polar and non-polar solvents. Where multiple sets of
data were available, the data from monomer or organic solvents were used in
preference to data from aqueous solutions.
Molecular weight and other parameters are calculated from structure using
estimation methods from Aspen Plus, except in those few cases where vapor
pressure data was provided in the datasheets.
In the INITIATO databank, components are named using industry-standard
acronyms. Each component is given an alias summarizing the number of each
type of atom: C, H, O, N, P, S, CL, F, etc. For cases where the same alias
matches several components, a counter is added to make the distinction (e.g.
1,-2, etc).
Segment Databank
In the Segment Databank, a segment name comes from the name of the
monomer from which it originates. Therefore, in this databank component
names and aliases follow the same conventions as those for the Pure
Component Databank.
A label is added to the monomer name to identify the segment as either a
repeat unit,-R, an end group,-E, or a branch point, -B (e.g. for butadiene
segments: C4H6R1or BUTADIENER1 corresponding to the repeat unit
26 3 Component Classification
CH2CH=CHCH2, C4H5E1 or BUTADIENEE1 corresponding to the end
group CH=CHCH=CH2 and C4H5B or BUTADIENEB corresponding to the
branch segment CH2 CH CH CH ).
Polymer Databank
The Polymer Databank does not follow the conventional nomenclature. The
polymer aliases are the typical acronyms used in industry or academia, and
the polymer names consist of the repeat unit name enclosed in parentheses
and preceded by the prefix Poly (e.g. PS or POLY(STYRENE) for polystyrene).
Segment Methodology
The segment approach to characterizing components is a fundamental
methodology which affects almost every functionality within Aspen Polymers.
Segments are used as the building blocks for polymers. Once you have
specified the types of segments in the polymer, the segment composition and
degree of polymerization defined as component attributes may be used to
define the size and composition of the polymer.
For oligomers, although component attributes are not used, the number of
each segment must be specified directly.
Most of the Aspen Polymers physical property models calculate polymer and
oligomer properties from segment properties. This is done by taking into
account the degree of polymerization and the segment composition. The
calculated properties should be the same for both oligomers and polymers,
assuming that the oligomer structure and molecular weight were specified
correctly. Note that this is true for mass-based properties only. Mole-based
properties will be different between polymer and oligomer if their apparent
molecular weights are different.
Within the polymerization reaction models, segments also play a key role. As
polymerization progresses, the models map the reacting monomers into the
corresponding segments and return rates of change for the segment
composition.
Specifying Components
To specify components within your model you need to know the following:
Item For
3 Component Classification 27
Property parameter databank The species in the system
selections
IUPAC names All conventional components or you need their
physical properties (molecular weight, boiling point,
Antoine constants, etc.)
Segment structure All polymers and oligomers (define whether you want
to include any end groups or branch points)
Polymer properties to be All polymers, that is, degree of polymerization,
tracked segment composition
Additional characteristics All additional characteristics for catalysts, or ionic
initiators
Selecting Databanks
For an Aspen Polymers simulation, you generally retrieve physical property
data from the following databanks:
Pure component databank (PURE12)
Polymer databank (POLYMER)
Polymer segment databank (SEGMENT)
Initiator databank (INITIATOR)
You can also use other Aspen Plus databanks, user databanks, or in-house
databanks. Appendix A provides descriptions of the polymer and segment
databanks and the parameters they contain.
If you selected a polymer template to start your simulation, the correct
databanks are already specified.
If you did not select a polymer template, or if you want to modify the
databank selection:
1 From the Data Browser, click Components.
2 From the Components folder, click Specifications.
3 On the Selection sheet, click the Databanks tab to open the databank
selection form.
28 3 Component Classification
To define component names and types:
1 On the Selection sheet, in the Component ID field, specify an ID for
each component.
This ID is used to refer to the component in all subsequent input, and is
also used to identify the component in the simulation report.
2 For polymers, oligomers, and segments, specify the component type in
the Type field.
By default, all components are assumed to be standard conventional
components. For Aspen Polymers simulation you must correctly identify
the component types:
Use For
Specifying Segments
The Type of each polymer or oligomer segment must be specified on the
Polymer Characterization Segments sheet. Segments can be repeat units,
end groups or branch points attached to three or four branches.
To access the segments definition input form:
1 From the Data Browser, click Components.
2 From the Components folder, click Polymers.
3 From the Polymers folder, click Characterization.
To define segments:
On the Segments sheet, assign a type to the segments from the Type
field.
Specifying Polymers
For each polymer you must define the component attributes to be tracked. All
components specified Polymer in the Components Specifications folder
require component attributes.
To access the polymer input specifications:
1 From the Data Browser, click Components.
2 From the Components folder, click Polymers.
3 From the Polymers folder, click Characterization.
4 From the Characterization form, click the Polymers tab.
To specify component attributes for the polymers in your simulation:
3 Component Classification 29
1 In the Polymer ID field, select the polymer.
2 If you want to retrieve a predefined set of component attributes, in Built-
in attribute group select a grouping. The attribute summary table is
filled in.
For a complete discussion of Aspen Polymers component attributes, see
Polymer Structural Properties on page 32.
or
If you do not want to use a predefined set of attributes, or if you want to
change the attribute selection for a given group, click the attribute table
or click Edit to open the attribute list.
3 Click specific attributes to add or remove them from the list.
Repeat these steps for each polymer.
Specifying Oligomers
For each oligomer you must specify an ID and a structure in terms of number
and name of contained segments.
To access the oligomers definition input form:
1 From the Data Browser, click Components.
2 From the Components folder, click Polymers.
3 From the Polymers folder, click Characterization.
4 From the Characterization form, click the Oligomers tab.
To define oligomers:
1 In the Oligomer field, select the oligomer.
2 In the Segment field, enter the name of a segment contained in the
oligomer.
3 Repeat these steps for each oligomer.
You can define as many segments as needed for an oligomer.
30 3 Component Classification
4 Select the list of properties or component attributes to be tracked for that
component. Click the attribute list table or Edit to open the attribute list.
5 Click specific attributes to add or remove them from the list for the
component.
References
Bailey, J., & Ollis, D. F. (1986) Biochemical Engineering Fundamentals (2nd
Ed.). New York: McGraw-Hill.
Brandrup, J., & Immergut, E. H. (Eds.). (1989). Polymer Handbook (3rd Ed.).
New York: John Wiley & Sons.
Danner R. P., & High, M. S. (1992). Handbook of Polymer Solution
Thermodynamics. New York: American Institute of Chemical Engineers.
Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and
Engineering. New York: John Wiley and Sons.
3 Component Classification 31
4 Polymer Structural
Properties
This section discusses the use of component attributes for tracking polymer
structural properties in a simulation model.
Topics covered include:
Structural Properties as Component Attributes, 32
Component Attribute Classes, 33
Component Attribute Categories, 34
Component Attribute Initialization, 46
Component Attribute Scale Factors, 50
Specifying Component Attributes, 51
Structural Properties as
Component Attributes
Component attributes provide a convenient framework to associate structural
characterization data to components in a flow stream. They are carried
throughout the flowsheet along with state and composition information, and
effectively extend the stream structure.
Aspen Polymers (formerly known as Aspen Polymers Plus) uses component
attributes as a vehicle for tracking important modeling information for
polymers, ionic initiators and Ziegler-Natta catalysts (U.S. Patent No.
5,687,090). For example, there are component attributes to store:
Segment composition (segment fraction or segment flow)
Copolymer composition and average sequence length
Degree of polymerization (number, weight, and z-average)
Molecular weight (number, weight, and z-average)
Degree of branching (long and short)
Degree of cross-linking (cross-link density)
Molecular architecture (physical arrangement of segments within the
polymer molecule)
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
* Although the dimension is NSEG, these attributes only apply to diene segments, other elements
will be set to zero.
i = Segment index
i = Segment index
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
site j
SZMOM 0( j) Zeroth moment of ---- 2 NSITE Mole
chain length flow
distribution at site j
SFMOM 1 ( j ) First moment of
chain length
1 ( j ) = ( i, j )
1
0 NSITE Mole
flow
distribution at site j
SSMOM 2( j) Second moment of ---- 2 NSITE Mole
chain length flow
distribution at site j
STMOM 3( j ) Third moment of ---- 2 NSITE Mole
chain length flow
distribution at site j
SSFLOW 1 ( i , j ) Mole flow of ---- 2 NSEG, Mole
segments of type I NSITE flow
at site j
SSFRAC Fp ( i, j ) Mole fraction of Fp ( i, j ) = 1 ( i, j ) / 1 ( j ) 0 NSEG; Unitless
segments of type I NSITE
at site j
SEFRAC Fe ( i, j ) Fraction of chain Fe ( i, j ) = 1 ( i, j ) / 1( i, j ) 0 NEND, Unitless
end segments of ends NSITE
type i at site j
SLCB LCB( j ) Number of long ---- 2 NSITE Mole
chain branches at flow
site j
SSCB SCB( j ) Number of short ---- 2 NSITE Mole
chain branches at flow
site j
SFLCB FLCB( j ) Long chain 103 LCB( j ) 0 NSITE Unitless
branching frequency FLCB( j ) =
at site j 1 ( j )
SFSCB FSCB( j ) Short chain 103 SCB( j ) 0 NSITE Unitless
branching frequency FSLB( j ) =
at site j 1 ( j )
i = Segment index
j = Site number
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
i = Segment index
j = Site number
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
i = Segment index
j = Site number
Equation for recalculating class 0 attributes only. Class 2 attributes are integrated.
User Attributes
Generic component attributes are available for tracking user-specified data.
These may be used to track additional properties not available through the
pre-defined attributes.
User component attributes are available as Class 0 through Class 2 attributes.
You must supply a Fortran subroutine to return rates of change for Class 2
attributes and recalculate Class 0 attributes. This would typically be a user
kinetic routine.
User attributes DPSDN and DPSDW are designed to hold data related to
particle size distributions of solid polymers or monomers. The number flow
rates (DPSDN) have units of inverse time. Since particle flow rates are often
very high the user may wish to apply appropriate scaling to define this
attribute on a relative basis (for example use this attribute to track flow rates
in trillions of particles/sec). The DPSDW attribute tracks the mass flow rate of
each element of the distribution. User subroutines are required to use this
advanced feature.
The following table lists the available user component attributes:
Attribute Description Unit Type Dimension
SFRAC SFRAC 1
SFLOW / SUM (SFLOW) 2
1 / NSEG 3
ZMOM ZMOM 1
FMOM / DPN 2
FMOM*MWSEG / MWN 3
PDI*FMOM*FMOM / SMOM 4
FMOM SUM (SFLOW) 1
PMASS / MWSEG 2
SMOM SMOM 1
FMOM*DPW 2
FMOM*MWW / MWSEG 3
FMOM*FMOM*PDI / ZMOM 4
ZMOM 5
TMOM TMOM 1
SMOM*DPZ 2
SMOM*MWZ / MWSEG 3
LCB LCB 1
FMOM*FLCB / 1.E3 2
SCB SCB 1
FMOM*FSCB / 1.E3 2
PSDZMOM PSDZMOM 1
PSDFMOM PSDFMOM 1
PMASS / PDENS 2
PSDSMOM PSDSMOM 1
PSDTMOM PSDTMOM 1
VOLN VOLN 1
PSDFMOM / PSDZMOM 2
0.0 3
VOLV VOLV 1
PSDSMOM / PSDSMOM / PSDFMOM 2
0.0 3
VOLZ VOLZ 1
PSDTMOM / PSDSMOM 2
0.0 3
DIAV DIAV 1
(6.0*PSDFMOM / / PSDZMOM) 2
0.0 3
PDV PDV 1
(PSDZMOM*PSDSMOM) / (PSDFMOM) 2
0.0 3
LSFRAC LSFRAC 1
LSFLOW / SUM (LSFLOW) 2
1 / NSEG 3
LZMOM LZMOM 1
LPFRA*ZMOM 2
LFMOM / LDPN 3
LFMOM*LMWSEG / LMWN 4
LPDI*LFMOM*LFMOM / LSMOM 5
LFMOM SUM (LSFLOW) 1
LZMOM*LDPN 2
LZMOM*LMWN / LMWSEG 3
LZMOM*LSMOM / LPDI 4
LSMOM LSMOM 1
LFMOM*LDPW 2
LFMOM*LMWW / LMWSEG 3
LFMOM*LFMOM*LPDI / LZMOM 4
Composite Aggregate Polymer Attribute Set
ASFRAC ASFRAC 1
ASFLOW / SUM (ASFLOW) 2
1 / NSEG 3
AZMOM AZMOM 1
APFRA*ZMOM 2
AFMOM / ADPN 3
AFMOM*AMWSEG / AMWN 4
APDI*AFMOM*AFMOM / ASMOM 5
AFMOM SUM (ASFLOW) 1
AZMOM*ADPN 2
AZMOM*AMWN / AMWSEG 3
AZMOM*ASMOM / APDI 4
ASMOM ASMOM 1
AFMOM*ADPW 2
AFMOM*AMWW / AMWSEG 3
AFMOM*AFMOM*APDI / AZMOM 4
SSFRAC SSFRAC 1
SSFLOW / SUM (SSFLOW) 2
1 / NSEG 3
LSSFRAC LSSFRAC 1
LSSFLOW / SUM (LSSFLOW) 2
1 / NSEG 3
LSZMOM LSZMOM 1
LSPFRA*SZMOM 2
LFSMOM / SLDPN 3
LSFMOM*LSMWSEG / SLMWN 4
LSPDI*LSFMOM*LSFMOM / LSSMOM 5
LSFMOM SUM (LSSFLOW) 1
LSZMOM*LSDPN 2
LSZMOM*LSMWN / LSMWSEG 3
DSQRT (LSZMOM*LSSMOM / LSPDI) 4
LSSMOM LSSMOM 1
LSFMOM*LSDPW 2
LSFMOM*LSMWW / LSMWSEG 3
LSFMOM*LSFMOM*LSPDI / LSZMOM 4
Site Based Aggregate Polymer Attribute Set
ASSFRAC ASSFRAC 1
ASSFLOW / SUM (ASSFLOW) 2
1 / NSEG 3
Specifying Component
Attributes
There are several categories of components for which you can specify
component attributes:
Polymers
Site-based components
Conventional components
References
Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc.
Distribution Functions
In the majority of cases, the distribution functions proposed in the literature
are based on a statistical approach and use one of three types of
mathematical functions: binomial, Poisson or Gaussian.
The parameters in these distribution functions can easily be calculated from
the polymer average properties (degree of polymerization, polydispersity
index, etc.). The following are the common distribution functions that have
been applied to the calculation of polymer property distributions:
Schulz-Flory Most Probable (Flory, 1936, 1953; Schulz, 1935, 1939)
Schulz (Schulz, 1935, 1939)
Weibull-Tung Generalized Exponential (Tung, 1956; Weibull, 1951)
Normal (Biesenberger & Sebastian, 1983)
Wesslau Logarithmic Normal (Wesslau, 1956)
Lansing Logarithmic Normal (Lansing, 1935)
Poisson (Biesenberger & Sebastian, 1983)
Zimm (Zimm, 1948)
Stockmayer Bivariate (Stockmayer, 1945)
In addition to these distribution functions, a method using the moments of
distributions is also available (Tompa, 1976). Of these functions, two have
greater importance for Aspen Polymers.
Mole-Fraction Distribution
F ( r ) = p r 1 (1 p ) (number distribution)
Weight-Fraction Distribution
W ( r ) = rp r 1 (1 p )2 (weight distribution)
Where:
p = Extent of reaction
r = Size of the molecule or number of segments
For addition polymerizations p is the probability that a growing live polymer
molecule will propagate. For step-growth reactions, p is the fractional
conversion of monomer end groups.
From these distributions, the number, weight, and z-average degree of
polymerization are:
1
DPn =
(1 p )
(1 + p )
DPw =
(1 p )
F ( r ) = p r 1 (1 p )
PDI = 1 + p
To generate the distribution, p can be calculated from degree of
polymerization as:
1
p = 1
DPn
Note that the polydispersity approaches two as p unity.
and
Density Function
S
F ( S ) = f ( s) ds
s0
Where:
s0 = Initial value of s
f ( s) = Density function
Average Properties
The average properties can be calculated as ratios of the moments. Number
average is the ratio of first to zeroth moment, 1 / 0 . Weight or Volume
average is the ratio of second to first moment, 2 / 1 . Z-average is the ratio
of third to second moment, 3 / 2 .
For the case of chain length distribution the moment frequency distribution is
given by:
m = n mQn
PDI = 2 0 / 21
A similar definition of moments for the frequency distribution can be applied
to molecular weight. Typically, in Aspen Polymers it is applied to chain length.
Then the average molecular weight values are determined using the average
degree of polymerization and average segment molecular weight.
K p [ M ][ R o r 1 ]
[R ] = K [M ] + K
o
r
[ M ] + K fT [T ] + (K tc + K td )[ R o ]
p fm
Where:
[ R ] = 2K
I d f [ I ] = Initiation rate
Rtd + R f K td [ Ro ] + K fm [ M ] + K fT [T ]
= =
Rp K p[ M ]
Rtc K tc [ Ro ]
= =
Rp K p [ M ]
Where:
Rp = K p [ Ro ][ M ] = Propagation rate
The equations for the rate of generation and consumption of radicals can be
written as follows:
[ R ] = 1 + + + [ R ]
o
l
o
1
[R ] = 1+ + [R ]
o
r
o
r 1
[ R ] = [ R ]( + )
o
r
o r
Where:
1
=
1+ +
The rate of production of polymer molecules of chain length r , RFp ( r ) is
given by:
(
1 d V [ Pr ] )
( )
r 1
1
RFP ( r ) = = K fm[ M ] + K fT [T ] + K td [ Ro ] [ R o r ] + K tc [ Ro s ][ Ro r s ]
V dt 2 s =1
Substituting [ R of ] gives:
RFP ( r ) = K p [ Ro ][ M ]( + ) + ( + )( r 1) r
2
rRFP ( r )
( + ) + 2 ( + )( r 1) r r
W (r ) = = = ( + ) + ( + )( r 1) r r +1
1+ + 2
rR
r =1
FP (r)
In other words, W(r) is the weight chain length distribution of dead polymer
chains produced in a small time interval t to t+dt, in a batch reactor. W(r) is
also the weight chain length distribution of dead polymer chains produced in a
CSTR operating at steady-state.
If << , which is the case when the polymer chains are formed by chain
transfer or by termination by disproportionation, this equation reduces to:
r 1 2
r +1 1
W ( r ) = r 2
= r
1+ 1+
Where:
1 / (1 + ) = Probability of growth for a polymer radical
Pn =
1 (1 + + ) 1
W (r ) + +
r 1 r 2 2
Pw (2 + 3) + 2
PDI =
Pn ( + )2
Copolymerization
The chain length distribution equation on page 61 applies to both homo- and
co-polymerization with two or more monomer types. When chain growth
polymerizations are done with active center types other than radicals
(Ziegler-Natta, metallocene, etc.) = 0 in the equation, and the
instantaneous chain length distribution becomes a single parameter
distribution, which is Florys most probable distribution with a polydispersity
index of 2.0.
This equation is the main expression used in Aspen Polymers to generate
chain length distribution. Within the context of a polymerization reactor, this
expression is valid for the case of linear chains of a homopolymer produced in
a single CSTR at steady-state.
CSTR in Series
For the case of two CSTRs in series, the end product polymer distribution is a
composite that is a weighted average of the distributions of polymer produced
in the first and the second reactor:
m1 m
Wout ( r ) = * W1 ( r ) + 2 * W2 ( r )
m m
Where:
m = m1 + m2 = Total mass of polymer produced in the first and second reactor
per unit time
i log10 (upper )
ri = max i, alog
N
point
Where i varies between one and the specified number of points Npoint, and
upper is the user-specified upper bound of the distribution. This spacing
provides good resolution over the entire spectrum of molecular weights, with
emphasis on the low molecular weight species that are more likely to be lost
in fractionation steps. To ensure accuracy, the upper bound should be set at
Wrlocal = r ( + ) + ( + )(r 1) exp[ r ( + )]
2
For multi-site kinetics (Ziegler-Natta):
j
Wrlocal
,j = r ( j + j ) j + ( j + j )(r 1) exp r ( j + j )
[ ]
2
W local
=
j
m j Wrlocal
,j
r
j
mj
For plug-flow reactors, the values of and are calculated at each axial step
during the numerical integration. The local distribution for the reactor is
calculated by summing the instantaneous distributions (from either equations
local
for Wr given previously) at each step over all the steps from the reactor
inlet (z = 0) to the reactor outlet (z = L).
For single-site kinetics:
Wr , z = r ( z + z ) z + z ( z + z )(r 1) exp[ r ( z + z )]
2
L
m z Wr , z
W r
local
= z =0
L
m
z =0
z
j,z
Wr , j , z = r ( j , z + j , z ) j , z + ( j , z + j , z )(r 1) exp r ( j , z + j , z )
[ ]
2
L
m j,z Wr , j , z
W local
r, j = z =0
L
m
z =0
j,z
The local site-based and composite distributions are stored in the reactor
results form and can be viewed from the Reactor folder Results subfolder,
Distributions sheet and plotted using the Aspen Plot Wizard.
m k Wr ,k
Wr feed
= k =1
N feeds
m k =1
k
GPC Distributions
If the user selects the GPC Distribution format, the distribution is calculated
as rWr .
W + Wi
wi = (ri +1 ri ) i +1
2
For GPC curves (distribution stores rWi ):
wi =
(ri +1 ri ) Wi +1 + Wi
2 r ri
i +1
Where:
w
i =1
i 1.0
If the calculated area is below unity, the specified upper bound of the
distribution may be too low. If the calculated area is greater than one, the
number of points in the distribution may need to be increased to improve the
accuracy of the distribution calculations.
For chain-length distributions, the value r refers to the molecular size. The
number average and weight average degree of polymerization can be
calculated as:
1
N points wi N points
Pn = Pw = 1
w (r + ri )
2 (ri +1 + ri )
1 2 i i +1
i =1 i =1
M n = 1
(r + r )
Mw = 1
2 w (r i i +1 + ri )
i =1 2 i +1 i i =1
The area under the distribution curve and the number- and weight-average
properties of the distribution can be generated by the plot wizard and
displayed on the distribution plots.
For unit operation blocks, the number- and weight-average properties of the
distribution may be verified against the local polymer results, displayed on
the Polymer Results sheet for each reactor.
For streams, the number- and weight-average properties of the distribution
may be verified against the polymer component attributes shown in the
stream table.
Requesting Distribution
Calculations
In order to track distributions in your simulation, you must select the
distribution characteristics. After the simulation is complete you must retrieve
the distribution data for plotting. You can display and plot the distribution
data for the polymerization reactor, or you can display a distribution table for
a stream or for the entire flowsheet.
References
Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization
Engineering. New York: Wiley-Interscience.
Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: Wiley-
Interscience.
Flory, P. J. (1936). Molecular Size Distribution in Linear Condensation
Polymers. J. Am. Chem. Soc., 58, 1877.
Flory, P. J. (1953). Principles of Polymer Chemistry. Ithaca, NY: Cornell
University Press.
Hamielec, A. E. (1992). Polymerization Processes. In B. Elvers, S. Hawkins, &
G. Schulz (Eds.), Ullmanns Encyclopedia of Industrial Chemistry (5th Ed.)
A21, (pp. 324-330). New York: VCH.
Lansing, W. D., & Kramer, E.O. (1935). Molecular Weight Analysis of Mixtures
by Sedimentation Equilibrium in the Svedberg Ultracentrifuge. J. Am. Chem.
Soc., 57, 1369.
Peebles, L. H., Jr. (1971). Molecular Weight Distribution in Polymers. New
York: Wiley-Interscience.
Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere
Publishing.
Schulz, G. V. (1935). Uber die Beziehung zwischen Reaktionsgeschwindigkeit
und Zusammensetzung des Reaktionsproduktes bei
Makropolymerisationsvorgngen., Z. Physik. Chem., B30, 379.
Schulz, G. V. (1939). Uber die Kinetik der kettenpolymerisationen. V. Der
Einfluss verschiedener Reaktionsarten auf die Polymolekularitt. Z. Physik.
Chem., B43, 25.
Stockmayer, W. H. (1945). J. Chem. Phys., 13, 199.
Tompa, H. (1976). The Calculation of Mole-Weight Distributions from Kinetic
Schemes. In C.H. Bamford & C.F.H. Tipper (Eds.), Comprehensive Chemical
Kinetics, 14A. New York: American Elsevier.
Tung, L. H. (1956). Fractionation of Polyethylene. J. Polymer Sci., 20, 495.
Weibull, W. (1951). A Statistical Distribution Function of Wide Applicability. J.
Appl. Mech., 18, 293.
Polymer Properties
Polymer properties fall into many categories:
Structural properties
Thermophysical properties - which provide an indication of the
thermodynamic behavior of polymers
Thermochemical properties - which provide information on thermal
stability
Transport properties
Processing and end-use properties - which provide information about
processability and performance during end-use
Polymer structural properties do not provide a direct measure of the
performance of the polymer product during processing or during its end use.
However, there is a relationship between polymer structural properties and
the end use properties. For this reason, it is important to account for such
properties within polymer process simulation models.
70 6 End-Use Properties
Prop-Set Properties
A property set is a collection of thermodynamic, transport, and other
properties that you can use in:
Stream reports
Physical property tables and Analysis
Unit operation model heating/cooling curve reports
Distillation column stage property reports and performance specifications
Reactor profiles
Design specifications and constraints
Calculator and sensitivity blocks
Optimization and Data-Fit blocks
Aspen Plus has several built-in property sets that are sufficient for many
applications. The list of built-in property sets is determined by the Template
you choose when creating a new run.
You can use a built-in property set and modify it to fit your needs, or you can
create your own property sets. To see the built-in sets available or to select
one, use the drop-down list on any property set list box. The list prompts
describe the contents of each built-in property set.
For information on defining a property set, see the Aspen Plus User Guide.
The following table summarizes key property sets for the major
thermophysical and transport properties of interest in polymer process
simulations:
Property Valid Qualifiers
Set
Name Description Phase Comps. Temp. Pres.
6 End-Use Properties 71
End-Use Properties
The end-use or processing properties of interest for polymers include
properties that describe their performance in the last stage of the polymer
manufacturing process. Also of interest are properties relating to their
performance when they reach the consumer.
The following table summarizes some end-use properties:
Category Property Availability in
Aspen Polymers
72 6 End-Use Properties
Properties Molecular Melt Density
Weight Index
6 End-Use Properties 73
Intrinsic Viscosity
The intrinsic viscosity is given as:
= K M w + JM w
Where:
= Intrinsic viscosity
Mw = Weight-average molecular weight
Zero-Shear Viscosity
For some ethyl branched paraffinic monodisperse polymers, Arnett and
Thomas reported an empirical correlation for zero-shear viscosity as a
function of molecular weight, number of branched sites per 1000 carbon
atoms, and temperature (Arnett & Thomas, 1980):
d (1 + cn) bn
3
ln 0 = a ln M w + e + B( n )
T
Where:
0 = Zero shear viscosity in Poise
Mw = Molecular weight
74 6 End-Use Properties
Density of Copolymer
Randall and Ruff presented an empirical correlation for semicrystalline
copolymer density (Randall & Ruff, 1988):
a n
= a + b(1 ) i i
2
c a i =1
Where:
= Actual density
c = Crystalline density
a = Amorphous density
Melt Index
Karol and colleagues suggested a Quackenbos equation for high density
polyethylene prepared with chromocene-based catalysts (Karol et al., 1973;
Quackenbos, 1969):
MI = a( bM w + cM n )
d
Where:
MI = Melt index
a = . 1018
10
b = 0.2
c = 0.8
d = -3.9
Mw = Weight-average molecular weight
6 End-Use Properties 75
Melt Index Ratio
The Quackenbos equation can also be used to correlate melt index ratio.
References
Arnett, R. L. & Thomas, C. P. (1980). Zero-Shear Viscosity of Some Ethyl
Branched Paraffinic Model Polymers. J. Phys. Chem., 84, 649-652.
Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc.
Bicerano, J. (1996). Prediction of Polymer Properties. New York: Marcel
Dekker.
Foster, G.N. (1993). Short Course: Polymer Reaction Engineering. Ontario,
Canada: McMaster Institute for Polymer Production Technology.
76 6 End-Use Properties
Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ:
Prentice Hall.
Hamielec, A. E. (1996), Polymer Reactor Modeling Technology (Course
Notes). Cambridge, MA: Aspen Technology, Inc.
Karol, F. J., Brown, G. L., & Davison, J. M. (1973) Chromocene-Based
Catalysts for Ethylene Polymerization: Kinetic Parameters. J. of Polymer
Science: Polymer Chemistry Edition, 11, 413-424.
Quackenbos, H. M. (1969). Practical Use of Intrinsic Viscosity for
Polyethylenes. J. of Applied Polymer Science, 13, 341-351.
Randall, J. C. & Ruff, C. J. (1988). A New Look at the 'Run Number' Concept
in Copolymer Characterization. Macromolecules, 21, 3446-3454.
Rudin, A. (1982). The Elements of Polymer Science and Engineering. New
York: Academic Press Inc., Harcourt Brace Jovanovich.
Sinclair, K. B. (1983). Characteristics of Linear LPPE and Description of UCC
Gas Phase Process, Process Economics Report. Menlo Park, CA: SRI
International.
6 End-Use Properties 77
7 Polymerization Reactions
Polymerization Reaction
Categories
Over the years, many classifications have been developed for polymerization
reactions. One classification divides them into condensation and addition
polymerization.
Condensation Polymerization
Condensation polymerization results in the elimination of a smaller molecule,
water for example, through the reaction of bi- or polyfunctional monomers.
Addition Polymerization
Addition polymerization, on the other hand, does not produce small molecule
byproducts. The repeating units within the polymer have the same structure
as the monomers from which they originated.
78 7 Polymerization Reactions
The problem with this classification is that while it describes differences in the
molecular structure of the resulting polymer, it does not fully capture the
differences in the reaction mechanism. Furthermore, a given polymer can be
made by more then one pathway, one which would result in an addition
polymer, and one which would result in a condensation polymer, by this
classification.
For example, Nylon-6 can be made through a caprolactam, and therefore be
labeled an addition polymer, or through an -aminohexanoic acid, and in this
case be labeled a condensation polymer.
Step Growth
7 Polymerization Reactions 79
n activation complex carbon bond
Ionic Anion or cation Dissociation Monomers add on at ion
pair
Step-Growth Polymerization
Step-growth polymerization retains the definition given for condensation
polymers for the majority of cases. That is, monomers react with each other
to eliminate small molecules. Step-growth polymers are formed through the
same reaction type occurring between functional groups located on any
combination of monomers, oligomers, or polymer chains. The polymer chains
continue to grow from both ends as polymerization progresses. The reactions
occur at a relatively slow rate and chains grow slowly.
Some examples of step-growth polymers include polyamides, polyesters,
polycarbonates, and polyurethanes (See Polymer Structure in Chapter 2 for a
discussion of polymer types based on molecular structure).
Chain-Growth Polymerization
Chain growth polymers are formed through the addition of monomers to an
active center (free-radical, ion, or polymer-catalyst bond), in a chain
reaction, at a very fast rate. Furthermore, several different types of reaction
occur to initiate, propagate, and terminate polymer growth. Examples of
80 7 Polymerization Reactions
chain growth polymers include various polyolefins, polyvinyls, and several
copolymers (styrenic copolymers, for example).
7 Polymerization Reactions 81
Solution processes are carried out in the presence of an inert solvent
Interfacial processes are carried out in the interface between an organic
phase and an aqueous phase
Built-in Models
The polymerization reaction models available in Aspen Polymers are
summarized in the following table:
Model Name Chemistry Processes Polymers
Step-growth
82 7 Polymerization Reactions
Model Name Chemistry Processes Polymers
EMULSION Free-radical Emulsion SBR, SBA
ZIEGLER-NAT Ziegler-Natta / metallocene Bulk, HDPE, PP, LLDPE
coordination complex solution
IONIC Anionic/Cationic group Solution PIB, SBR, PEO
transfer
Generic
In addition to models for the chemistries and process types listed, there is
one model available for generic polymer modification reactions. This model
follows a standard power-law scheme and is used to represent reactions
involving modifications to segments of polymers made through one of the
conventional reaction schemes. One of the standard Aspen Plus reaction
models can also be used in conjunction with the polymerization reaction
models. The standard Aspen Plus reaction models are:
For more information about these models, consult the Aspen Plus User Guide
and Aspen Plus User Models.
User Models
There are cases where the built-in models do not provide the features
necessary to model specific polymerization kinetics. Some of the
polymerization reaction models provide capabilities to incorporate user
reactions. In addition, the USER reaction model provides the capabilities for
defining user kinetic schemes.
The USER reaction model is structured to allow the specification of the
reaction stoichiometry. In addition, there are vectors for entering user real
and integer parameters. This input information along with the reaction vessel
contents, in the form of the stream structure, is made available to a user
supplied Fortran subroutine during calculations.
Note that component attributes are part of the stream structure. There is an
update and initialization scheme to automatically process these attributes.
The user supplied Fortran subroutine can return rates for components and
component attributes.
From the subroutine, Aspen Plus utilities including physical property routines,
math utilities, and stream handling utilities can be accessed. Some of these
utilities are documented in Appendix C.
7 Polymerization Reactions 83
References
Aspen Plus User Models. Cambridge, MA: Aspen Technology, Inc.
Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc.
Dotson, N. A, Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization
Process Modeling. New York: VCH Publishers.
Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ:
Prentice Hall.
Hamielec, A. E. (1992). Polymerization Processes. In B. Elvers, S. Hawkins, &
G. Schulz (Eds.), Ullmanns Encyclopedia of Industrial Chemistry (5th Ed.)
A21, (pp. 324-330). New York: VCH.
Odian, G. (1991). Principles of Polymerization, 3rd Ed. New York: John Wiley
& Sons.
Rudin, A. P. (1982). The Elements of Polymer Science and Engineering.
Orlando, FL: Academic Press.
Sun, S. F. (1994). Physical Chemistry of Macromolecules. New York: John
Wiley & Sons.
84 7 Polymerization Reactions
8 Step-Growth
Polymerization Model
Summary of Applications
Step-growth polymerization can be used to model various polycondensation
and specialty plastic processes. Some of the applicable polymers are
described below:
Aliphatic polycarbonates - Transesterification of diols with lower dialkyl
carbonates, dioxolanones, or diphenyl carbonate in the presence of
catalysts such as alkali metal, tin, and titanium compounds.
Aromatic polycarbonates - Reaction product of bisphenols with carbonic
acid derivatives. May be prepared by transesterification, solution
polymerization, and, most often by interfacial polymerization.
Step-Growth Processes
Several commodity polymers, including polyesters, nylons, and
polycarbonate, are manufactured through step-growth polymerization
processes. This section examines some of the major processes that can be
represented using the step-growth polymerization kinetics model.
Polyesters
Direct Esterification
The direct esterification process involves the reaction of ethylene glycol with
terephthalic acid. The terephthalic acid is mixed with excess ethylene glycol to
form a solid-liquid paste. In the continuous process, the monomer paste is
typically fed to a well-mixed reactor, the primary esterifier, which operates at
temperatures of 250-290 C and pressures ranging from one to several
atmospheres. Typical residence times range from one to four hours in this
stage of the process.
A solid at room temperature, terephthalic acid has limited solubility in the
polymer solution, even at the relatively high process temperatures. Further,
the dissolution rate of TPA may be limited by the solid-liquid mass transfer
rate, especially if the average particle size is large, or when the reactor
operates at high temperatures and pressures.
The following figure illustrates a continuous direct esterification process for
PET:
Glycol Recovery
The ethylene glycol from the esterification distillation columns can be recycled
directly to the esterification reactors, to the paste mixing tank, or, in the case
of high-quality products, it can be collected for further processing to remove
contaminants. The companies which license PET technology use a wide
variety of glycol recovery and recycling schemes. All of these recycling
schemes can be simulated using conventional distillation, flash, and heat
exchanger models available in Aspen Plus.
Transesterification Process
In the transesterification process, dimethyl terephthalate (DMT) is used
instead of terephthalic acid (TPA). One advantage of this process is the
relatively high solubility of DMT, which eliminates the solid-liquid mass
transfer problem in the first stage of the process. A second advantage is the
low acidity of DMT, which reduces several of the side reaction rates and
results in a higher quality polymer. The limitations of the transesterification
process include increased monomer cost, production of methanol as a by-
product (instead of water), and reduced reactivity in the finishing stages.
The transesterification process produces methanol as a reaction by-product.
The methanol is distilled from ethylene glycol through distillation columns.
Recovered glycol may be recycled to the reactor, the paste mixing tank, or
accumulated for additional processing.
It is desirable to minimize the concentration of methylester ends in the feed
to the polymerization section. Obtaining high conversions is very important in
the DMT process because the reverse reaction of methanol with PET is more
highly favored than the reaction of water and PET. A wide variety of
proprietary reactors are used to effect high end-group conversion during the
transesterification process.
Continuous Polymerization
The continuous polymerization process is the same for the direct esterification
and transesterification processes. Typically, the polymerization section
consists of one or more CSTR reactors (pre-polymerization reactors) followed
by one or more horizontal finishing reactors (polymerization reactors).
These reactors consist of a series of rotating blades or disks which lift polymer
from a pool at the bottom of the reactor into a vapor space over the pool. The
design criteria of these reactors are to maximize surface area generation
while minimizing back-mixing. In polyester processes, the finishing reactors
are almost always limited by the liquid-vapor mass transfer rates. In some
cases, the pre-polymerization reactors are also limited by mass transfer.
The reactors in the polymerization section operate at increasingly higher
temperatures and lower pressures to enhance the devolatilization of excess
glycol and reaction byproducts such as water, methanol, and acetaldehyde.
Reactor residence times range from thirty minutes to four hours depending on
the number and type of reactors in the polymerization section.
Vapor from the polymerization section is scrubbed by spray-condenser loops
composed of a contacting vessel, accumulation tank, pump, and heat
exchanger. In most plants, vacuum is generated through venturi jets
operated by steam or vaporized glycol. In some process configurations, the
Operating Conditions
The esterification and transesterification sections of PET processes frequently
operate below the melting point of the polymer. Under these operating
conditions, the process can be considered solution polymerization. The
polymerization reactors operate above the melting point of the polymer in a
true melt-phase polymerization. The step-growth reaction model may be used
for both modes of operation. In most cases, the same reaction kinetics apply
to both solution- and melt-phase reaction processes.
Final Products
The continuous melt-phase PET processes generally produce polymer with an
average intrinsic viscosity of approximately 0.6 dl/g, which corresponds to a
number-average degree of polymerization near 100 units. This product may
be directly spun as clothing fiber, partially oriented yarn (POY), film, or it may
be cooled and chipped for on- or off-site use.
Recent increases in consumer recycling programs and consumer preference
for unbreakable bottles has created a very large market for polyester bottles.
These bottles are molded from a higher molecular weight polyester chip which
is produced by a solid state process. Fundamentally, the step-growth model
can apply to solid-state polymerization. However, at this time, Aspen
Polymers does not include a solid-state polymerization (SSP) reactor model.
Semi-rigorous SSP models can be developed using a series of CSTR reactors.
Solid phase polymer solutions can be treated as a liquid phase in Aspen
Polymers. The property system switches between liquid-phase property
models and solid-phase property models when the temperature drops below
the melting point of the polymer component.
Nylon-6
Nylon-6 is produced by ring-opening polymerization of -caprolactam. Water
and caprolactam are fed to a primary reactor where the ring-opening reaction
takes place. The primary reactor may be a single (liquid) phase tubular
reactor, CSTR, or one of a variety of proprietary reactors.
The following figure illustrates a continuous melt-phase nylon-6 process:
Nylon-6,6
Nylon-6,6 is manufactured by two types of processes. In the most common
process, dyadic nylon salt is first produced by mixing adipic acid (ADA) in an
aqueous solution of hexamethylene diamine (HMDA). A newer process
involves the direct melt polymerization of the two monomers.
Salt Preparation
In the traditional salting process, the formation of nylon salt ensures
stoichiometric ratios of the two monomers, allowing the production of high
molecular weight polymers. In the salt solution process, solid adipic acid is
dissolved in an aqueous solution of HMDA. The resulting aqueous salt solution
is concentrated by further addition of the monomers and/or by partial
evaporation.
An alternative salting process uses methanol as the primary solvent. Solutions
of adipic acid and HMDA in methanol are prepared separately in continuously
stirred heated tanks. These solutions are mixed in a reactor where the nylon
salt is generated. Most of the nylon salt precipitates out of solution due to the
low solubility of the nylon salt in methanol. A small amount of the salt,
however, remains dissolved in the reactor, resulting in the generation of some
short-chain oligomers. The salt slurry is centrifuged to remove the solid salt.
Methanol is used as a washing solution in the centrifuge to further purify the
salt. The methanol is purified in a distillation column and recycled. The solid
nylon salt is dried and collected for use on- or off-site.
Final Stage
In the final stages of polymerization, wiped-wall evaporators are used to
finish the reaction at high temperatures (up to 300C) and medium vacuum
pressures (760-200 torr). Typical finishing reactor residence times range from
20-60 minutes. The removal of water and excess monomers from the liquid
phase may be limited by the mass transfer rate.
Melt-Phase Polymerization
Recent developments in nylon-6,6 polymerization have led to the
development of continuous melt-phase polymerization processes. Adipic acid
and hexamethylene diamine solutions are fed to a tubular primary reactor,
which operates at very high pressures (approximately 1000 psig),
temperatures around 275C, and residence times of 15-30 minutes. Under
these conditions, boiling does not occur in the reactor.
The pressure is throttled down to 250-350 psig through a series of valves or
tubes of successively larger diameter. The pressure profile must be adjusted
to minimize cooling caused by the rapid evaporation of steam, which can
cause the polymer solution to freeze.
In the final stage, the polymer is brought close to chemical equilibrium (with
dissolved water and excess monomers) in a wiped film evaporator.
Polycarbonate
Polycarbonate is a relatively strong polymer with good optical and mechanical
properties. It is used in several applications including car body parts
(frequently blended with PBT), specialty films, and laser disc media.
Historically, most polycarbonate was produced by interfacial polymerization of
bisphenol-A (BPA) with phosgene. In the interfacial process, the reactions are
relatively fast, but the reaction rate is limited by the mass transfer rates of
the reactants from the bulk liquid phases into the swollen polymer phase.
A limited amount of polycarbonate is produced from BPA and phosgene in a
solution polymerization process. The reaction is carried out by solution
polymerization in pyridine. The pyridine solvent captures chlorine from the
phosgene groups, resulting in pyridine chloride as a reaction by-product.
The monomers, BPA and DPC, are fed in a carefully controlled ratio to a series
of CSTRs. Phenol, which is generated as a reaction by-product, is vaporized in
the reactors and must be condensed and recycled. Distillation columns are
used to recover residual monomers from phenol.
The CSTRs are followed by a series of wiped film evaporators and horizontal
finishing reactors which operate at successively lower pressures to enhance
the removal of residual monomers and phenol. These reactors are limited by
the mass transfer rate of phenol from the melt.
Nucleophilic Reactions
Step-growth polymerization involves reactions between monomers containing
nucleophilic and electrophilic functional groups. Nucleophilic groups are
electron-strong groups, typically alcohols (~OH), amines (~ NH 2 ), or water.
Nucleophilic Substitution
In nucleophilic substitution reactions, a nucleophilic group from one reactant
(the nucleophile) displace a nucleophilic group in the other reactant (the
electrophile), resulting in two new products. (Note: Electrophilic groups are
highlighted in each of the following figures.) Nucleophilic substitution
reactions tend to be highly reversible.
O O
CH OH + HO C HOH + CH3O C
3
Nucleophilic Electrophilic Nucleophilic Electrophilic
Species Species Species Species
Forward Reaction Reverse Reaction
Nucleophilic Addition
In nucleophilic addition reactions, the electrophile and nucleophile combine to
form a new functional group. These reactions are typically irreversible.
O
CH3 OH + O C N CH 3 O C NH
Nucleophilic Electrophilic
Species Species
Currently, the step-growth reaction generation algorithm is limited to
condensation reactions. Pseudocondensation reactions must be defined
through the user reaction feature or through the segment-based power-law
reaction model.
In some reverse reactions and re-arrangement reactions, the electrophile
may be a polymer or oligomer. These reactions occur at the bonds which link
two segments together. To fully describe these reactions, the two segments in
the electrophile must be identified. In this case, we refer to the electrophile as
the victim reactant and the nucleophile as the attacking reactant. The
victim reactant includes a nucleophilic segment and an electrophilic segment.
Attacking Victim Victim
Nucleophilic
Nucleophilic Electrophilic
Species Species Species
O O O O
CH3OH + O(CH2)2O C C O(CH2)2OH + CH3O C C
The following table lists the role of electrophiles and nucleophiles in several
step-growth polymerization processes, as well as the typical reacting
CH CH2
Reaction Nomenclature
Polymerization reactions are classified by chemical mechanism, by the
number of reacting components, and by the influence a reaction has on the
chain length distribution. This section describes the basic types of reactions
found in step-growth polymerization and serves as a glossary of reaction
nomenclature.
Intermolecular reactions involve two or more molecules.
Intramolecular reactions involve two sites on the same molecule.
Condensation reactions are polymerization reactions which produce a small
molecule as a by-product. Typically, the condensate is a volatile compound
such as water, methanol, acetic acid, or phenol. Step-growth reactions
involving chlorine end groups result in hydrochloric acid or chlorinated
hydrocarbon condensate products.
Reverse condensation reactions are where condensate molecules cleave an
existing polymer chain, producing two smaller chains. Reverse condensation
reactions near the end of a polymer molecule can generate free monomers.
Pseudocondensation reactions are nucleophilic addition reactions. These
reactions involve rearrangement of atoms in two different functional groups,
resulting in a new functional group. No by-products are produced by
pseudocondensation reactions. Pseudocondensation reactions can involve two
monomers, a monomer and a polymer end group, or two polymer end
groups.
Addition reactions are reactions in which small molecules, including free
monomers, dyadic salts, and cyclic monomers and dimers react with the end
Forward Pn + Pm Pn + m1 + M Yes
Polycondensation
Reverse M + Pn Pn m + Pm+1 Yes
Polycondensation
Re-arrangement Pn + Pm Pn + m q + Pq Yes
Ring Opening W + Cn Pn No
Ring Addition Pn + Cm Pn + m No
Nucleophilic Ring-Closing Pn Cn + W No
Substitution
Cyclodepolymerization Pn Pn m + Cm No
Side Reactions
Several of the key side reactions are also acid-catalyzed. In the PET process,
these reactions include the formation of diethylene glycol, or DEG, from
ethylene glycol. The transesterification process does not involve acids, and
substantially less DEG is produced.
An analogous reaction generates tetrahydrofurane (THF) in the PBT process.
Like DEG formation, THF formation is accelerated by acid end groups. Since
Polymerization Stage
The polymerization stage involves chain building reactions. There are two
main growth mechanisms. Condensation reactions occur between two
polymer end groups, releasing water or methanol. Polymerization reactions
occur between diol end groups in different polymer molecules, generating a
molecule of free glycol.
The polymer end group distribution and molecular weight distribution are
randomized by redistribution reactions.
Condensation O O O O
1
HO(CH2)x OH + HO C C OH HO(CH2) x O C C OH + H2O
2
O O O O
3
O(CH2) x OH + HO C C OH O(CH2) x O C C OH + H2O
4
O O O O
5
HO(CH2)x OH + HO C C HO(CH2) x O C C + H2O
6
O O O O
7
O(CH2) x OH + HO C C O(CH2) x O C C + H2O
8
Polymerization O O O O
9
O(CH2)x OH + HO(CH2)x O C C OH O(CH2)x O C C OH + HO(CH2)x OH
10
O O O O
11
O(CH2)x OH + HO(CH2)x O C C O(CH2)x O C C + HO(CH2)x OH
12
Rearrangement O O O O
13
O(CH2)x OH + O(CH2)x O C C O(CH2)x O C C + HO(CH2)x O
14
Condensation O O O O
15
HO(CH2)x OH + CH3O C C OCH3 HO(CH2) x O C C OCH3 + CH3OH
16
O O O O
17
O(CH2)x OH + CH3O C C OCH3 O(CH2)x O C C OCH3 + CH3OH
18
O O O O
19
HO(CH2) x OH + CH3O C C HO(CH2)x O C C + CH3OH
20
O O O O
21
O(CH2)x OH + CH3O C C O(CH2)x O C C + CH3OH
22
Polymerization O O O O
23
O(CH2)x OH + HO(CH2)x O C C OCH3 O(CH2)x O C C OCH3 + HO(CH2)x OH
24
End-group O O O O
25
Exchange H2O + CH3O C C HO C C + CH3OH
26
x = 2 for polyethylene-terephthalate
x = 3 for polypropylene-terephthalate
x = 4 for polybutylene-terephthalate
The following table describes how to assign rate constants to each of the
reactions listed in the previous table:
Attacking Victim Victim
Reaction Nucleophilic Electrophilic Nucleophilic
No. Species Species Species
1 EG TPA none
2 H2O T-TPA T-EG
Many of the side reactions in the polyester process are not included in the
reaction generation scheme, and must be added to the model as user
reactions. These reactions are:
Reaction
Type Reaction Stoichiometry
DEG Formation U1
HO(CH2)2OH + HO(CH2)2OH HO(CH2)2O(CH2)2OH + H2O
U2
HO(CH2)2OH + HO(CH2)2O HO(CH2)2O(CH2)2O + H2O
U3
O(CH2)2OH + HO(CH2)2O O(CH2)2O(CH2)2O + H2O
Thermal O O U4 O O
Scission C C O(CH2)2O C C OH + H2C CHO
Acetaldehyde O O U5 O O O
Formation C C O(CH2)2OH C C OH + HCCH3
O O U6 O O O
O(CH2)2OH + C C OCH CH2 C C O(CH2)2O + HCCH3
Cyclic Trimer U7 G T
Formation HOT G T G T GH T G + H2 O
U8 G T
U9 G T
HG T G T G T GH T G + HO(CH2)2OH
U10 G T
U11 G T
G T G T G T GH O(CH2)2OH + T G
U12 G T
U11 Reaction is first order with respect to linear molecule with the
following segment sequence:
~B-EG : B-TPA : B-EG : B-TPA : B-EG : B-TPA : T-EG
option 1: assume this concentration = T-EG concentration and use
power-law constant T-EG = 1*
option 2: use the following equation, based on the most-probable
distribution, to estimate the concentration of this linear oligomer. This
equation can be implemented as a user-rate constant correlation
EG ] [ B TPA]
3 3
[ B EG ] NUCL = [T EG ] + [T DEG ] + 2 *[ B EG ] + 2 *[ B DEG ]
[ P ] = [TNUCL
2
ELEC
NUCL 0
ELEC = [T TPA] + 2 *[ B TPA]
Cyclic Oligomers
As the reactions proceed, intramolecular reactions involving linear polymer
molecules generate cyclic oligomers. Cyclic oligomers ranging from the dimer
through rings ten units long are reported in the literature. The concentration
of each successive cyclic oligomer (dimer, trimer, etc.) falls off sharply, in
accordance with the most probable distribution.
Reactions involving cyclic compounds are not considered in the reaction
generation algorithm in the step-growth model. These reactions, including
ring opening, ring closing, ring addition, and cyclodepolymerization, must be
specified as user reactions.
CL C6H11NO O -Caprolactam
NH
Major Reactions
The major reactions in the nylon-6 melt polymerization process are shown
here:
Reaction Type User-Specified Reactions (Forward and Reverse
Reactions Defined Separately)
U1 H2O = 1, CL = 1
forward
U1 ACA = 1
reverse
U2 H2O = 1, CD = 1 (Multiply group-based pre-exponential factor by 2.0)
forward
U2 Reaction is first order with respect to linear dimer P2 with the following segment
reverse
sequence:
T-NH2 :T-COOH
option 1: assume P2 concentration = ACA concentration and use power-law constant
ACA = 1*
option 2: use the following equation, based on the most-probable distribution, to
estimate concentration of P2 The denominator in this equation can be implemented
as a user rate constant, with first-order power-law constants for T-NH2 and T-COOH.
[ P ] = [T NH
2
[T NH 2]
[T COOH ]
2] + [ R NY 6] [ T COOH ] + [ R NY 6] 0
U3 ACA = 1, CL = 1
forward
U3 See U2 reverse reaction
reverse
U4 T-NH2 = 1, CL = 1
forward
U4 T-NH2 = 1 (this approximation assumes most T-NH2 end groups are attached to
reverse repeat units)*
U5 ACA = 1, CD = 1
forward
U5 Reaction is first order with respect to linear trimer P3 with the following segment
reverse
sequence:
T-NH2 : R-NY6 : T-COOH
option 1: assume P3 concentration = ACA concentration and use power-law constant
ACA = 1*
option 2: use the following equation, based on the most-probable distribution, to
estimate concentration of P3 The denominator in this equation can be implemented
as a user rate constant, with first-order power-law constants for T-NH2, R-NY6, and
T-COOH.
[ P ] = [T NH
2
[T NH 2]
[ R NY 6]
[T COOH ]
2] + [ R NY 6] [T COOH ] + [ R NY 6] [T COOH ] + [ R NY 6] 0
U6 T-NH2 = 1, CD = 1
forward
U6 T-NH2 = 1 (this approximation assumes most T-NH2 end groups are attached to
reverse repeat units)*
*
To avoid numerical problems, set power-law exponents to 110 8 for reactants which do not
appear in the rate expression
0 = Concentration zeroth moment, mol/L (approximately = 0.5 * ([T-COOH] + [T-NH2])
Modeling Approaches
There are two modeling approaches:
Simplified
Detailed
The component definitions for both modeling approaches are:
Component ID Databank ID Component Structure Component Name
Note: The component names used in this table are used in the successive
tables to document the reactions.
The detailed modeling approach treats the HMDA and ADA segments as
discreet molecular units. Using this assumption, the dissolved salt is a dimer
made up of one hexamethylene diamine end group and one adipic acid end
group. This approach is more rigorous because it considers every possible
reverse reaction, including terminal monomer loss. To use this approach,
define the HMDA repeat group as a bifunctional nucleophile (NN-GRP), and
the ADA repeat group as a bifunctional electrophile (EE-GRP).
The solid-liquid phase equilibrium (reaction C1) is represented as previously
described. The reactions involving the dissolved salt, U1-U6, must be defined
as user reactions. Reactions 1-7, which do not involve the salt, are generated
by the model automatically.
The reactions for a detailed Nylon-6,6 salt process model are shown here:
Reaction Type Phase Equilibrium Reactions (Use Power-Law
In the reaction stoichiometry equations above, the colon (:) indicates connections
between segments
A subset of these identifiers can be used to assign the same rate constant to
several different reactions. For example, reactions 3-7 can be lumped
together by specifying T-NH2 as the attacking nucleophilic species and by
leaving the victim species identifiers blank (unspecified).
Rate constants can be assigned to reactions 1-7 in the detailed model using
the identifiers summarized here:
Reaction No. Attacking Victim Victim
Nucleophilic Electrophilic Nucleophilic
Species Species Species
A subset of these identifiers can be used to assign the same rate constant to
several different reactions. For example, reactions 3-7 can be lumped
together by specifying T-HMDA as the attacking nucleophilic species and by
leaving the victim species identifiers blank (unspecified).
Each reaction involving the dissolved salt must be defined as a user-reaction
in the Step-Growth model. The forward and reverse reactions are treated as
two separate reactions. The stoichiometry of each reaction was shown
previously in the reactions table for the detailed modeling approach. The
power-law exponents are in the following table.
Several of the reverse reactions require a particular sequence of segments in
order to occur. The concentration of molecules with these particular
sequences can be assumed (for example, assume the linear trimer
concentration is the same as the dissolved salt concentration) or they can be
estimated from statistical arguments. The following table shows both
techniques. The statistical approach is more rigorous, but it requires writing a
[P4 ] = [T ADA]
2[ B HMDA]
[T ADA] + 2[ B ADA] [T HMDA] + 2[ B HMDA]
2[ B ADA] [T HMDA]
0
[T ADA ] + 2[ B ADA] [T HMDA ] + 2[ B HMDA]
U3 DIS-SALT = 1, ADA = 1, multiply group rate constant by 2.0
forward
U3 Reaction is first order with respect to water and polymer molecule P3,aa with the
reverse
following segment sequence:
T-ADA : B-HMDA : T-ADA
option 1: assume P3,aa concentration = ADA concentration and use power-law
constants ADA = 1, H2O = 1*
option 2: set power-law exponent for H2O = 1 and use the following equation, based
on the most-probable distribution, to estimate concentration of P3,aa (this equation
can be implemented as a user rate constant).
2
2[ B HMDA]
[ P ] = [T ADA
3,aa
[T ADA]
] + 2[ B ADA] [T HMDA] + 2[ B HMDA] 0
U4 Reaction is first order with respect to water and polymer molecule P3, BB with the
reverse
following segment sequence:
T-HMDA : B-ADA : T-HMDA
option 1: assume P3, BB concentration=HMDA concentration and use power-law
constants HMDA=1, H2O=1*
option 2: set power-law exponent for H2O = 1 and use the following equation, based
on the most-probable distribution, to estimate concentration of P3, BB (this equation
can be implemented as a user rate constant).
2
[ P ] = [T HMDA
3,aa
[T HMDA]
2[ B ADA]
] + 2[ B HMDA] [T ADA] + 2[ B ADA] 0
U5 DIS-SALT = 1, T-ADA = 1
forward
U5 H2O = 1, T-ADA = 1, set power law constants for B-ADA, B-HMDA to 1E-10 to avoid
reverse numerical problems
U6 DIS-SALT = 1, T-HMDA = 1
forward
U6 H2O = 1, T-ADA = 1, set power law constants for B-ADA, B-HMDA to 1E-10 to avoid
reverse numerical problems
*
To avoid numerical problems, set power-law exponents to 110 8 for reactants
which do not appear in the rate expression
These reactions are generated by the Step-Growth model if the HMDA repeat
group is defined as a bifunctional nucleophile (NN-GRP), and the ADA repeat
group as a bifunctional electrophile (EE-GRP).
Side reactions that are not shown may be included in the model as user
reactions.
Rate constants can be assigned to reactions 1-7 using the identifiers for the
detailed model summarized on page 115.
A subset of these identifiers can be used to assign the same rate constant to
several different reactions. For example, reactions 3-7 can be lumped
together by specifying T-HMDA as the attacking nucleophilic species and by
leaving the victim species identifiers blank (unspecified).
PHOH C6H6O OH
Phenol
The following table shows the main reactions in this process. These reactions
are generated by the model if the carbonate group is defined as a bifunctional
electrophile (EE-GRP) and the BPA group as a bifunctional nucleophile
(NN-GRP) .
Reaction Model-Generated Step-Growth Reactions (Define B-BPA as
Type NN-GRP, B-DPC as EE-GRP)
The following table shows how to assign rate constants to each of the
reactions shown in the previous table:
Reaction No. Attacking Victim Victim
Nucleophilic Electrophilic Nucleophilic
Species Species Species
chain length distribution. The number average polymer properties (Pn, Mn)
are calculated from the moments. These component attributes can be used
to calculate secondary properties, such as polymer viscosity, melting point,
end group concentrations, intrinsic viscosity, melt flow index, etc. Correlations
relating secondary properties to the polymer moments can be implemented
using a User Prop-Set Property subroutine, as described in the Aspen Plus
User Guide.
The rate of change of polymer mass is calculated as follows:
Nseg
R s ,i * Mwi
Rp = 1
Mw p
End 1
Repeat 2
Branch-3 3
Branch-4 4
The rate of change of the zeroth moment ( 0 ) is calculated from the rate of
change of the first moment ( 1 ) and the segment type ():
0 1 1
= 2
t t t
The factor of accounts for the fact that each connection links two
segments (without this correction the points of connection are counted twice).
This method is best illustrated through these examples:
Valid Reaction Type Stoichiometry 1 0
No Initiation M P1 MR +1 +1 0
Yes Branching Pn + M Pn +1 R + M B3 + E +1 +1 0
Yes Branching Pn + Pm Pn + m R + E B3 + R 0 +1 -1
This method lets you specify most classes of reactions. However, special care
must be taken to ensure that the reaction is defined in a manner that is
consistent with the previous equation.
By default, the model solves the zeroth moment (ZMOM) and segment flow
rates (SFLOW attributes) as independent variables. This can cause a
discrepancy between these variables, especially in flowsheets with high
polymer recycle flow rates. This discrepancy, in turn, can lead to convergence
problems in downstream reactors.
To avoid this problem, you can force the model to calculate the zeroth
moment directly from the segment flow rates by checking the explicitly solve
0 = 1 12
This option cannot be invoked if two or more reaction models are referenced
from a single reactor block.
Phase Equilibria
The step-growth model can be used to simulate reactions in single-phase
(vapor or liquid), two-phase (VL), or three-phase (VLL) systems. Each step-
growth reaction model is associated with a particular reaction phase, specified
on the Options sheet. The user can consider simultaneous reactions in
multiple phases by referring to two or more reaction models in a reactor.
Typical applications of this model include melt-phase polymerization and
solution polymerization. Slurry, suspension, and emulsion processes involving
step-growth kinetics can also be simulated with this model.
Interfacial polymerization involves a solvent phase, an organic monomer
phase, and a polymer phase. The reaction rate is usually limited by the rate
of mass transfer of monomers from the organic phase to the reacting polymer
phase. The mass-transfer limits across the liquid-liquid interface are not taken
into account by the standard model. These systems can be simulated by
developing a custom reactor model in Aspen Custom Modeler or Aspen Plus,
or by writing an appropriate concentration basis subroutine for the step-
growth model.
Solid-state polymerization involves crystalline and amorphous solid polymer
phases and a vapor phase. The reaction kinetics may be limited by the rate of
mass transfer of volatile reaction by-products from the amorphous solid phase
to the polymer phase. None of the standard reactor models in Aspen Polymers
are designed for solid-state polymerization. Solid-state polymerization models
can be developed in Aspen Custom Modeler and interfaced to the step-growth
polymerization model through the Aspen Custom Modeler / Aspen Polymers
Interface.
Mass transfer limitations in thin-film or horizontal finishing reactors can be
considered by customizing the Step-Growth model using the available
concentration basis subroutine or by developing an appropriate user reactor
model in Aspen Plus or Aspen Custom Modeler.
Reaction Mechanism
The Step-Growth reaction model applies to condensation polymerization. In
the future the model will be extended to cover pseudocondensation and ring-
addition polymerization. The model accounts for any combination of
monofunctional and bifunctional monomers. Cyclic monomers and
multifunctional monomers, however, are not included in the standard reaction
scheme.
User-defined stoichiometric reactions can be added to the model to account
for reactions which are not included in the standard reaction scheme. These
reactions use a power-law rate expression which can be extended to more
Model Structure
This section outlines the structure of the Step-Growth kinetics model. It
examines the theoretical framework in detail. The assumptions and limits of
the algorithms are documented.
Segments
The preferred method of segmenting the polymer component is to define
segments corresponding to the monomers which are used to produce the
polymer. This technique has two distinct advantages. First, the property
models in Aspen Polymers use the monomer as a reference point for
molecular size. Second, the reaction kinetics usually involve adding
monomers to the end of growing polymer chains. Defining segments
corresponding to the monomers makes it easy to write reactions
corresponding to monomers and segments, for example monomer A
segment A.
The Step-Growth model assumes that the polymer is segmented in this
manner. For monadic polymers such as nylon-6, this technique is
straightforward. This method of segmenting the polymer is a bit unusual for
dyadic polymers, such as PET, because it treats them as alternating
copolymers. Thus, a molecule of PET with 100 PET units is defined as having a
degree of polymerization of 200 in this model (100 terephthalate units and
100 glycol units).
Monofunctional monomers, such as benzoic acid, always correspond to an
end-group segment in the model. Bifunctional monomers can end up inside a
linear polymer chain as a repeat unit, or may be located at the end of the
chain as an end group. Each symmetric bifunctional monomer (diacids, diols,
diamines, etc.) corresponds to one repeat segment and one end-group
segment. Asymmetric bifunctional monomers (monomers with two different
types of end groups) correspond to one repeat unit and two end-group
segments. Multifunctional monomers can correspond to several segments, as
shown:
Monomer Monomer Corresponding Segment Formulas
Type Formula
End-Groups Repeat Unit Branch-3 Branch-4
Each functional group in the model is assigned a name and type. The names
are used to distinguish between different groups with the same chemical
functionality.
The following table shows the types of functional groups found in common
monomers and the condensate products:
Reacting Functional Groups
Monomer Monomer
Leaving Groups Segment Groups
Type Formula
Structure Type Structure Type Structure Type
Reacting Species
Since polymer components do not have a fixed structure, polymerization
reactions must be written in terms of the polymer segments. The segments
and standard components that make up the step-growth reaction network are
referred to as reacting species. Each of these reacting species is made up of
one or more reacting functional groups.
Once the reacting groups are defined, the structure of each reacting species is
specified by defining the number of each reacting group in each reacting
species. It is not necessary to specify a zero when a particular group is not in
the species being defined.
Oligomer Fractionation
You can choose to include one or more oligomer components in the model.
When this feature is used, the model will fractionate the polymer distribution
between the polymer component and the various oligomer components. The
fractionation algorithm assumes that the polymer follows the most probable
distribution. These assumptions are valid when the reactions are reversible
molecule, Wab
Condensation - Pn , xa + Pm, yb Pn + m, xy + Wab Find every combination by which
Polymer Addition nucleophilic end segments, Pxa , can
react with end segments, Pyb , to give a
condensate molecule, Wab
Reverse Condensation Wab + P2, xy M xa + M yb Find every combination by which a
- Terminal Monomer condensate molecule, Wab , can react
Loss Wab + Pn , xy Pn1, xa + M yb with a polymer molecule at the
boundary between a nucleophilic repeat
segment, x, and an electrophilic end
group segment, y
Reverse Condensation Wab + Pn , xy Pn m, xa + Pm, yb Find every combination by which a
- Scission condensate molecule, Wab , can react
with a polymer molecule at the
boundary between a nucleophilic repeat
segment, x, and an electrophilic repeat
segment, y
Forward Pn , za + Pm, yx Pn + m1, yz + M xa Find every combination by which a
Polycondensation nucleophilic end group segment, Pza ,
can react with a polymer molecule at
the boundary between a nucleophilic
repeat segment, x, and an electrophilic
end segment, y
Reverse M za + Pn , yx Pn m, yz + Pm+1, xa Find every combination by which a
Polycondensation nucleophilic monomer, M xa , can react
with a polymer molecule at the
Model-Generated Reactions
There are two steps required to assign rate constants to model generated
reactions. First, the rate constant values are specified in the Step-Growth
Rate Constant form (SG-RATE-CON sentence). Then each set of rate
constants is assigned a number for identification. Once the rate constants sets
are defined, they can be assigned to the generated reactions.
Equation
Eai 1 1 b
T i
Tref specified rate = [ Nucl ][ Elec] f n f e P Ci ko i e
RT T Tref
U ( flagi )
i Tref
Eai
Tref unspecified rate = [ Nucl ][ Elec ] f n f e P Ci ko i e RT
T bi U ( flagi )
i
Nomenclature
Symbol Description
* The concentration basis may be changed to other units using the Concentration
basis field on the Options sheet or using the optional concentration basis
subroutine.
The reactions follow second order kinetics: one order with respect to the
nucleophilic reactant and one order with respect to the electrophilic reactant.
A-Nucl-
Reaction Spec A-Elec-Grp V-Elec-Spec V-Elec-Grp V-Nucl-Spec V-Nucl-Grp
1 O O
HO(CH2)2OH ~H in none ~OH in acid
O O
HOC COH C C
alcohol
2 H2O ~H O O O O
~O(CH2)2OH ~O(CH2)2O~
C COH C C
5 HO(CH2)2OH ~H in
O O O O none ~OH in acid
C COH C C
alcohol
6 H2O ~H O O O O
~O(CH2)2OH ~O(CH2)2O~
C C C C
9 HO(CH2)2OH ~H in
O O O O none ~OH in acid
HOC COCH3 C C
alcohol
10 H2O ~H O O O O
~O(CH2)2OH ~O(CH2)2O~
C COCH3 C C
11 HO(CH2)2OH ~H in
O O O O none ~OCH3
HOC COCH3 C C
alcohol
12 CH3OH ~H O O O O
~O(CH2)2OH ~O(CH2)2O~
C COCH3 C C
It is not necessary to specify all of the reaction identifiers. For example, the
only time it is necessary to specify the attacking nucleophilic species and the
attacking electrophilic group is when this species contains more than one type
of group and the two groups are not equally reactive.
Case 1 Assign rate constant sets 1 and 2 to all of the model-generated reactions
1 1, 2 unspecified unspecified unspecified unspecified unspecified unspecified
Case 2 Assign rate constant sets 1 and 2 to reactions between alcohol groups in ethylene glycol
and any acid groups
Assign rate constant sets 3 and 4 to reactions between alcohol groups in the polymer
and any acid groups
Assign rate constant set 5 to reverse reactions involving methanol
Assign rate constant set 6 to reverse reactions involving water
1 1, 2 HO(CH2)2OH unspecified unspecified unspecified unspecified ~OH in
acid
2 3, 4 ~O(CH2)2OH unspecified unspecified unspecified unspecified ~OH in
acid
3 5 H2O unspecified unspecified unspecified unspecified unspecified
Case 3 Assign rate constant sets 1 and 2 to reactions between alcohol groups in ethylene glycol
and terephthalic acid
Assign rate constant sets 3 and 4 to all other reactions involving acid groups
Assign rate constant set 5 to reactions between water and glycol end groups
Assign rate constant set 6 to all other reverse reactions involving water
Assign rate constant set 7 to reactions between ethylene glycol and the methylester end
groups in the polymer
Assign rate constant 8 to all other reactions
1 1, 2 unspecified O O unspecified unspecified unspecified
HO(CH2)2OH HOC COH
User Reactions
The model cannot predict all types of reactions based on the specified
structures. Reactions which are not predicted by the model can be included as
user-specified reactions. These can include thermal scission reactions,
monomer or segment reformation, end-group modification, etc.
The user-specified reactions apply a modified power-law rate expression, as
shown here:
Equation
Eai 1 1 bi
T
R T Tref
U ( flag i )
Tref specified k net ,i = [Catalyst i ] ko i e
T
ref
Eai
Tref unspecified k net ,i = [Catalysti ] ko i e RT
T bi U ( flag i )
Assign User Rate Constants is used: ratem = activitym ( C ) k j
amj
j i net ,i
= ( C )k
amj
Assign User Rate Constants is not used: ratem j
(m = i)
j net ,i
Nomenclature
Symbol Description
* The concentration basis may be changed to other units using the Concentration
basis field on the Options sheet or using the optional concentration basis
subroutine.
You can modify the standard rate expression using the optional user rate
constant feature. The rate constant form includes a parameter called the
user flag which identifies an element in an array of user rate constants. This
array is calculated by a user-written Fortran subroutine. The standard rate
expression is multiplied by the user rate constants as shown.
User Subroutines
The Step-Growth model can be customized by applying user-written
subroutines. There are three types of subroutines available. The concentration
basis for the model can be changed through a user basis subroutine. This
subroutine can also be used to calculate the volume (RCSTR and RBatch) or
area (RPlug) of the reacting phase. A user rate-constant subroutine can be
used to extend the standard rate expression for model-generated or user-
specified reactions. A user kinetics routine can be used to add reactions to the
model which are too difficult to represent using the power-law approach, or to
calculate user attributes for polymer characteristics which are not tracked by
Aspen Polymers. These routines can be used together in any combination.
SUBROUTINE USRMTS
1 SOUT, NSUBS, IDXSUB, ITYPE, XMW,
2 IDSCC, NPO, NBOPST, NIDS, IDS,
3 NINTB, INTB, NREALB, REALB, NINTM,
4 INTM, NREALM, REALM, NIWORK, IWORK,
5 NWORK, WORK, NCPM, IDXM, X,
6 X1, X2, Y, DUM1, FLOWL,
7 FLOWL1, FLOWL2, FLOWV, FLOWS, VLQ,
8 VL1, VL2, VV, VSALT, VLIQRX,
9 VL1RX, VL2RX, VVAPRX, VSLTRX, RFLRTN,
* IFLRTN, CRATES, NTCAT, RATCAT, CSS,
1 VBASIS, IPOLY, NSEG, IDXSEG, AXPOS,
2 TIME )
* When using molar concentrations, this parameter is volume of the reacting phase
in m 3 in RCSTR and RBatch or the cross-sectional area of the reacting phase in m3
in RPlug.
Example 1 illustrates how to use the user basis routine to convert the
concentration basis from the standard molar concentration basis (mol/L) to a
mass concentration basis (mol/kg). (Note: the current version of Aspen
Polymers supports several concentration basis through the CONC-BASIS
keyword located on the Options form, we retain this example as a
demonstration). Using these units, the reaction rates are calculated in units of
mol/kg-sec. These rates are multiplied by the holdup basis (VBASIS) for the
reactor in the Step-Growth model. For this reason, the holdup basis must be
consistent with the concentration basis, e.g., it must be in kg. The holdup
basis pertains to the reacting phase, it does not include the phases which do
not react.
Note: This excerpt does not include the argument list and declarations
section of the user basis routine.
The plug flow reactor model in Aspen Plus assumes that the vapor and liquid
move at the same velocity through the reactor (e.g., no-slip conditions). This
assumption is not consistent with the physical reality of polymer finishing
reactors or wiped-film evaporators. The subroutine in Example 2 gets around
the no-slip assumption in RPlug, allowing you to specify the volume occupied
by the liquid phase. In this example, the user specifies the first integer
argument in the RPlug block as 1 and specifies the first real argument as
the volume fraction of the reactor occupied by the liquid phase.
Example 2: A User Basis Routine to Specify Liquid Volume in RPlug
UFRAC = 1.D0
IF ( REALB(1) .NE. RGLOB_RMISS ) UFRAC =
REALB(1)
IF ( INTB(1).EQ.1 ) THEN
Note: This excerpt does not include the argument list and declarations
section of the user basis routine.
Argument Descriptions
Variable Usage Type Dimension Description
[C ] = 1 + ([aC+ bT])[ I ]
eff
actual
Where:
[Ceff ] = Effective catalyst concentration, mol/L
T = Temperature, K
a,b = Equation parameters
The net rate expression can thus be written as:
[C ] E* 1 1
actual R T Tref
rate = [Q] ko e
1 + ( a + bT )[ I ]
Where:
ko = Pre-exponential factor, (L/mol)/sec
E* = Activation energy
R = Gas law constant
Tref = Reference temperature for ko
[Q] = Concentration of component Q, mol/L
Argument Descriptions
Variable Usage Type Dimension Description
* Area in RPlug
The user kinetic subroutine returns the rate of change of the reacting species
and the Class 2 component attributes (zeroth moment and segment flow
rates). The subroutine may be applied to calculate user component attributes
(CAUSRA etc.) to track color or other polymer properties which are related to
the thermal history of the polymer.
Example 4 illustrates how the concentration of a color body can be tracked
through user kinetics routine. The example assumes that the polymer color is
proportional to the amount of unknown color bodies which are generated by
side reactions. These unknown side reactions are sensitive to the thermal
history of the polymer, according to an Arrehnius rate expression. The
activation energy and pre-exponential factors of this expression are stored as
the first and second REAL parameters for the user kinetics model.
INTEGER IDUSRA(2)
DATA IDUSRA /'CAUS','RA '/
C.....GAS CONSTANT IN KCAL/MOL-K...
RGASKC = 1.987D-3
C.....locate CAUSRA attribute: LUSRA points to location in SOUT...
LUSRA = SHS_LCATT( 1, IPOLY, IDUSRA )
C.....LURAT points to this attribute in the RATCAT vector...
LURAT = LUSRA - NCOMP_NVCP
C ----------------------------------------------------------------------
C Get the rate constants from the list of REAL parameters in the
C user-kinetics section of the Step-Growth Subroutine form
C REAL(1) A_CF Color Formation pre-exponential, 1/min
C REAL(2) E_CF Color Formation activation energy, kcal/mol-K
C ----------------------------------------------------------------------
A_CF = 0.D0
E_CF = 0.D0
IF ( NREALK .GT. 1 ) THEN
IF ( REALK( 1 ) .GE. RGLOB_RMISS ) REALK( 1 ) = 0.D0
IF ( REALK( 2 ) .GE. RGLOB_RMISS ) REALK( 2 ) = 0.D0
A_CF = REALK( 1 ) / 60.D0
E_CF = REALK( 2 )
END IF
C Calculate color formation rate in color-units/cubic-meter/second
RATCAT( LURAT ) = A_CF * DEXP( -E_CF / ( RGASKC*TEMP ) )
RETURN
Note: The work array is used to store intermediate results in the calculations.
The size of the work array must be specified in the subroutine form and must
be large enough to avoid overwriting the end of the array.
INCL-COMPS List
The reactor models in Aspen Polymers use mass-balance equations for each
reacting component. In order to make the reactor models fast, components
which do not appear in the reactions are excluded from these calculations.
The list of reacting components is automatically generated by the Step-
Growth model. This list includes the polymer component, listed oligomers,
components which appear in the list of reacting species, components which
appear as products or reactants in the user-specified reactions, and
components in the INCL-COMPS component list.
When user concentration basis or user kinetics subroutines are applied in a
model, these subroutines can include reactions involving components which
do not otherwise appear in the list of reacting components. These
components should be added to the INCL-COMPS list to ensure they appear in
the mass-balance equations.
Packed Vectors
Aspen Plus frequently uses a technique called packing to minimize
simulation time. The user models previously described use packed vectors to
track the mole fractions of each phase (vectors X, X1, X2, and Y). These
vectors contain NCPM elements (Number of Components Present in the Mixed
substream). The component index associated with each element is listed in
the vector IDXM. All other vectors used by the model, including the rates
vectors and the component concentration vectors, are unpacked.
Example 6: Calculating Unpacked Component Concentrations
Calculate unpacked component concentrations of the first liquid phase given
the packed mole fractions of the first liquid phase and the molar volume of
the first liquid phase.
IF ( VL1 .GT. 0.D0 .AND. FLOWL1.GT.0.D0 ) THEN
DO 10 I = 1, NCPM
CSS(I) = X1( IDXM( I ) ) / VL1
10 CONTINUE
END IF
Note: NCPM steps were required to load the concentration vector. Since
NCPM is always less than or equal to NCC (total number of conventional
components), there is a reduction in the required number of steps to perform
the operation.
Use the User Subroutines forms to specify the names and parameters for
optional user subroutines.
Use this sheet To
Note: Use the Catalyst Species field to associate a rate constant with a
particular catalyst. If you leave this field blank the model drops the catalyst
term from the rate expression.
Use the Catalyst Order field to specify the reaction order with respect to the
catalyst (the model assumes first order by default).
Note: You must specify the Valid Phases keyword for each reactor model
referencing the kinetics to ensure the specified reacting phase exists.
If the Reacting Phase option is set to Liquid-1 or Liquid-2 the model
assumes two liquid phases exist. When the named phase is not present, the
model prints a warning message and sets the reaction rates to zero. There
are two options for handling phase collapse:
Select the Use bulk liquid phase option to force the model to apply the
specified reaction kinetics to the bulk phase when the named phase
disappears.
Select the Suppress warnings option to deactivate the warning
messages associated with phase collapse.
References
Billmeyer, F. W. (1971). Textbook of Polymer Science. New York: Wiley.
Gupta, S. K, & Kumar, A. (1987). Reaction Engineering of Step-Growth
Polymerization. New York: Plenum.
Jacobsen, L. L., & Ray, W. H. (1992). Unified Modeling for Polycondensation
Kinetics. J. Macromol. Sci.-Rev. Macromol. Chem. Phys.
Kaufman, H. S., & Falcetta, J. J. (Eds). (1977). Introduction to Polymer
Science and Technology: An SPE Textbook. New York: Wiley.
McKetta, J. J. (Ed.). (1992). Encyclopedia of Chemical Processing and Design,
39 & 40. New York: Marcel Dekker.
Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere.
Summary of Applications
The free-radical bulk/solution polymerization model is applicable to bulk and
solution polymerization processes. Some examples of applicable polymers
are:
General purpose polystyrene - Made by polymerization of styrene
monomer with or without solvent fed continuously to reactor.
High impact polystyrene - Made by polymerization of an unsaturated
rubber dissolved in styrene in a solution process. Also produced in mass-
suspension processes.
Poly(vinyl chloride) - Produced in bulk polymerization using monomer-
soluble free radical initiators. Most of the homopolymers and copolymers
of vinyl chloride, however, are produced by suspension polymerization.
Poly(vinyl acetate) - Produced industrially by the polymerization of vinyl
acetate in bulk or solution processes. Also produced in suspension and
emulsion processes. Both batch and continuous processes are used.
Free-Radical Bulk/Solution
Processes
Free-radical polymerization accounts for a large proportion (more than 40%
by weight) of the commodity grade polymers. It is employed in the synthesis
of countless homo- and copolymers using monomers that are either
monosubstituted ethylenes ( RHC = CH 2 ) or 1,1-disubstituted ethylenes
( R1 R2C = CH2 ) .
Free-radical polymerization usually takes place with the monomer in the liquid
phase. Several types of processes are used. A solvent or suspending medium
may be used, and the polymer formed may be soluble, insoluble, or swelled
by the monomer and solvent. Commercially important processes for free-
radical polymerization include bulk, solution, suspension, and emulsion
polymerization.
Dni (vinyl ) Polymer chain of length n reacting at an internal double bond of type i
(e.g., a diene segment of type i in the vinyl configuration)
ij
f TDB Fraction of reactions between species i and j resulting in the formation of
a terminal double bond of type i
Ik Standard initiator of type k
Mj Monomer of type j
Pni (cis ) Live polymer chain of length n having an active diene segment of type i
in the cis configuration.
Pni (trans ) Live polymer chain of length n having an active diene segment of type i
in the trans configuration.
R Primary radicals
Xk Inhibitor of type k
Symbol Description
ij
fTDB Fraction of reactions between species i and j resulting in the formation of
a terminal double bond of type i
i Molar fraction of diene segment i in the vinyl configuration (zero for non-
diene segments) (related to VINYLFRA attribute)
k Concentration of undecomposed initiator fragment k in the bulk polymer
(live + dead) (related to FRAGFLOW attribute)
Rate Constant
Ea VP 1 1
k = ko exp f g
(3.1)
R R T Tref
Where:
ko = Pre-exponential factor in l/sec for first order reactions,
and m / kmol s for second order reactions
3
Initiation
The initiation step involves the generation of reactive free-radicals followed by
the addition of a monomer molecule (chain initiation) to form chain radicals of
unit length ( P1i ) . The non-chain or primary radicals ( R ) may be generated by
the thermal decomposition of a chemical initiator, a catalyzed initiation
reaction involving electron transfer from ions, or by thermal/radiation induced
mechanisms. Three types of standard initiation reactions are included in the
built-in kinetics:
Initiator decomposition reaction
Induced initiation reaction
Catalyzed initiation reaction
The initiator decomposition reaction accounts for primary radical generation
from the thermal decomposition of chemical initiators.
The induced initiation reaction can be configured to account for the generation
of radicals by thermal and radiation induced mechanisms from the monomers
themselves, with or without the use of a coinitiator or promoter.
The catalyzed initiation reaction can be used to account for redox initiation,
which has found wide application in aqueous emulsion polymerization
systems.
The most commonly used radical generation method is the thermal
decomposition of chemical initiators (usually peroxide or azo compounds)
which decompose to form radicals when heated to an appropriate
temperature. Only small amounts of the chemical initiator (less than 1 wt. %
based on monomer) are needed. However, due to their high activation
energies chemical initiators have a relatively narrow useful temperature range
(approx. 30C) over which the decomposition rates are neither too fast nor
too slow.
Some processes, notably bulk polystyrene polymerization, use initiators with
two active sites. These bifunctional initiators decompose in two stages,
providing greater control over the molecular weight distribution of the
product.
The free-radical model includes two reactions associated with bifunctional
initiators:
Bifunctional initiator decomposition (primary decomposition)
Secondary initiator decomposition (primary decomposition)
The primary decomposition reaction generates a pair of radicals, an
undecomposed initiator fragment, and optional by-products. The
undecomposed fragment is tracked using the FRAGFLOW polymer
component attribute.
The initiator fragment decomposes in the secondary decomposition
reaction, generating a free radical and a polymeric radical.
M j + Ck P1 + 1 B1 + 2 B2 R si = k si CCk CM j (h )
j kj kj kj kj aj bj cj
The induced initiation reaction can also account for the effects of using an
initiator or promoter (Ck ) to increase the rate of radical generation.
The special initiation reactions generate live polymer directly, thus this
reaction does not contribute to radical generation.
RBkj1 = 1kj kickj C Ik CCj RBkj2 = 2kj kickj C Ik CCj For mass balance purposes, the
polymer mass generation rate is incremented by the initiator mass
consumption rate, less the mass formation rate of by-products.
I kB k R + k Rk + 1,k B1 + 2,k B2 k
Rbid = kbid
k
C Ik
k
This rate expression ( Rbid ) describes the rate for the primary decomposition
of bifunctional initiator k. Each primary decomposition reaction generates an
undecomposed fragment. The generation rate of undecomposed fragments is
equal to the initiator decomposition rate:
RF ( k ) = kbid
k
C Ik
The user can specify more than one bifunctional initiator to model systems
where multiple initiators with different half-lives are used to control the
initiation rate over the course of the polymerization.
The model assumes that the each site in the bifunctional initiator generates
two radicals. A fraction of the radicals generated by decomposition undergo
radical recombination in the radical-cage, leading to stable byproducts. The
initiator efficiency factor, k , is used to specify the fraction of radicals which
are not destroyed by the cage effect. This factor can be adjusted using a
built-in or user-defined efficiency gel effect correlation.
k
The rate constant kbid is calculated using a modified Arrhenius equation
(Equation 3.1 on page 166) with three parameters: pre-exponential factor,
activation energy and activation volume. As noted previously, the activation
volume accounts for the pressure dependence of the rate constant. This
parameter is typically non-zero only at high pressures.
The rate expression can be modified using an optional built-in or user-defined
gel effect correlation as described later in the text.
To complete the initiation process, the reactive primary radicals ( R , Rk )
react with monomer by the chain initiation reaction to form polymer chain
radicals of unit length. Note that the undecomposed initiator fragment k is
j ,k
conserved in the polymer chain ( P1 ) . This fragment is eventually destroyed
by the secondary decomposition reaction described in the next sub-section.
The chain initiation reactions are shown below:
Each fragment decomposition event generates a new live end. The model
assumes that the fragments are randomly distributed across the bulk polymer
molecules and that the penultimate segment attached to the fragment
becomes a live end. The generation rate of live ends of type i from the
decomposition of initiator fragment k can be written as:
d 0 ( j ) k k 1
j
= k k sid
dt 0 1
The byproduct formation rates are determined by:
Propagation
The chain radicals grow or propagate by the addition of monomer molecules
to form long polymer chains ( Pni ) . The propagation reaction is represented
by:
Head-to-Head Propagation
When reactions occur between substituted vinyl monomers or 1,3 dienes, the
repeat units usually join the chain in a head-to-tail configuration, as shown
below (here HTT = head-to-tail). A portion of the monomers may join the
chain in the head-to-head configuration, as shown in the second reaction
below. Head-to-head unions can also result from termination by combination
as described later.
head-to-tail dyad
H HTT Propagation H H2 H
C CH2* + C C C CH2*
R R R R
head-to-head dyad
HTH Propagation H H
C CH* + C C C CH2*
H2 H2
R R R R
The head-to-head dyads disturb the normal regularity of the chain. As a
result, the head-to-head fraction of the polymer can have a strong influence
on the crystallinity of the polymer, and thus influence the mechanical
properties of the final product.
The model can track head-to-head additions using the optional HTH
Propagation reaction. The polymer attributes HTHFLOW and HTHFRAC
(head-to-head flow and fraction) must be included in the list of attributes on
the Polymers, Polymers subform.
The model does not explicitly track normal head-to-tail additions. Instead, the
standard propagation reaction is used to track the total (head-to-head and
head-to-tail) propagation rate. The head-to-head propagation reaction
explicitly tracks the head-to-head propagations. This design allows the user to
fit the overall propagation rate first, and then refine the model by adding
head-to-head additions.
The HTHFLOW attribute is a scalar value. The overall rate of change of the
head-to-head flow Rhth is calculated by summing the head-to-head additions
across all pairs of monomers. Termination by combination also generates
head-to-head pairs as discussed later. The net rate expression for head-to-
head dyads can be written as:
i =1 j =1
Pni + Ak Dn + R ij
Rtra = ktra
ij
CAk Pni
Pni + S k Dn + R ij
Rtrs = ktrs
ij
CS k Pni
For transfer to agent or solvent the transfer radicals are assumed to have the
same reactivity as the primary radicals formed by initiation. The case where
the transfer radical has a different reactivity than the primary radical may be
added in a future version.
Propagation Terminal
double bond
+ n-1 M segment
P1= Pn=
The terminal double bond segments can react with live end groups through
terminal double bond polymerization reactions as described later in this
section. These reactions lead to the formation of a molecule with a long chain
branch.
The model optionally tracks terminal double bonds using the polymer
component attribute TDBFLOW, which contains one element for each type of
segment.
The chain transfer to monomer reaction does not always generate a terminal
double bond. The terminal segment may undergo a re-arrangement reaction,
which destroys the double bond site. The model parameter TDB fraction
( f ) can be used to specify the fraction of chain transfer to monomer
ij
TDB
reactions that generate a terminal double bond.
The reaction rate of the chain transfer to monomer reaction is defined as:
Pni + M j Dn + fTDB
ij
(
P1 j = + 1 fTDB
ij
)
P1 j ij
Rtrm = ktrm
ij
CMj Pni
Where Rtrm ( ) is the rate of consumption of monomer j and live polymer end
ij
groups of type i and the generation rate of live ends of type j. The generation
( )
j=
rate of terminal double bonds of type j Rtrm is defined by:
j=
Rtrm = fTDB
ij ij
ktrm CMj Pni
Termination
Bimolecular termination of radicals may involve primary radicals ( R ) and
chain radicals ( Pnj ) . However, the concentration of primary radicals is usually
much lower than the concentration of chain radicals. Hence, only bimolecular
termination involving chain radicals is included in the built-in kinetic scheme.
In termination, the chain radicals are destroyed and live chains are converted
to dead polymer chains.
Intermolecular termination occurs by one of two mechanisms, combination
(coupling) or disproportionation. Many monomers (e.g. MMA) show both types
Termination by Combination
In termination by combination, two live polymer end groups react with each
other, forming a single dead chain with a head-to-head segment pair. Each of
these reactions, on average, doubles the molecular weight of the polymer.
The figure below shows an example for poly(styrene).
Pn Dn+m
Pm
H H
C CH + HC C C C C C
H2 H2 H2 H2
The reaction rate depends on the concentration of the live end groups:
Termination by Disproportionation
In disproportionation reactions, the radical at the end of one chain attacks a
hydrogen atom at the second-to-last carbon atom in the second chain,
forming two dead polymer molecules with no net change in molecular weight.
Disproportionation results in one of the dead chains having a saturated end-
group while the other will have an end-group with a terminal double bond. For
example:
Pn Pm Dn= Dm
H CH3 CH3 CH3 CH3
CH C + C CH2 C C + HC CH2
H
C O C O C O C O
The reaction rate depends on the concentration of the live end groups:
Rtdi = = fTDB
ij
ktdij Pni Pnj
Inhibition
Inhibition is included as an additional termination mechanism. This involves
reaction between a chain radical and a small molecule (inhibitor or impurities)
to form a dead chain:
Pni + Dm Dn + Pmj ij
Rtrp = ktrp
ij
m j Dm Pni
Beta-Scission
A simplified beta-scission reaction is included in the built-in kinetics. It is
limited to reactions where a live chain undergoes scission to form a dead
chain of the same length and a primary radical:
Pni fTDB
i
Dni = + (1 fTDB
i
) Dn + R Rbsi = kbsi Pni
This reaction can be used to simulate backbiting reactions which form short-
chain polymer radicals (see Short Chain Branching).
The beta scission reaction usually generates a terminal double bond
corresponding to the live end i. In some special cases, the double bond may
not form or may be unstable. The terminal double bond fraction parameter,
i
f TDB , can be used to specify the fraction of beta-scission reactions which
generate a terminal double bond (by default, this parameter is unity). Thus,
the rate of generation of terminal double bonds from the beta-scission
i=
reaction, Rtd , can be defined as:
Rtdi = = fTDB
ij
ktdij Pni Pnj
Pni + M j Pnj+(1trans ) j
Rtrans = i ktrans
ij
CMj 0i
ij ij
In the equations above, k cis and k trans are, respectively, the net rate
constants for cis and trans propagation of monomer j onto a chain with a live
end i. The standard reaction scheme does not include any reactions which
consume the cis and trans end groups. Further, the model does not constrain
the cis and trans reaction rates in any manner; the model user must ensure
that the cis and trans propagation rates are lower than the net propagation
rate.
Calculation Method
In the Aspen Polymers free-radical bulk/solution polymerization model, the
polymer chain length distribution averages and molecular structure properties
are calculated using the population balance and method of moments
approach, based on the built-in kinetics shown in the Built-in Free-Radical
Polymerization Kinetic Scheme figure on page 162.
Population balance equations are used to account for the concentration of
live polymer chains and combined polymer chains of length n. The f-th live
and combined polymer chain length distribution moments are defined as
follows:
jf = n f Pnj
n=0
Nm
f = n f Pnj + Dn
n=0 j =1
For homopolymerization the index f is a scalar variable and the active
segment superscript j may be dropped for the live polymer moment definition
as there is only one segment type. Hence, for homopolymerization there will
be one zeroth moment, one first moment, one second moment and so on for
the live and combined polymer. However, for copolymerization, the index f
will be a vector whose elements denote the monomer with respect to which
the moment is defined. For copolymerization with respect to every active
segment, there will be one zeroth moment, N m first moments,
N m ( N m -1) second moments and so on.
Nm+
2
For example, for copolymerization with three monomers, the vector index f
can have the following values for the first moment:
1 0 0
f = 0 , 1 , 0
0 0 1
representing the first moment with respect to segment one, two and three
respectively. The application of the moment definitions to the live and bulk
polymer population balance equations yields the live and bulk polymer chain
length distribution moment equations. The general moment equations are
listed in the following figures. The various zeroth, first, second, etc. moment
d if f
NM N CI
c
= [ (n j )] k pij CMj R + ktrm CMj 0i + k sijk CCkjk C Mjjk (h ) jk
ij a b
dt i =1 k =1
N BI
1i 0k
+ k k sid
k
f
k =1 1 0
NM
f NM
+ k ijp CMj ( j ) ai k pji CMi fj j fj
f
f a
i =1 a =0 a i =1
NM NM
+ ktrp
ij
f +j 0i ktrpji 1i fj
i =1 i =1
NM NM
+ k scb
ij
if k scb
ji
fj
i =1 i =1
(ktdij + ktcij ) 0i fj
NM
i =1
NM
f j= i
f NM
+ k a f a ktdb
ij
tdb 0 fj
ji i =
i =1 a =0 a i =1
NM f
f NM
+ k ijpdb j a if a k pdb
ji
i 1 fj
i =1 a =0 a i =1
where j contains some terms for reactions leading to the formation of dead
polymer
NM NM NA NS NX
j = kbsj + ktrm
ji
CMi + ktrpji 1i + ktrajk C Ak + ktrsjk CSk + k xjk C Xk
i =1 i =1 k =1 k =1 k =1
The moments with respect to terminal double bonds are approximated:
1 2
1i = i0= i2= i0= etc...
0 0
In the final term of the equation, the symbol represents the molar fraction
i
NM NM
1 N M f f ij i j
ktcij 0i fj + ktc a f a
i =1 j =1 2 i =1 a =0 a
NM NM f
f j i = N M N M ij i j = N M N M ij i j =
+ ktdb ji
f a a ktdb f 0 ktdb 0 f
i =1 j =1 a =0 a i =1 j =1 i =1 j =1
NM NM f
f j NM NM NM NM
+ k pdb ji
a f a a +1 i
k ij
i
pdb f 1 j
k ijpdb 0i 1+ f j
i =1 j =1 a =0 i =1 j =1 i =1 j =1
d i , j
dt
( )
= k ijp 0i CMj + k pji 0j CMi + kitc, j 0i 0j
Phase Equilibrium
The polymerization model currently considers a single-phase system (vapor or
liquid), two-phase system (vapor and liquid), or three-phase (VLL) system
when calculating concentrations for the reaction kinetics. For single-phase
systems, the reacting phase may be either vapor or liquid. In multi-phase
systems, reactions can occur in one or more phases simultaneously. Each
reaction object is associated with a single reacting phase, identified on the
options form.
Gel Effect
Bimolecular termination reactions between chain radicals become diffusion
controlled at high polymer concentrations or high conversion leading to an
initial increase in the polymerization rate and molecular weight. This condition
is known as the gel effect or Trommsdorff effect. At high polymer
concentrations, the increased viscosity of the reaction medium imposes a
diffusional limitation on the polymer chains, which leads to lower effective
termination rates. Typically the termination rate coefficients are affected first
by the gel effect because they involve diffusion of two bulky polymer radicals.
Eventually at high enough conversions, even the propagation, initiation, chain
transfer reactions, and the initiator efficiency are lowered by the gel effect.
Hence, in general it may be necessary to allow gel/glass effects for all the
polymerization reactions in the built-in kinetic scheme.
Diffusional Limitation
The diffusional limitation is usually modeled by multiplying the low conversion
reaction rate coefficients, ko , by a gel effect factor, GF, that decreases with
increasing conversion. Hence the effective rate coefficient for a reaction is
given by:
keff = koGF
Several empirical and semi-empirical correlations relating the gel effect factor
to conversion and operating conditions are available in the literature.
Currently two of these have been implemented as built-in correlations. Users
will be able to use these gel effect correlations simply by specifying the
correlation number and the parameters. The built-in correlations are:
Correlation Number 1:
a1
GF =
1 + a2 X pa3
Where:
Xp = Weight fraction of polymer
Correlation Number 2:
a10
GF =
1
A
a X
9 p
[(
exp BX p + CX p2 + DX 3p )]
With:
A = a1 + a2T
C = a5 + a6T
D = a7 + a8T
Where:
X p = Weight fraction of polymer
T = Temperature in Kelvin
This correlation has ten user specified parameters, a1 to a10 .
Users may also include their own gel effect correlation by specifying a
correlation number greater than the number of built-in gel effect correlations
(currently two) . In this case, users must provide the correlation for the gel
effect factor in the form of a Fortran subroutine. The user gel effect
subroutine argument list is documented here:
User Gel Effect Subroutine Arguments
Argument Descriptions
Variable I/O Type-Spec Dimension Description
(i) 1 (i)
i =1
1
DPN = i =1
LDPN = Nm
0
( j)
i =1
0
1 ( i ) 1 ( i )
SFRAC( I ) = Nm LSFRAC( I ) = Nm
(i)
i =1
1 (i)
i =1
1
Nm
2 0
( j)
j =1
0
PDI = 2 LPFRAC =
Nm 0
i (1)
i =1
0 ( j )
LEFRAC( I ) = Nm
( j)
j =1
0
The branching frequencies are calculated from the rate of chain transfer to
polymer and the rate of backbiting reactions. The branching frequencies are
reported in terms of number of branches per thousand segments in the
polymer.
Structural Properties
Frequently some of the polymer properties are reported in terms of other
properties that are related to these structural properties. These include
properties such as melt flow rate or melt index, viscosity numbers, or K-
values, etc. User-property subroutines can be set up for calculating some of
these polymer properties from the polymer moments and structural
properties.
Specifying Free-Radical
Polymerization Kinetics
Accessing the Free-Radical Model
To access the Free-Radical polymerization kinetic model:
1 From the Data Browser, click Reactions.
Listing Reactions
The Free-Radical model generates reactions based on the list of reacting
species. You can view the system-generated reactions, then assign rate
constant parameters to these reactions.
You can view a list of the system-generated reactions on the Reactions
sheet. In the Reaction summary listing for each reaction, the first column
indicates the reaction type. The second column lists the reactants, and the
last column lists the products. The Data Browser window can be resized to
better view the reaction listing. Use the following options:
Click To
Adding Reactions
To add a new reaction to the scheme click New to open the Add Reaction
subform:
1 In Reaction type, select a type for the new reaction. The Reaction
scheme for that type is displayed.
2 In the reactant fields (for example, Initiator, Catalyst) enter the
reactants of the categories allowed for that reaction type.
3 Where applicable, specify reaction by-products and stoichiometric
coefficients.
4 Click Cancel to discard the new reaction
or
Click New to add a new reaction
or
Editing Reactions
To edit a reaction, click Edit to open the Edit Reaction subform:
1 Modify the Reaction type as needed.
The Reaction scheme for that type is displayed.
2 Modify reactants as needed.
Adding Gel-Effect
Use the Gel-Effect sheet to add gel effect to reactions:
1 To activate the form, click Use Gel Effect.
2 In Sentence ID, enter a unique integer identifier.
3 In the Corr. No. field, specify a gel effect correlation number (use a
number greater than 100 for user-defined gel effect correlations).
4 In Parameters, list the parameters for the gel effect correlation.
When the specified correlation number is larger than the number of built-
in correlations, you must also enter the gel-effect subroutine name in the
Subroutine box.
5 To repeat steps 1-4 for additional gel-effect correlations, in the Sentence
ID field, click New.
Note: You must specify the Valid Phases keyword for each reactor model
referencing the kinetics to ensure the reactor models are consistent with the
reaction models.
Summary of Applications
The emulsion polymerization model is applicable to emulsion polymerization
processes where nucleation occurs by both the micellar and homogeneous
mechanisms or to seeded polymerization. Some of the applicable polymers
are described below:
Styrene - A component of synthetic rubber and paper coating
Butadiene - Synthetic rubber, impact modifier in ABS and HIPS
Tetrafluroethylene - Polytetrafluroethylene (PTFE), fluoropolymers Viton
Vinylacetate - Polyvinylacetate (PVA) adhesives, paint formulation
Methylmethacrylate - Surface coating applications.
Acrylic Acid - Minor component in paints
2-chloro-1,3-butadiene (chloroprene) - Neoprene rubber
Butyl Acrylate - Surface coatings
Butyl Methacrylate - Comonomer in surface coatings
Vinyl Chloride - PVC used in floor covering and coatings
Emulsion Polymerization
Processes
Emulsion polymerization is an industrially important process for the
production of polymers used as synthetic rubber, adhesives, paints, inks,
coatings, etc. The polymerization is usually carried out using water as the
dispersion medium. This makes emulsion polymerization less detrimental to
the environment than other processes in which volatile organic liquids are
used as a medium.
In addition, emulsion polymerization offers distinct processing advantages for
the production of polymers. Unlike in bulk or solution polymerization, the
viscosity of the reaction mixture does not increase as dramatically as
polymerization progresses. For this reason, the emulsion polymerization
process offers excellent heat transfer and good temperature throughout the
course of polymer synthesis. This process is always chosen when the polymer
product is used in latex form.
Particle Formation
To appreciate the complexities of emulsion polymerization, a basic
understanding of the fundamentals of particle formation and of the kinetics of
the subsequent particle growth stage is required. A number of mechanisms
have been proposed for particle formation. It is generally accepted that any
one of the mechanisms could be responsible for particle formation depending
on the nature of the monomer and the amount of emulsifier used in the
recipe.
The two common mechanisms for particle formation are:
Micellar nucleation
Homogeneous nucleation
With micellar nucleation, micelles, which are aggregates of emulsifier
molecules, act as the site of nucleation.
With homogeneous nucleation, the radicals produced in the aqueous phase
polymerize with dissolved monomer and precipitate out to form precursor
particles. The precipitated precursor particles coagulate with each other until
a stable particle is formed.
Micellar Nucleation
Micellar nucleation is considered to be the primary mechanism for particle
formation (Harkins, 1945; Smith & Ewart, 1948) in those emulsion
polymerization systems for which the monomer is very sparingly soluble in
water, and where the concentration of emulsifier is above the critical micelle
concentration (CMC). As the name implies, the micelles, which are formed
when the emulsifier concentration is above the CMC, act as the site for
particle nucleation.
The reaction mixture consists of water, monomer, emulsifier and a water-
soluble initiator. The monomer is dispersed in the form of droplets in the
water by agitation. The droplets formed are stabilized by the emulsifier
molecules which are adsorbed on the droplet surface. In addition to the
droplets, monomer is also found dissolved in the aqueous medium and
solubilized inside the micelles.
Similarly, the emulsifier is found in three locations: in the micelles, dissolved
in the aqueous medium, and adsorbed on the monomer droplets. Since a
water soluble initiator is used, the initiator molecules will be mainly found
dissolved in the water medium.
When a typical emulsion polymerization recipe is heated, the initiator
dissociates in the aqueous medium and produces initiator radicals. Upon
propagating with monomer in the water phase the initiator radicals form
oligomeric radicals and enter the micelles, which are aggregates of emulsifier
molecules inside which a small amount of monomer is entrapped. The
capturing of a radical by micelle and reaction with the entrapped monomer
signifies the formation of a particle from a micelle. As the propagation takes
Stage I
The time required for particle nucleation to be complete is also called the
nucleation time or the nucleation period, and usually lasts 10-15 minutes in
conventional polymerization systems. This is commonly referred to as the
seed stage, or Stage I, in the emulsion polymerization industry. After the
nucleation or seed stage, the number of particles in the reaction mixture
remains constant if particles do not agglomerate.
Stage II
The stage following the seed stage is called the growth stage or Stage II of
the emulsion polymerization. In Stage II, the polymer particles grow through
a steady diffusion of monomer from the monomer droplets to the particles.
Since the number of particles remains constant and the particles are
saturated with monomer, this stage is marked by a constant rate of
polymerization and could easily be observed on a conversion vs. time plot.
Stage II is considered complete when the monomer droplets are totally
depleted.
Stage III
In Stage III, the monomer finishing stage, the reaction mixture consists of
the monomer swollen polymer particles and the aqueous medium. Further
polymerization of the monomer in the particles takes place. This results in a
decrease of the particle size due to higher density of the polymer compared to
the monomer. During Stage III, the concentration of monomer dissolved in
the aqueous phase falls rapidly, as does the concentration in the polymer
particles. The final product obtained at the end of Stage III is called latex.
The following figure illustrates the stages in a micellar nucleation emulsion
polymerization reaction:
k p M p n MWm 1
v s = (3.5)
Na dp p
Where:
f = Initiator efficiency
kd = Rate constant for initiator dissociation
I = Initiator concentration
Na = Avogadro's number
kp = Propagation constant
Homogeneous Nucleation
Homogeneous nucleation is the mechanism for particle formation when
monomers are more water soluble and level of emulsifier is not high enough
for the formation of micelles in the recipe.
The following figure shows a detailed picture of kinetic events that take place
during particle formation by homogeneous nucleation:
dN N a (i + kde nN / N a )
jcr +1
k pw M w
Rhomo = =
dt N agg k pw M w + ktw Rw + kap Ap + kam Am
In the above equation Rw refers to the concentration of live radicals in the
water phase and is given by:
R =
( + k
i nN / N a )
de 1 jcr +1
w
k pw M w + ktw R + kap Ap + kam Am 1
w
Where:
k pw M w
=
k pw M w + ktw Rw + kap Ap + kam Am
Refer to the table of page 204 for the explanation of the symbols in the above
equations.
Particle Growth
Stage II, the growth stage, starts after the completion of the seed stage in
the in situ seed process . In the in situ seed process, the micelles are used for
the generation of the seeds. In the case of an external seed process, a well
characterized seed is used as the starting material for emulsion production. If
quality control tests indicate that the particle number and particle size
distribution of the seed particles will not result in the desired end-product
specifications, the batch is normally terminated. Therefore, in the growth
stage it can be assumed that the desired number of particles, with the desired
particle size distribution has already been formed.
It is generally agreed that the growth process is a well understood process
and amenable to control. The growth reaction is responsible for developing
molecular properties (molecular weights, composition, etc.) and morphology
(core-shell, particle size distribution). Since the growth reaction lasts about
Radical Balance
The radical balance in the aqueous phase is controlled by the kinetic events
that are responsible for the radical generation and the radical consumption in
= + mn Y 2 (3.7)
With:
v s N a2 k a Rw N a2 v
= = = k a Rw (3.8)
N p k tp N p k tp
RI v s N a2
= (3.9)
N p ktp
kde v s N a
m= (3.10)
ktp
2 N p ktp ktw
Y= (3.11)
ka2 v s N a2
The emulsion polymerization model nomenclature is shown here:
Symbol Description
f Initiator efficiency
Particle Phase
Particles containing n free-radicals are depleted in the particle phase in three
analogous ways. By equating the rate of formation to the rate of depletion of
particles containing n free-radicals the recurrence formula is obtained:
(n + 2)(n + 1) n(n 1)
N n 1 ( N a / N p ) + N n +1k de (n + 1) + N n + 2 ktp = N n ( N a / N p ) + k de n + ktp
Nav N a v
(3.12)
This recurrence formula was first developed by Smith and Ewart, in a slightly
modified form (Smith & Ewart, 1948). Equation 3.12 can be solved for the
a = 8 (3.14)
The simultaneous solution for n (Equation 3.13) and the stationary steady
state equation for the radical balance in the aqueous phase (Equation 3.6)
completely define the kinetics of the emulsion polymerization.
Activated Initiation
The mechanism for activated initiation is given as:
k kj
I k + A j
act
nkj R + x *
Where:
Ik = Initiator molecule
dR
R kj
act = = nkj f kj kact
kj
CI k C A j
dt
Where:
kj
kact = Rate constant for activated initiation
f kj = Efficiency factor
Redox Initiation
The mechanism for redox initiation is given as:
k
I k + Fe + +
k ox
nk R + Fe + + + + Y * (oxidationslow)
Fe + + + + Re
k re
Fe + + + x * (reductionfast)
Similar to activated initiation, redox initiation is used in emulsion
polymerization reactions to promote decomposition of initiators at a much
lower temperature. For example, redox initiation is employed in cold rubber
production. It is also used in emulsion polymerization reactions where high
radical flux is needed.
=
dt k koxk CI k + kred CRe
Where:
CFet = Total concentration of the iron in the aqueous phase
Absorption by micelles:
k
Rj + N m
am
N1 Ram = kamamCN m CR
j
Desorption:
k
N i
de
N i1 + R Rde = kdeiCN i
Where:
am = Area of a single micelle
Ea VP 1 1
k = k o exp
R R T Tref
Where:
ko = Pre-exponential factor in l/sec for first order reactions,
and m / kmol s for second order reactions
3
The second term in the exponential function contains the activation volume
and is important for high pressure polymerization systems. For detailed
Ea
k = ko exp
RT
assuming zero activation volume.
Model Assumptions
The emulsion polymerization process is extremely complex and involves
phenomena for which a complete theoretical understanding has not been
reached. Important assumptions are made in the emulsion polymerization
model:
The reaction mixture is perfectly mixed
Particles are formed by the micellar or the homogeneous mechanism
No agglomeration or breakage of particles occurs
No secondary nucleation occurs
All particles have the same average number of radicals and hence the
same volumetric growth rate
The particle size distribution is unimodal, with moments of PSD sufficient
to describe the PSD
There are no mass transfer limitations on the polymerization reactions
Molecular weight is controlled by chain transfer reactions
k i2 = k i1 / k iLL
k iLL values are only available when there is sufficient monomer present in the
swollen polymer particles to form a separate monomer phase if polymer were
removed. If the 3-phase flash does not detect a separate monomer phase,
k iLL values will not be available, and the algorithm will transfer all monomer
from the aqueous phase to the polymer phase.
In addition, there are two rigorous phase equilibrium approaches to handle
the thermodynamics of monomer partitioning. The first rigorous approach
assumes the presence of two liquid phases. The distribution of water,
monomers, and polymers is determined by isofugacity relationships, and the
fugacities of various species are computed by the physical property option set
chosen for the system. The second approach performs rigorous four phase
(vapor-liquid-liquid-polymer) flash calculations based on a newly available
flash algorithm.
F ( v, t ) ( v F ( v, t ))
+ = kam Am N a [ R ]w ( v v m ) + Rhomo( v v h ) (3.15)
t v
In Equation 3.15 the right-hand side represents the nucleation of particles
from miceller and homogeneous nucleation. Refer to the table on page 204
for an explanation of the variables used. The volumetric growth rate is v for
a single unswollen particle (Equation 3.5):
k p M p n MWm
v = (3.16)
Na dp
The general population balance equation can be converted to the equivalent
moment equations. The j-th moment of the particle size distribution is given
as:
j = j F ( , j )d (3.17)
0
User Profiles
In addition to the polymer properties reported through the component
attributes, other model calculations are reported through User Profile
variables. The following user profile variables may be requested from the
model:
Specifying Emulsion
Polymerization Kinetics
Accessing the Emulsion Model
To access the Emulsion polymerization kinetic model:
1 From the Data Browser, click Reactions.
2 From the Reactions folder, click Reactions.
The Reactions object manager appears.
3 If the kinetic model already exists, double-click the desired Reaction ID in
the object manager or click Edit to get to the input forms.
4 To add a new model, from the Reactions object manager, click New. If
necessary, change the default ID for the reaction.
5 Select Emulsion as the reaction type and click OK.
Use the Phases forms to enter information related to phase partitioning and
particle growth. Use the following options:
Use this sheet To
Listing Reactions
The Emulsion model generates reactions based on the list of reacting species.
You can view the system-generated reactions, then assign rate constant
parameters to these reactions.
You can view a list of the system-generated reactions on the Specifications
Reactions sheet. In the Reaction summary listing for each reaction, the first
column indicates the reaction type. The second column lists the reactants,
and the last column lists the products. The Data Browser window can be
resized to better view the reaction listing. Use the following options:
Click To
Adding Reactions
To add a new reaction to the scheme, click New to open the Add Reaction
subform:
1 In Reaction type, select a type for the new reaction.
The Reaction scheme for that type is displayed.
2 In other reactant (for example, Initiator, Catalyst) fields, enter the
reactants of the categories allowed for that reaction type.
3 Click Cancel to discard the new reaction
or
Click New to add a new reaction
or
Editing Reactions
To edit a reaction, click Edit to open the Edit Reaction subform:
1 Modify the Reaction type as needed.
The Reaction scheme for that type is displayed.
2 Modify reactants as needed.
Adding Gel-Effect
Use the Gel-Effect sheet to add gel effect to reactions:
1 Enter a unique integer identifier in No.
2 In the Reaction field, specify the reaction to which you would like to
apply gel effect.
3 In the Corr. No. field, specify a gel effect correlation number.
4 In Parameters, list the parameters for the gel effect correlation.
References
Barton, J., & Capek, I. (1994). Radical Polymerization in Disperse Systems.
New York: Ellis Harwood.
Blackley, D. C. (1975). Emulsion Polymerization: Theory and Practice.
London: Applied Science Publishers Ltd.
Gilbert, R. G. (1995). Emulsion Polymerization: A Mechanistic Approach.
Boston: Academic Press.
Hamielec, A. E., & Tobita, H. (1992). Polymerization Processes. In Ullmans
Encyclopedia of Industrial Chemistry, A21, 305. New York: VCH Publishers.
Harkins, W. D. (1945). J. Chem. Phys., 13, 301.
Odian, G. (1991). Principles of Polymerization, 3rd. Ed. New York: John Wiley
& Sons.
OToole, J. T. (1965). Kinetics of Emulsion Polymerization. J. Appl. Polym.
Sci., 9, 1291.
Poehlein, G. W. (1986). Emulsion Polymerization. In H.F. Mark, N. M. Bikales,
C. G. Overberger, and G. Menges, (Eds.). Encyclopedia of Polymer Science &
Technology, 6, 1. New York: Wiley-Interscience.
Ponnuswamy, S. R., & Hamielec, A. E. (1997). Emulsion Polymerization:
Theory and Practice. Lecture notes for intensive short course on polymer
reaction engineering held at Burlington, ON, Canada, April 28-30.
Smith, W. V., & Ewart, R. H. (1948). J. Chem. Phys., 16, 592.
Summary of Applications
The Ziegler-Natta polymerization model is applicable to processes utilizing
coordination catalysts for the production of stereospecific polymers.
Some examples of applicable polymers are:
Linear low density polyethylene - Ethylene is copolymerized with an alpha-
olefin, such as 1-butene, 1-hexene, or 1-octene. Commercial processes
include low pressure, slurry-phase processes, solution-phase processes,
low pressure, gas phase processes.
High density polyethylene - Ethylene homopolymers or copolymers with
high alpha olefins with density 0.940 g / cm 3 and higher. Commercial
Ziegler-Natta Processes
Ziegler-Natta polymerization accounts for a significant fraction of the
polyethylene polymers and all the polypropylene homopolymers and
copolymers produced commercially. The commercial production of these
polyolefins is done exclusively by continuous processes using several different
processes and reactor types operating over a wide range of conditions.
High density polyethylene (HDPE) and linear low density polyethylene (LLDPE)
are produced via catalyzed polymerization processes. The operating
conditions for the catalyzed processes are relatively less severe compared to
the high pressure processes for LDPE production. The pressure generally
ranges from 10-80 atm while the temperatures range from 80-110C. The
pressure and temperature may be as high as 200 atm and 250C in some of
the solution polymerization processes.
Catalyst Types
There is a variety of catalysts used for ethylene polymerization including
supported and unsupported heterogeneous catalyst systems and
homogeneous catalyst systems. The Ziegler-Natta transition metal (Ti) based
catalysts are the most widely used.
However, there are numerous variations of these catalysts. Some vanadium
based catalysts are also used. Chromic oxide on silica catalysts are used in
the Phillips loop reactor process, while the Union Carbide Unipol process may
use either Ziegler-Natta (Ti) or chromium compounds on silica catalysts.
More recently, several manufacturers have been developing commercial
processes using metallocene based catalysts, mainly zirconium and titanium.
These catalysts are believed to be single site catalysts that are capable of
producing high yields, combined with narrow molecular weight and copolymer
composition distributions.
All commercial isotactic polypropylene homopolymer (PP) is manufactured
using heterogeneous Ziegler-Natta catalyst systems. The catalyst consists of
a solid transition metal halide, usually TiCl3 , with an organoaluminum
compound cocatalysts, such as diethylaluminum chloride (DEAC), or a MgCl2
supported TiCl4 . AlEt3 catalyst.
Bulk Loop - fluid --- Supported Ti 60-80 30-40 20 1-2 Ethylene & Himont
(Liquid bed others Mitsui
Pool)
+
Second
Stage
CSTR - --- Supported Ti 60-75 30-40 30-40 2 Ethylene Sumitomo
CSTR
CSTR - --- Unsupported 40-75 30-40 20 2-5 Ethylene Dart
stirred or supported El Paso
horizontal Ti
bed
Diluent CSTR Liquid Ti/V 0-20 5-20 --- 1 Ethylene, Montedison
Slurry monomers Butene, Dutral
& diluents dienes
Multistage Fluid bed - --- Supported Ti 60-80 20 20 3-5 Ethylene & Sumitomo
Gas fluid bed others Union
Carbide
Vertical --- Unsupported 70-90 20 20 4 Ethylene & BASF
stirred bed of supported others ICI
- stirred Ti
USI
bed
Horizontal --- Supported Ti 70-90 20 20 4 Ethylene & AMOCO
stirred bed others Chisso
-
horizontal
stirred bed
Reaction Steps
There are a few key elementary reactions that apply to almost all catalyzed
addition polymerization systems. These include the three basic reaction steps:
Chain initiation
Propagation
Chain transfer (spontaneous and to small molecules such as monomer,
solvent and chain transfer agents)
For chromium and metallocene catalyst systems, additional reactions for long
chain branching via terminal double bond polymerization must also be
included.
In addition to the polymerization reactions, there are reactions affecting the
catalyst active sites on which the polymerization reactions take place. These
include catalyst site activation, inhibition and deactivation. The catalyst
reactions and the polymerization reactions occur simultaneously during the
polymerization.
A comprehensive kinetic scheme for the catalyzed multi-site homo- and
copolymerization of any number of monomers has been built into Aspen
Polymers.
Catalyst States
The multi-site catalyst states and the types of reactions affecting them are
shown here:
Site Types
In the figure, potential sites and dead sites are considered to be independent
of site type. The user specifies the number of site types to be included for a
particular simulation.
A vacant site is an active site that does not have a polymer or other
molecule attached to it.
A propagation site has a growing polymer molecule attached to it.
Inhibited sites have small molecules such as hydrogen or poisons
attached, temporarily blocking it from becoming propagation sites. The
small molecule may dissociate from an inhibited sited, which then
becomes a vacant site once again. Therefore, the site inhibition reaction is
considered reversible.
Am Cocatalysts m
Em Electron donor m
Mj Monomer j
Nm Number of monomers
Xn Inhibitor n
k
0,i Zeroth moment of live polymer with respect to active
segment of type i and active site of type k
Polymerization Mechanism
The catalyst active site is attached to one end of a live polymer chain via a
metal-carbon bond. It is generally accepted that polymerization proceeds via
a two-step mechanism. In the first step, monomer is complexed to the
transition metal site. The second step is the coordinated insertion of the
Copolymerization Mechanism
For copolymerization, the built-in kinetic scheme allows the user to specify
the number of monomer types used. Similarly the user has the flexibility to
specify the number of each type of reactive species present in the
polymerization: catalysts, cocatalysts, chain transfer agents, solvents, etc.
The user is able to tailor the built-in kinetics to model a specific catalyzed
polymerization system by selecting a subset of the reactions shown in the
Built-In Ziegler-Natta Catalysts and Polymerization Kinetic Scheme figure on
page 227. However, it is important that the subset include a chain initiation,
propagation, and at least one chain transfer or active site deactivation
reaction to produce dead polymer.
Rate Expressions
The rate expression for each reaction is generally written as a product of the
rate constant and the concentrations of the reacting species. In many of the
reactions, one of the reacting species is a polymer chain while the other is a
small molecule such as monomer, chain transfer agent, cocatalyst, etc. A
reaction order with respect to the small reacting molecule is included for
some of the reactions. This reaction order has a default value of one.
The rate constants for each reaction at sites of type k are calculated at the
reaction temperature using the Arrhenius equation shown below. The user
specified rate constant parameters are pre-exponential factor ( kok ) , activation
energy ( Ea k ) at sites of type k, and the reference temperature.
Rate Constant
E ak 1
k = k o exp -
k k 1
R T Tref
Where:
ko = Pre-exponential factor in 1/sec for first order reactions
Catalyst Pre-Activation
Some of the chromium catalysts used in these processes exhibit slow
activation with induction period. This slow activation can be modeled by
catalyst preactivation reaction. The precatalyst goes to catalyst that further
undergoes site activation, initiation and propagation.
Chain Initiation
Chain initiation involves the reaction of a monomer molecule at a vacant
active site to form a live polymer molecule of unit length at that site. This
reaction converts a vacant active site to a propagation site. The chain
initiation reaction is shown below:
Propagation
The live polymer at each active site type grow or propagate through the
addition of monomer molecules to form long polymer chains. The propagation
reaction is represented by:
As a result, there will be twelve rate constants ( k pk ,ij ) , where the subscript i
refers to the active segment type while the second subscript j refers to the
propagating monomer type. The superscript k refers to active site type. For
the terminal model the rate of propagation is dependent only on the
concentration of live polymer with active segment i at active site k and the
concentration of the propagating monomer j.
In Aspen Polymers Version 3.0 and higher, another propagation reaction has
been added to account for formation of atactic polymer. This reaction has the
same form as the main propagation reaction:
Pnk, i + M j Pnk+ i ,i k
R paij = k paij
k
0k, j (CMi )
O kpaMi
(atactic propagation)
k
but uses a different rate constant ( k paij ) . When the atactic propagation
reaction is included in the simulation, the main propagation reaction should
be considered to account for the formation of all polymer whether it is
isotactic or atactic. Hence the main propagation reaction is also termed the
total propagation. The atactic propagation reaction only accounts for the
formation of atactic polymer. The atactic content of the polymer is then
calculated from the ratio of atactic to total polymer.
Site Deactivation
The catalyst site deactivation step involves the deactivation of active sites,
vacant and propagation, to form dead sites. Depending on the catalyst
system and operating conditions, the deactivation rate may be high or low.
There are several different site deactivations reactions included in the built-in
kinetic scheme. They include site deactivation by cocatalyst, by electron
donors, by hydrogen, by monomer, by poisons, and spontaneous site
deactivation. Different catalyst systems tend to be deactivated by a different
subset of the reactions.
The deactivation rate constants are assumed to be dependent only on the site
type and not on the polymer segment attached to a site. Therefore, the same
rate constant is applied to both vacant and propagation sites of the same
type. Note that deactivation rates shown in the Built-In Ziegler-Natta
Catalysts and Polymerization Kinetic Scheme figure on page 227 are per unit
of active (vacant and propagation) site concentration.
Site Inhibition
Inhibited sites have small molecules such as hydrogen or poisons attached.
As a result, inhibited sites are temporarily blocked from becoming
propagation sites. The site inhibition reaction is considered reversible.
Therefore, the small molecule may dissociate from an inhibited site which
then becomes a vacant site once again. The user must specify rate constant
Cocatalyst Poisoning
For some catalyst systems, additional amounts of cocatalysts are fed to the
reactor to counteract the effect of any poisons present . This is modeled as a
cocatalyst poisoning reaction in the built-in kinetics. The product of this
reaction is designated as a byproduct in the list of reactive species. The
byproduct is considered to be inert and does not participate in any reaction.
Phase Equilibria
The polymerization model currently considers a single-phase system (vapor or
liquid), two-phase system (vapor and liquid), or three-phase (VLL) system
when calculating concentrations for the reaction kinetics. For single-phase
systems, the reacting phase may be either vapor or liquid. In multi-phase
systems, reactions can occur in one or more phases simultaneously. Each
reaction object is associated with a single reacting phase, identified on the
options form.
Rate Calculations
The Ziegler-Natta polymerization kinetic model supplies to the reactor models
the reaction rates for the components and the rate of change of polymer
attributes (e.g. the chain length distribution moments) . The component
reaction rates are computed from the kinetic scheme by summing over all
reactions that involve the component. The site based moment rates are
derived from a population balance and method of moments approach similar
to that described in the Calculation Method section on page 182.
Note: The TDB segment should be of type end segment and should not be
used as a repeat segment for a particular monomer (see Step 2).
4 Continue listing other types of reacting species, for example, solvents,
transfer agents, etc.
5 Select the Generate Reactions option if you want the reactions to be
generated automatically.
Listing Reactions
The Ziegler-Natta model generates reactions based on the list of reacting
species. You can view the system-generated reactions, then assign rate
constant parameters to these reactions.
You can view a list of the system-generated reactions on the Reactions
sheet. In the Reaction summary listing for each reaction, the first column
indicates the reaction type. The second column lists the reactants, and the
last column lists the products. The Data Browser window can be resized to
better view the reaction listing. Use the following options:
Click To
Adding Reactions
To add a new reaction to the scheme, click New to open the Add Reaction
subform:
1 In Reaction type, select a type for the new reaction.
The Reaction scheme for that type is displayed.
2 In other reactant (for example, Initiator, Catalyst) fields, enter the
reactants of the categories allowed for that reaction type.
3 Click Cancel to discard the new reaction
or
Click New to add a new reaction
or
Editing Reactions
To edit a reaction, click Edit to open the Edit Reaction subform:
1 Modify the Reaction type as needed.
The Reaction scheme for that type is displayed.
2 Modify reactants as needed.
References
Albright L. F. (1985). Processes for Major Addition-Type Plastics and Their
Monomers, 2nd Ed. Florida: Krieger Pub.
Brockmeier, N. F. (1983). Latest Commercial Technology for Propylene
Polymerization. In R.P. Quirk (Ed.), Transition Metal Catalyzed
Polymerizations - Alkenes and Dienes. New York: Academic Pub.
Choi, K-Y, & Ray, W. H. (1985a). Recent Developments in Transition Metal
Catalyzed Olefin Polymerization - A Survey. I. Ethylene Polymerization. J.
Macromol. Sci. Rev. Macromol. Chem. Phys., C25 (1), 1.
This section covers the ionic polymerization kinetic model available in Aspen
Polymers (formerly known as Aspen Polymers Plus). The cationic, anionic and
group transfer addition polymerization kinetics can be modeled using this
model.
Topics covered include:
Summary of Applications, 241
Ionic Processes, 242
Reaction Kinetic Scheme, 242
Model Features and Assumptions, 250
Polymer Properties Calculated, 251
Specifying Ionic Polymerization Kinetics, 252
Summary of Applications
Some examples of applicable polymers are given in below:
Polystyrene - Anionic polymerization is used to produce narrow molecular
weight distribution polystyrenes in small quantities. Cationic
polymerization is used to produce low molecular weight polystyrenes for
coatings and glues. Block copolymers of styrene and butadiene are
produced commercially with anionic polymerization.
Polyisobutylene - Low-to-medium molecular weight poly isobutylene is
produced commercially by polymerization of high purity isobutylene in
isobutane or hexane diluent using aluminum chloride or hexane trifluoride
as a catalyst.
Polybutene - Polybutenes are produced in solution by copolymerizing
isobutylene and n-butene using aluminum chloride or hexane trifluoride as
a catalyst.
Polybutadiene - Block copolymers of styrene and butadiene are produced
commercially with anionic polymerization.
Polyoxides - Examples are poly ethylene oxide (PEO) and poly propylene
oxide (PPO). Continuous tubular or column reactors or semibatch
Ionic Processes
Many specialty polymers are manufactured by ionic polymerization processes.
For the description of a specific ionic process, refer to the References section.
Ionic polymers fall in the category of addition polymers, i.e., the reactive
species grow in length by continuous addition of monomer units. However,
there are several features that distinguish the ionic polymerization processes
from other addition polymerization processes like free-radical and Ziegler-
Natta:
Different propagating species are often present in ionic processes. These
species may be free ions, tight ion pairs, loose ion pairs, dormant esters,
etc. Moreover the propagating species are often in equilibrium.
Association or aggregation phenomena is common in BuLi type of
initiators for anionic polymerization. The associated initiator is not reactive
and is in equilibrium with its dissociated form. The association phenomena
also takes place with growing polymer chains, which reduces the actual
number of chains growing at any given time. This phenomena affects both
the conversion and polymer properties.
Exchange reaction takes place between live and dormant polymer. The
active species transfer from one polymer to another. This reaction controls
the molecular weight distribution of the final polymer. If the exchange
reaction rate constant >> propagation rate constant, then for increasing
monomer conversion the polydispersity approaches a limiting value of 1.0.
Ionic reactions are a strong function of solvent, initiator and operating
conditions and are susceptible to poisons.
Chain transfer and termination reactions may be negligible or absent in
certain polymerization processes thus leading to formation of living
polymers.
Reaction Steps
There are a few key elementary reactions that apply to all ionic
polymerization systems. These include the three basic reaction steps:
Formation of active species
Chain initiation
Initiator Attributes
The initiator in ionic model has three attributes which are solved along with
moment equations:
AI m Associated initiator, m
Cn Catalyst, n
Ip Initiator, p
Mj Monomer, j
Xm Exchange agent, m
The ionic model is a terminal model, implying that the rate constants are
functions of only terminal segment of the polymer chain.
Rate Constant
Eai 1 1
k i = k io exp -
R T T
ref
Where:
ko = Pre-exponential factor in 1/sec for first order reactions
and m3/kmol-sec for second order reactions
Ea = Activation energy in mole enthalpy units
R = Universal constant
T = Reaction temperature in Kelvin
Tref = Reference reaction temperature in Kelvin (default is
1E38)
AI m n m,p I p
The association and dissociation of initiator is observed in alkyl-Lithium type
of initiators in nonpolar solvents for anionic polymerization. n-butyl-Li exists
as hexamer whereas s-BuLi and t-BuLi exist as tetramers for styrene
polymerization. The dissociated initiator further reacts with monomer to form
growing polymer with unit chain length in chain initiation step. This reaction
can also be used to represent self-ionization of some strong acids
Chain Initiation
The active species incorporate monomer to form propagating species with
unit chain length:
P0i + M j P i
j,j
The initiator (in dissociated form) directly reacts with monomer to form
propagating species with unit chain length. A counter-ion may be formed
( d I 2 = 1) :
I m + M j Pi j,j + d I 2 CIi
The transfer active species incorporate monomer to form propagating species
with unit chain length:
P0t,i + M j P i
j,j
Propagation
The growing polymer with an active species at the end of the chain may grow
or propagate through the addition of monomer molecules to form long
polymer chains. The propagation reaction is represented by:
Pn,ki + M j Pn+i j , j
where monomer j is being added to a polymer chain of length n, with an
active segment of type k and active species of type i. The resulting polymer
chain will be of length n+1 and the active segment will be of type j. The
Copolymerization
For copolymerization, there will be N m * N m * N site propagation reactions that
may have different reactivities. For example, with two monomers and three
site types, the monomer being added could be monomer 1 or monomer 2
while the active segment type could be segments from monomer 1 or
monomer 2 at each site type. As a result, there will be twelve rate constants
( k pi ,kj ) , where the subscript k refers to the active segment type while the
second subscript j refers to the propagating monomer type. The superscript i
refers to active species type.
For the terminal model the rate of propagation is dependent only on the
concentration of live polymer with active segment k on active species i and
the concentration of the propagating monomer j.
Association or Aggregation
The propagating species initiated by alkyl-Lithium type of initiators in anionic
polymerization also exhibit the association phenomena like the initiator. The
association of live polymeric species is usually dimeric in nature. The
associated polymer Qni + m, k is tracked as a separate polymer and does not
participate in any other reactions:
Exchange
Exchange reactions exchange the growing active species between two
different growing polymers. If both free ions and ion pairs are growing, then
the counter-ion can exchange between the two polymeric species. There can
be exchange reaction between dormant polymer (with ester as growing
species which does not propagate) and ion pairs/free ions. The exchange
reaction can also take place between an exchange agent (e.g., alcohol end
group in solvent or starter) and a growing polymer. If exchange reaction with
a small molecule does not produce a P0 species, then d EXA = 0 . The exchange
between growing species and dormant species takes place in polyether
polyols (propylene oxide). The dormant species can be an alcohol:
Pn,ki + Pm,p
j
Pn,kj + Pm,p
i
Chain Transfer
There are four types of chain transfer reactions:
Spontaneous
Monomer
Dormant polymer formation
Chain transfer agent
Spontaneous chain transfer can lead to formation of a dead polymer molecule
and an active species caused by proton loss, e.g., cationic polymerization of
poly isobutylene:
Monomer
i
Pn,k + M j Dni + P ij, j
Chain transfer to monomer in polyethers (propylene oxide) can form dormant
species (alcohol) . The dormant species is modeled as a live polymer with a
different site type but it does not have the usual chain initiation and
propagation reactions. This dormant polymer can participate in exchange
reactions:
Chain Termination
The growing polymer chain with ion pairs as active species can be
spontaneously terminated by combination with counter ion (bTCI = 0) , e.g.,
cationic polymerization of polystyrene, tetrahydrofuran, polyisobutylene. A
growing free ion active species can terminate by reacting with its own counter
ion (bTCI = 1) :
Coupling
Coupling reactions are encountered in thermo-plastic elastomer production.
For example, to make styrene-butadiene-styrene (SBS) TPE, styrene is added
first, and then half of the butadiene is added. Introducing a coupling agent to
this reaction system will form SBS polymer. In this example i=j=1 and k=2.
Phase Equilibria
The polymerization model currently considers a single-phase system (vapor or
liquid), two-phase system (vapor and liquid), or three-phase (VLL) system
when calculating concentrations for the reaction kinetics. For single-phase
systems, the reacting phase may be either vapor or liquid. In multi-phase
systems, reactions can occur in one or more phases simultaneously. Each
reaction object is associated with a single reacting phase, identified on the
options form.
By default the reacting phase is assumed to be the liquid phase (for VLL
systems, the reacting phase must be specified). Several reaction models can
be referenced from a single reactor block to account for reactions in each
phase.
Rate Calculations
The ionic polymerization kinetic model supplies to the reactor models the
reaction rates for the components and the rate of change of polymer
attributes (e.g. the chain length distribution moments) :
The component reaction rates are computed from the kinetic scheme by
summing over all reactions that involve the component.
Dissociated Aggregate
Polymer,
i
Q
n + m, k
if ,k = n f Qni + m,k
n m
Bulk Polymer
Nseg
if = n f {Pni,k + Qni ,k } + Dni
k k
Nseg Nseg
= k
i
f ,k + if ,k + n f Dni
k n
Adding Reactions
To add a new reaction to the scheme, click New to open the Add Reaction
subform:
1 In Reaction type, select a type for the new reaction.
The Reaction scheme for that type is displayed.
2 In other reactant (for example, Initiator, Catalyst) fields enter the
reactants of the categories allowed for that reaction type.
3 Click Cancel to discard the new reaction
or
Click New to add a new reaction
or
Editing Reactions
To add or edit a reaction, click Edit to open the Edit Reaction subform:
1 Modify the Reaction type as needed.
The Reaction scheme for that type is displayed.
2 Modify reactants as needed.
References
Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization
Engineering. New York: Wiley.
Bikales, M., Overberger, & Menges. (1985). Encyclopedia of Polymer Science
and Engineering, 2nd Ed. New York: Wiley Interscience.
Chang, C. C., Miller, J. W., & Schorr, G. R. (1990). Fundamental Modeling in
Anionic Polymerization Processes. J. of Appl. Pol. Sci., 39, 2395-2417.
Chang, C. C., Halasa, A. F., & Miller, J. W. (1993). The Reaction Engineering
of the Anionic Polymerization of Isoprene. J. of Appl. Pol. Sci., 47, 1589-1599.
Compton, R. G. (Ed.). (1992). Mechanism and Kinetics of Addition
Polymerizations. Comprehensive Chemical Kinetics, 31.
Fathi, H., Hamielec, A. E., & Davison, E. J. (1996). Modelling of Anionic
Solution Polymerization of Butadiene - The Effects of Chain Termination and
Long Chain Branching on Molecular Weight Distribution Development. Polymer
Reaction Eng., 4, No. 4.
Summary of Applications
The segment-based power-law reaction model can be used to simulate
polymerization reactions using a simple power-law type rate expression. This
may be useful when simulating new processes that do not fit well into the
other built-in models in Aspen Polymers, or when a very detailed mechanistic
reaction model is not necessary.
The segment-based power-law model is the best choice for simulating step-
growth addition processesfor example, the production of polyurethane.
This model may also be used to represent processes involving changes to
polymer segments. The underlying kinetics are basic power law reactions in
which segments and monomeric components may participate. Some
examples of applicable polymers are:
Polyvinyl alcohol (PVA) - Alcoholysis of polyvinylacetate
Chlorinated polyethylene (CPE) - Chlorination of polyethylene
Polymethylmethacrylate (PMMA) - Recovery of methylmethacrylate from
PMMA
Polyisobutylene - Chain scission of polyisobutylene
Reaction Categories
Regardless of the end effect of the polymer modification reaction, the events
taking place fall into one of two categories based on the site where they occur
on the polymer chain. The reactions may take place on:
Side groups
Polymer backbone: scission, depolymerization, cross-linking, or bond
changes
There are some fundamental issues that distinguish reacting polymers from
their low molecular weight counterparts. One obvious characteristic of
reacting polymers is the potential for steric hindrance. A reacting side group
may be too close to the polymer chain, for example. There may also be
changes in solubility as reaction progresses.
Furthermore, crystallinity has an effect on the polymer reactivity; in general,
for a semicrystalline polymer, only the amorphous region is able to react.
Conventional Species
Reactions involving all non polymeric species fall under this category.
Monomeric components may react among themselves to produce
intermediate species. These reactions are represented as Category I in the
Segment Based Model Reaction Categories figure on page 259.
CH3
C O
O OH
CH CH2 + CH3OH CH CH2 + CH3CO2CH3
Another example is the chlorination of polyethylene to produce chlorinated
polyethylene (CPE):
Chain Scission
A common polymer degradation reaction is chain scission. In this case, bonds
are broken along the polymer chain resulting in shorter polymer molecules
with lower molecular weight. Chain scission may be induced by several
factors. One example is the scission of polyisobutylene upon oxidation:
CH3 CH3
CH2 C CH2 CH2 C + CH2
CH2 CH2
Depolymerization
Depolymerization is the reverse of the propagation step of a polymerization
reaction. In such reactions, monomer molecules are lost from the polymer
chain. Depolymerization is often considered a degradation reaction. There
are, however, cases where it is brought on by design to recover monomer
from scrap polymer. An example depolymerization reaction is that of
polymethyl methacrylate to regenerate methyl methacrylate:
Propagation
Propagation reactions involve the addition of monomers to the end of a
growing polymer chain. Propagation is illustrated as Category V in the
Segment Based Model Reaction Categories figure on page 259.
Combination
There are other mechanisms through which polymer segments react with
each other. Some of these reactions, grouped as combination reactions,
include kinetic events where two polymer molecules combine into one. These
reactions are represented as Category VI in the Segment Based Model
Reaction Categories figure on page 259.
Branch Formation
Branch formation occurs when a polymer molecule attaches to another
polymer chain, converting a repeat unit to a branch point. Monomers can also
react with repeat units to initiate branch formation. Branch formation is
illustrated as Category VII in the Segment Based Model Reaction Categories
figure on page 259.
Cross Linking
Cross linking occurs when a repeat unit in one chain reacts with a repeat unit
in another chain, forming a cross link (branch 4) segment. Cross linking is
illustrated as Category VIII in the Segment Based Model Reaction Categories
figure on page 259.
Eai 1 1 bi
T
R T Tref
U ( flag i )
Tref specified i
k net ,i = [Catalysti ] k o i e
T
ref
Eai
T bi U ( flag i )
i
Tref unspecified *
k net ,i = [Catalysti ] k o i e RT
ratem = activity m C k
a mj
Assign User Rate Constants is used: j
j i net ,i
ratem = C k
amj
Assign User Rate Constants is not used: j net ,m
j
Nomenclature
Symbol Description
* The concentration basis may be changed to other units using the Concentration basis field on the
Specs sheet or using the optional concentration basis subroutine.
** The reference temperature may be specified globally on the Specs sheet or locally for each rate
constant set on the Rate-Constants sheet. If global and local reference temperatures are both
unspecified then this form of the equation is applied.
Where:
Fracs,i = Segment mole fraction
Mwsegavg = Nseg
Average segment molecular weight = SFRAC(i )* Mw
1
i
R s ,i * Mwi
Rp = 1
Mw p
End 1
Repeat 2
Branch-3 3
Branch-4 4
0 1 1
= 2
t t t
The factor of accounts for the fact that each connection links two
segments (without this correction the points of connection are counted twice).
This method is best illustrated through these examples:
Valid Reaction Type Stoichiometry 1 0
No Initiation M P1 MR +1 +1 0
Yes Branching Pn + M Pn +1 R + M B3 + E +1 +1 0
Yes Branching Pn + Pm Pn + m R + E B3 + R 0 +1 -1
User Subroutines
The segment-based power-law model can be customized by applying user-
written subroutines. There are two types of subroutines available. The
concentration and holdup basis for the model can be changed through a user
basis subroutine. A user rate-constant subroutine can be used to extend the
standard reaction rate expression. These routines can be used together in any
combination.
SUBROUTINE USBBAS
1 SOUT, NSUBS, IDXSUB, ITYPE, XMW,
2 IDSCC, NPO, NBOPST, NIDS, IDS,
3 NINTB, INTB, NREALB, REALB, NINTM,
4 INTM, NREALM, REALM, NIWORK, IWORK,
5 NWORK, WORK, NCPM, IDXM, X,
6 X1, X2, Y, DUM1, FLOWL,
7 FLOWL1, FLOWL2, FLOWV, FLOWS, VLQ,
8 VL1, VL2, VV, VSALT, VLIQRX,
9 VL1RX, VL2RX, VVAPRX, VSLTRX, RFLRTN,
* IFLRTN, CRATES, NTCAT, RATCAT, CSS,
1 VBASIS, IPOLY, NSEG, IDXSEG, AXPOS,
2 TIME )
Argument Descriptions
Variable Usage Type Dimension Description
* When using molar concentrations, this parameter is volume of the reacting phase in m 3
in RCSTR and RBatch or the cross-sectional area of the reacting phase in m 2 in RPlug.
Note: The argument lists for the segment-based user basis routine and step-
growth user basis routine are identical. Both types of models can reference
the same basis routines.
Example 1 illustrates how to use the user basis routine to convert the
concentration basis from the standard molar concentration basis (mol/L) to a
mass concentration basis (mol/kg). (Note: the current version of Aspen
Polymers supports several concentration basis through the BASIS keyword
located on the Specs sheet. This example is a demonstration). Using these
units, the reaction rates are calculated in units of mol/kg-sec. These rates are
multiplied by the holdup basis (VBASIS) for the reactor in the segment-based
power-law model. The holdup basis must be consistent with the concentration
basis, e.g., in this case it must be in kg. The holdup basis pertains to the
reacting phase, it does not include the phases that do not react.
Example 1: A User Basis Routine For the Mass-Concentration Basis
Note: This excerpt does not include the argument list and declarations
section of the user basis routine.
The plug flow reactor model in Aspen Plus assumes that the vapor and liquid
move at the same velocity through the reactor (e.g., no-slip conditions). This
assumption is not consistent with the physical reality of polymer finishing
reactors or wiped-film evaporators. The subroutine in Example 2 circumvents
the no-slip assumption in RPlug, allowing you to specify the volume occupied
by the liquid phase. In this example, you specifiy the first integer argument in
the RPlug block as 1 and the first real argument as the volume fraction of
the reactor occupied by the liquid phase.
Example 2: A User Basis Routine to Specify Liquid Volume in RPlug
UFRAC = 1.D0
IF ( REALB(1) .NE. RGLOB_RMISS ) UFRAC =
REALB(1)
IF ( INTB(1).EQ.1 ) THEN
C - unpack the mole fraction vector into the
molar concentrations...
CALL SHS_UNPACK ( X , NCPMX, IDXM, CSS )
C - concentration = mole fraction divided by molar
volume of phase
DO 20 I = 1, NCOMP_NCC
Note: This excerpt does not include the argument list and declarations
section of the user basis routine.
Argument Descriptions
Variable Usage Type Dimension Description
[C ] = 1 + ([aC+ bT])[ I ]
eff
actual
Where:
[Ceff ] = Effective catalyst concentration, mol/L
T = Temperature, K
a,b = Equation parameters
The net rate expression can thus be written as:
[C ] E* 1 1
actual R T Tref
rate = [Q] ko e
1 + ( a + bT )[ I ]
Where:
ko = Pre-exponential factor, (L/mol)/sec
E* = Activation energy
R = Gas law constant
Tref = Reference temperature for ko
[Q] = Concentration of component Q, mol/L
The standard rate expression for side reactions is:
E* 1 1
R T Tref
Ci i * U ( j )
rate = koe
i
Where:
= Product operator
Ci = Concentration of component i
Packed Vectors
Aspen Plus frequently uses a technique called packing to minimize
simulation time. The user models previously described use packed vectors to
track the mole fractions of each phase (vectors X, X1, X2, and Y). These
vectors contain NCPM elements (Number of Components Present in the Mixed
substream). The component index associated with each element is listed in
the vector IDXM. All other vectors used by the model, including the rates
vectors and the component concentration vectors, are unpacked.
Note: NCPM steps were required to load the concentration vector. Since
NCPM is always less than or equal to NCC (total number of conventional
components), there is a reduction in the required number of steps to perform
the operation. Using packed arrays for calculations reduces overhead by
eliminating the need to check for zero values when carrying out mathematical
operations.
Specifying Segment-Based
Kinetics
Accessing the Segment-Based Model
To access the Segment-based power-law kinetic model:
1 From the Data Browser, click Reactions.
2 From the Reactions folder, click Reactions.
The Reactions object manager appears.
3 If the kinetic model already exists, double-click the desired Reaction ID in
the object manager or click Edit to get to the input forms.
4 To add a new model, from the Reactions object manager, click New. If
necessary, change the default ID for the reaction.
5 Select Segment-Bas as the reaction type and click OK.
Use the User Subroutines forms to specify the names and parameters for
optional user basis and rate constant subroutines.
Use this sheet To
Rate Constants Specify the name of the user kinetics routine, the number of
user rate constants calculated by the routine, and to give the
integer and real arguments for the user arrays for this routine
Basis Specify the name of the user concentration and holdup basis
routine and give the integer and real arguments for the user
arrays for this routine
Note: You must specify the Valid Phases keyword for each reactor model
referencing the kinetics to ensure the specified reacting phase exists.
If the Reacting Phase option is set to Liquid phase 1 or Liquid phase 2
the model assumes two liquid phases exist. When the named phase is not
present, the model prints a warning message and sets the reaction rates to
zero. There are two options for handling phase collapse:
Note: The Segment Concentration Basis field lets you select the
calculation method for the concentrations used within the reaction model.
When you select Use composite segment concentration the segment
mole fractions used to calculate the reaction rates are calculated from the
following equation:
Mw p
Fracs,i = Frac p * SFRAC( i )*
Mwsegavg
When you select Use segment concentration at specified site the
following equation is applied:
Mw p
Fracs ,i = Frac p * SSFRAC (i, j ) *
Mwseg avg
Where j refers the specified reacting site number.
In both cases the attribute rates of change are mapped to the component
attributes associated with the user-specified reacting site number (e.g.,
SSFLOW(i,j), SZMOM(i,j), etc.)
Note: Reaction rates are defined on a molar basis (moles per volume per
time). The time units for the pre-exponential factors are specified directly on
the Rate Constant form.
By default, the concentration units are assumed to be in SI units (kmole/m3
or mole/L).
You can change the concentration basis to other units using the
Concentration Basis field of the Specs sheet. Alternately, you may apply a
user basis subroutine.
4 In the Tref field, enter the reference temperature. If this field is left blank
the reference temperature will default to the user-specified global
reference temperature on the Specs form.
Note: Use the Catalyst Species field to associate a rate constant with a
particular catalyst. If you leave this field blank (empty) the model drops the
catalyst concentration term from the rate expression.
Use the Catalyst Order field to specify the reaction order with respect to the
catalyst (the model assumes first order by default).
References
Biesenberger, J. A., & Sebastian, D. H. (1983). Principles of Polymerization
Engineering. New York: Wiley.
Kroschwitz, J. (Ed.). (1990). Concise Encyclopedia of Polymer Science and
Engineering. New York: Wiley.
Odian, G. (1991). Principles of Polymerization, 3rd Ed. New York: Wiley.
Rodriguez, F. (1989). Principles of Polymer Systems. New York: Hemisphere.
Rudin, A. (1982). The Elements of Polymer Science and Engineering. New
York: Academic Press Inc.
Polymer Manufacturing
Flowsheets
Polymer production processes are usually divided into the following major
steps:
Monomer synthesis and purification
Polymerization
Recovery/separation
Polymer processing
The modeling issues of interest in each of these steps were discussed in
Chapter 1, and are summarized in the following figure. The focus here is on
the various unit operations required in these processing steps.
Polymerization
The polymerization step is the most important step in terms of capital and
operating costs. The desired outcome for this step is a polymer product with
specified properties (e.g. molecular weight distribution, melt index, viscosity,
crystallinity) for given operating conditions. The obstacles that must be
overcome to reach this goal depend on the type of polymerization process.
Polymerization processes may be batch, semi-batch, or continuous. In
addition, they may be carried out in bulk, solution, suspension, or emulsion.
Bulk continuous systems provide better temperature and molecular weight
control at the expense of conversion; batch systems offer less control over
molecular weight. In addition, they may result in a high viscosity product and
require high temperatures and pressures. Solution systems also provide good
temperature control but have associated with them the cost of solvent
removal from the polymer.
In summary, for the polymerization step, the mechanisms that take place
during the reaction introduce changes in the reaction media which in turn
make kinetics and conversion, residence time, agitation, and heat transfer the
most important issues for the majority of process types.
Recovery / Separations
The recovery/separation step is the step where the desired polymer produced
is further purified or isolated from by-products or residual reactants. In this
step, monomers and solvents are separated and purified for recycle or resale.
The important issues for this step are phase equilibrium, heat and mass
transfer.
Polymer Processing
The last step, polymer processing, can also be considered a recovery step. In
this step, the polymer slurry is turned into solid pellets or chips. Heat of
vaporization is an important issue in this step (Grulke, 1994).
References
Dotson, N. A, Galvn, R., Laurence, R. L., & Tirrell, M. (1996). Polymerization
Process Modeling. New York: VCH Publishers.
Grulke, E. A. (1994). Polymer Process Engineering. Englewood Cliffs, NJ:
Prentice Hall.
This section summarizes some typical usage of the Aspen Plus unit operation
models to represent actual unit operations found in industrial polymerization
processes.
Topics covered include:
Summary of Aspen Plus Unit Operation Models, 286
Distillation Models, 293
Reactor Models, 294
Mass-Balance Reactor Models, 294
Equilibrium Reactor Models, 296
Kinetic Reactor Models, 296
Treatment of Component Attributes in Unit Operation Models, 328
Reactor Models
Dupl
The Dupl block copies one inlet stream to two or more outlet streams. By
design, the mass flow rate and attribute rates out of this block will be greater
than the flow rates into the block, violating mass and attribute conservation
principles.
Frequently, the Dupl block is used as a shortcut to reduce the simulation time
required to model a process consisting of two or more parallel process lines.
For example, consider the process shown here:
Operating Conditions
R1A R1B R2A R2B R3A R3B
Temperature, 250 250 260 260 270 265
C
Pressure, torr 760 760 1200 1200 1500 1700
Volume, liter 2000 2000 1500 1500 1000 1200
Flash2
The Flash2 block carries out a phase-equilibrium calculation for a vapor-liquid
split. The chemistry feature of this block can be used to extend the phase
equilibrium to vapor-liquid-solid systems. The free-water option can be used
to extend the phase equilibrium calculations to include a free water phase in
addition to the organic liquid phase.
The Flash2 model can be used to simulate simple flash drums with any
number of feed streams. The model is also a good tool for representing spray
condensers, single-stage distillations, knock-back condensers, decanters, and
other types of equipment which effectively operate as one ideal stage.
The Flash2 model assumes a perfect phase split, but an entrainment factor
can be specified to account for liquid carryover in the vapor stream. The
entrainment factor is specified by the user, it is not calculated by the model.
If a correlation between the vapor flow rate and the entrainment rate is
available, this correlation can be applied to the model using a Fortran block
which reads the vapor flow rate calculated by the Flash block, calculates the
entrainment rate, and writes the resulting prediction back to the Flash block.
Note that this approach creates an information loop in the model which must
be converged.
The Flash2 block does not fractionate the polymer molecular weight
distribution. Instead, the molecular weight distribution of the polymer in each
product stream is assumed to be the same as the feed stream.
Flash3
The Flash3 block carries out phase-equilibrium calculations for a vapor-liquid-
liquid splits. The liquid phases may be organic-organic (including polymer-
monomer) or aqueous-organic. For aqueous-organic systems, the Flash3
model is more rigorous than the Flash2/free water approach described above.
The key difference is that the Flash3 model considers dissolved organic
compounds in the aqueous phase while the free water approach assumes a
pure water phase.
Generally, three-phase flashes are more difficult to converge than two-phase
flashes. Three-phase flash failures may indicate bad binary interaction
parameters between the components. The problem may also stem from
bogus vapor pressures or heats of formation. In general, it is a good idea to
study two-phase splits for the system in question before attempting to model
a three-phase decanter or reactor.
As with the two-phase flash, the three-phase flash is more stable if
temperature and pressure are specified. Other options, such as duty and
vapor fraction, are more difficult to converge. Temperature estimates may aid
convergence in duty-specified reactors.
FSplit
The flow splitter block, FSplit, is used to represent valves or tanks with
several outlets. The outlet flow rates can be specified on a mass, mole, or
volume basis, or they can be specified as a fraction of the feed stream. In
general, the fraction specifications are best because they are independent of
the feed stream flow rates. This makes the model more flexible and reliable
when using tools like SENSITIVITY or DESIGN-SPEC which might directly or
indirectly manipulate the stream which is being split. The FSplit block can also
be used with reactor models to account for back-mixing.
The FSplit block assumes that the class 2 polymer attributes split according to
mass mixing rules. For example, if the outlet stream is split 60:40, then the
class 2 attributes, such as the segment flow rates, are also split 60:40. This
approach is identical to assuming that the properties of the polymer in each
outlet stream are the same as the properties of the polymer in the inlet
stream.
Heater
Heater can be used to represent heaters, coolers, mixers, valves, or tanks.
The Heater block allows you to specify the temperature or heat duty of the
unit, but does not carry out rigorous heat exchange equations. Any number of
feed streams can be specified for the Heater block. This block follows the
same mixing rules as the Mixer model.
Mixer
The mixer block, Mixer, is used to mix two or more streams to form a single
mixed outlet. The mixer block can be used to represent mixing tanks, static
mixers, or simply the union of two pipes in a tee. The Mixer model assumes
ideal, adiabatic mixing. The pressure of the mixer can be specified as an
absolute value or as a drop relative to the lowest feed stream pressure.
The Mixer model is functionally equal to the Heater model, except it only
allows adiabatic mixing. For this reason, the Heater model may be a better
choice for modeling mixing tanks.
The Mixer block assumes that the class 2 polymer attributes are additive. For
example if stream A and B are mixed to form stream C, and the zeroth
moments of a polymer in stream A and B are 12 kmol/sec and 15
kmol/sec, then the polymer in the product stream has a zeroth moment of
12+15=27 kmol/sec.
Mult
The Mult block is used to multiply the flow rate of a stream. A common
application of this block is to collapse two parallel process line models into a
In this process, the A and B lines consist of identical equipment with the
same operating conditions. The Mult blocks HALF and TWICE are used to
divide the feed stream flow rate by two after R1, representing the split
between lines, and to double the product flow rate, representing the junction
of the parallel lines into a single line at R3. This technique avoids the
duplicate calculations for R2 A and B reactors, which should give the same
results. This technique can save a great deal of simulation time.
Pump
The Pump block changes the pressure of a stream. This block can be used to
represent an actual pump, or it can be used to represent pressure increases
due to liquid head in standpipes.
Pipe
The Pipe model is used to calculate pressure drops in pipelines. The
algorithms in this model are not designed for non-ideal fluids such as
polymers, so the pipe model should be used with caution in polymer process
models. A better option to calculate pressure drops in polymer pipelines is to
use RPlug with a user-written pressure-drop subroutine.
Sep2
The Sep2 block is a generic separation model that allows component
fractionation between two product streams. The products can be split
according to flow rate or fractional specifications. The Sep2 block is commonly
used to represent distillation columns or other separation equipment when
the product stream purity is well known and the details of the separation
process are not important. Compared to the Sep block, the Sep2 block has
more flexible input options, but it only allows two outlet streams.
The Sep2 block does not fractionate the polymer molecular weight
distribution. Instead, the molecular weight distribution of the polymer in each
product stream is assumed to be the same as the feed stream.
Distillation Models
Aspen Plus includes several shortcut distillation models (DISTL, SFRAC, etc.)
which can be used to represent distillation columns. These blocks do not
fractionate the polymer molecular weight distribution. Instead, the molecular
weight distribution of the polymer in each product stream is assumed to be
the same as the feed stream. The class-2 component attributes in each
product stream are set proportional to the mass flow rate of the attributed
component in each product stream.
With the exception of the RadFrac model, the rigorous distillation models in
Aspen Plus do not account for component attributes.
RadFrac
The RadFrac block is a rigorous multistage distillation model for two- and
three-phase systems. RadFrac allows polymer feed streams at any tray, but it
does not account for polymerization reaction kinetics. The molecular weight
distribution and other polymer properties are not fractionated between the
phases. Instead, the class-2 component attributes of the polymer components
are split at each stage in proportion to the polymer component mass
fractions. For example, if 90% of the polymer fed to a given tray goes to the
liquid phase leaving that tray, then 90% of the zeroth moment and other
class-2 attributes are assigned to the liquid phase on that tray.
RYield
The RYield reactor model is used to represent reaction equipment when
reaction kinetics are unknown or are unimportant, and the reactions result in
a product distribution with a known yield.
RYield calculates the product stream flow rates based on user-specified
reaction stoichiometries and yield distributions. The reaction stoichiometry
statements may include monomers, oligomers, or polymers, but may not
include segments. Instead, the segment information (SFLOW or SFRAC) must
be specified as component attributes in the COMP-ATTR sentence.
If polymer components are involved in any of the reactions, use the COMP-
ATTR form to specify molecular weight values (MWN, MWW or PDI) or degree
of polymerization (DPN, DPW or PDI ) for the polymer products. Specify the
SFRAC attribute for homopolymers or copolymers with a known product
polymer composition. For copolymers with product compositions which
depend on the feed flow rates of monomers or polymer segments, specify
dummy values for the SFLOW attribute and use a user-written Fortran block
to predict product segment flow rates which are consistent with the calculated
yield. Write the calculated results into the product stream of the RYield block.
When some of the specified reactions involve polymers, the reaction
stoichiometry must be written in a manner consistent with the reference
RGibbs
The RGibbs model uses the Gibbs free energy minimization technique to
determine the composition of each phase. This algorithm cannot predict the
product of equilibrium polymerization reactions. Polymer phase equilibrium,
however, can be predicted by the model. The RGibbs phase equilibrium
algorithm assumes that the composition and molecular weight distribution of
a polymer component is equal in each of the product phases. The class-2
component attributes of the polymer component are set in proportion to the
mass flow of the polymer component in each of the product phases. The mass
flow rates in the product phases are set by the Gibbs free energy
minimization algorithm.
To properly split component attributes among the RGibbs solution phases, use
the "Phase equilibrium only" option. With this the model can predict multiple
liquid phases such as three liquid phases. Surface tension effects are not
considered. If you are certain that there will be no vapor phase, uncheck the
"Include vapor phase" box to speed up calculations. Use one outlet stream for
each predicted phase, to separate out the component attributes of that
phase.
Pressure
Pressure can be specified as an absolute value or as a pressure drop relative
to the feed stream with the lowest pressure. In Aspen Plus, pressure drops
are expressed as non-positive pressure specifications given in absolute
pressure units.
Residence Time
The RCSTR model allows you to specify the effective hold-up in several
different ways. For single-phase reactors, you can specify the total reactor
volume or the total residence time. If the residence time is specified, then the
estimated reactor volume should be specified to improve the residence-
time/volume loop convergence (RT-LOOP).
When two or more condensed phases are present, the RCSTR model assumes
that each condensed phase has the same residence time. This no-slip
assumption implies that the volume ratios of the condensed phases in the
reactor are equal to the volume flow ratios of the condensed phases exiting
the reactor.
For multiphase reactors, specify the condensed phase volume or residence
time in addition to the total reactor volume. Do not specify the total residence
time, as this residence time is the average of the vapor and liquid phases. If
the reacting phase residence time is specified, provide an estimate for the
reacting phase volume. This will improve the reactor convergence. If
residence time convergence is troublesome, try adjusting the volume step
size.
Multiphase Reactors
The RCSTR model can be used to simulate single- or multiple-phase reactors.
The valid-phases keyword is used to define the number and type of fluid
phases present in the reactor.
Amorphous solid polymers are treated as a liquid phase in Aspen Polymers
(formerly known as Aspen Polymers Plus). Crystalline solids can be addressed
by defining a CISOLID substream to track the flow rate of each inert
crystalline solid.
Dissolving or crystallizing solids can be captured using the Chemistry feature
to define chemical equilibrium reactions between the solid and fluid phases.
Note, however, that the current version of RCSTR does not allow components
to appear in both kinetic reactions and in chemistry equilibrium reactions.
RCSTR Algorithm
The RCSTR model uses a trial-and-error technique to solve the mass and
energy balance equations. Trial-and-error solutions are difficult to reach when
the reaction rates are high, the variables cover several orders of magnitude,
when many equations must be solved simultaneously, and when the variables
are strongly related to each other. All of these conditions are found in
polymerization reaction kinetics, making reactor convergence especially
challenging.
A good understanding of the design of the RCSTR model is required in order
to troubleshoot convergence problems. Otherwise, it may be difficult to
The outer-most loop involves the volume and residence time of the CSTR.
There are many options for specifying the characteristic volume of a
multiphase CSTR. The following table shows the various calculations for
volume and residence times in RCSTR:
Specifications: Total reactor volume (Vol)
VR = R F v j f j ** f jv j Vj
Vj = VR j =
j
f v
k
k k
Ff j v j
VR Vj
R = V j = specifed *
Fvj f j j =
Ff j v j
j
Specifications: Total reactor volume (Vol), key phase volume fraction (Ph-
vol-frac)
VR Vj
R = V j = rjVR
Fvj f j j =
Ff j v j
j
Specifications: Total reactor volume (Vol), key phase residence time (Ph-
res-time)
VR
R = V j = j Ff j v j ** j = specified
F vj f j
j
Vj
VR = R F v j f j ** V j = rjVR j =
j Ff j v j
* If more than one condensed phase is present, and the key phase is liquid, then
the specified volume applies to the sum of the condensed phase volumes.
** This equation is solved by trial-and-error technique.
When residence time is specified instead of volume, the RCSTR model adjusts
the volume to satisfy the residence time specification.
EB LOOP
The second loop is the energy balance conservation equation (EB-LOOP). In
this loop, the reactor temperature is adjusted to match the specified reactor
duty. If the temperature is specified instead of the duty, this loop is by-
passed.
Since the reaction rates are very sensitive to temperature, large changes in
the reactor temperature between energy-balance iterations (EB-ITER) may
cause the mass-balance loop (MB-LOOP) to diverge. This problem can be
solved by providing a good temperature estimate (T-EST) in the ESTIMATES
form. If the problem persists, the maximum temperature step size (Max-
Tstep) should be reduced (the default, 50C, is rather large).
MB-LOOP
The next loop is the mass-balance loop (MB-LOOP). This loop uses a
multivariable solver to converge the conservation equations for component
mole flow and for the class two component attributes.
Two solvers are available: Broyden and Newton. The Broyden algorithm tends
to be relatively fast, but it may be unstable if the number of components and
attributes is large and the reaction rates are high. The Newton algorithm
tends to be slower, but more stable for many classes of problems. The
Newton algorithm calculates the response of each variable to each other
variable by perturbing the variables one at a time by a very small amount.
These perturbation steps require lots of simulation time, which makes each
iteration of the Newton algorithm slow.
The number of mass-balance iterations (MB-Maxit) is defined on the
convergence form. By default, the model allows 50 mass-balance iterations.
This default is sufficient for the Newton algorithm, but is usually too small for
the Broyden algorithm. For polymer reaction kinetics, the number of required
mass-balance iterations may be as high as 500.
Ri Fi in Fi out j Gi , jV j
For the component mole balance equations: = +
Si Si Si Si
R
Maximum error = MAX i i < MB TOL
Si
A secondary criteria is the root-mean-square scaled error, or RMS error:
2
1 R
RMS Error =
Ni
i S i
i
The CSTR mass-balance algorithm iterates until the maximum error falls
below the specified mass-balance tolerance or the maximum number of mass-
balance iterations is reached. If the maximum error criteria is reached, and
the RMS error is decreasing by a factor of ten on each iteration, the CSTR
model continues to iterate until the RMS error reaches the specified function
tolerance (FUNC-TOL). This allows the model to reach very tight convergence
tolerances when the convergence behavior is good.
Scaling Factors
The scaling factors play an important role in the convergence behavior of the
model. If the scaling factors are large, and the variables are small, then the
By default, the component scaling option is used. With this option, the
minimum scaling factors depend on the value of the TRACE parameter. The
trace scaling factor is effectively a minimum mole fraction. For components
with concentrations below the trace level, the scaling factors are set to a
minimum value.
The default scaling factors for component attributes are defined as constants
in an Aspen Plus Table Building System (TBS) data file, COMPATTR.DAT.
Although the default scaling factors are set to appropriate values for most
classes of reaction kinetics, the optimal values for a particular type of kinetics
may be different than the defaults. The default attribute scaling factors can be
adjusted using the Components Attr-Scaling form.
The scaling factors should make the scaled values as close to unity as
possible. For this reason, the scale factors are set to the predicted values
from previously converged passes through the RCSTR block. On the first pass
through the flowsheet, the scaling factors will be set to the estimated value
for the variable. Thus, component flow and component attribute estimates
can be used to set the initial scale factors.
The scaling factors for component attribute values are normalized with the
total mole flow rate of the outlet stream. This keeps the scaling factors
reasonable for models of any type of process, from bench scale to production
scale units.
The inner-most loop is the phase equilibrium loop, or flash equations. For this
reason, it is essential to have accurate physical properties over the entire
range of temperatures and pressures found in the process.
flash convergence without errors. If errors occur, try using the default value,
1 105 . If errors persist, the most likely cause is a physical property problem.
Initialization Options
The convergence behavior of the RCSTR model depends on how the model is
initialized. There are three initialization options for the RCSTR model.
Solver InitializationDo not use integration
By default, the solver algorithm initializes itself using previously saved
simulation results (retention). This saves time if the RCSTR block is inside
a flowsheet recycle loop, where the block will be run several times in
succession. It also saves time if the block is inside a sensitivity,
optimization, design-spec, or data-fit study.
Alternately, the user can force the model to restart from estimates every
time by checking the restart flag on the block-options form.
When retention is not available, or when the restart option is active, the
model uses user-specified estimates to initialize the solver algorithm.
Estimates can be provided for the reactor volume, phase volume, reactor
temperature, component flow rates, and component attribute values. The
component attribute estimates can be specified using class-2 or class-0
attribute values.
If estimates are not provided, the model initializes the variables using the
mixed feed stream (for example, the initial value of a component flow rate
may be set to the total flow rate of that component in all feed streams to
the reactor).
Integration InitializationAlways use integration
In the integration algorithm, the RCSTR is treated as a dynamic stirred-
tank reactor. The conservation equations are numerically integrated from
an initial condition to the steady-state condition. The initial compositions
in the reactor are set equal to those in the feed stream.
If temperature is specified in the reactor, then the temperature profile
during initialization can be ramped from the feed stream temperature to
the specified temperature over the interval of several residence times. If
duty is specified, then the duty can be ramped from adiabatic conditions
to the specified duty. Ramping allows the reactor to cold-start for
improved integration performance.
The numerical integration carries forward until the residual terms
(accumulation terms) drop below the specified mass-balance tolerance. At
this point, the model enters the solver and continues until the model
converges.
Note that initial guesses for component flow rates and component
attributes should not be provided when using the integration initialization
option unless the reactor exhibits multiple steady-state solutions. In this
case, initial estimates may be used to force the reactor towards a
particular solution.
Note: By default, the RCSTR model does not use integration (e.g., the trial
and error solution algorithm starts directly from the user-specified initial
guesses or from retention values). Optionally, the RCSTR model can be
initialized using an integration approach or a hybrid approach that uses
integration only when retention values are not available.
Mass balance not converged in maximum Try adjusting the trace parameter in order-of-
number of iterations. Some reacting magnitude steps from the default ( 1 103 )
components (catalysts, initiators) are present in down to the concentration of the trace
very small quantities. components. If this fails, reset trace to the
default value and try integration initialization.
Energy balance loop does not converge, or Verify that the reactor converges with the
mass-balance loop does not converge after the temperature specified. If not, see items listed
second energy balance loop iteration, or above, otherwise,
temperature step-size cutting (T-CUT) iterations provide a better temperature estimate (T-Est).
appear in the diagnostic messages If the problem persists, try adjusting the
maximum temperature step-size (Max-Tstep)
from 50C to 10C or even 5C.
Residence time loop does not converge, or Verify that the reactor converges with the
mass-balance loop does not converge after the residence time specified. If not, see items listed
second residence-time loop. above, otherwise, provide better volume
estimates. If the problem persists, try adjusting
the maximum volume step-size (Max-Vstep).
Verify that the correct residence time is
specified (condensed-phase residence time for
two-phase reactors).
Verify two phases exist if the reactor valid
phases=vapor-liquid.
Flash failures appear during the mass-balance This may be a physical property problem; it
loop; the step-size cutting (X-CUT) diagnostic may reflect overly-tight flash tolerances; or the
message appears. flash may be unstable when starting from
retention values Loosen the local and global
flash tolerance levels or increase the maximum
number of flash iterations.
Reactor converges but an error message says Check the molecular weights of each reactant
that the mass-balance does not close and product. Verify that reaction stoichiometry
is correct.
RPlug
The RPlug model represents an ideal plug-flow reactor with one or more
phases. The model assumes perfect radial mixing within and between the
phases, phase equilibrium, and no-slip conditions between the phases (e.g.,
the phases all have the same residence time). Dead zones, back-mixing, and
other types of non-ideal plug-flow behavior can be represented using RPlug in
combination with other blocks. The RPlug model does not allow multiple feed
streams. A mixer block must be used in conjunction with the RPlug block to
account for multiple feed streams.
Temperature
RPlug allows many options for specifying the reactor duty or temperature:
Type Specifications Calculations
RPlug allows one process stream and one heat media stream. Reactions can
occur only in the process stream. Heat transfer calculations are carried out
between the process stream and the heat media stream. The heat media
stream represents a coolant stream or a heating stream and the heat media
stream flows co- or counter-current to the process stream.
If a heat media stream is not specified, the model assumes a constant heat
media temperature and solve for the process fluid temperature.
The heat transfer rate or heat transfer coefficient value is calculated as a
function of axial position, stream conditions, etc., by a user-written Fortran
subroutine. This feature is used to develop rigorous models non-reactive heat
exchangers.
Pressure
The pressure at the reactor entry can be specified as an absolute value or as
a pressure drop relative to the feed stream. In Aspen Plus, pressure drops are
expressed as non-positive pressure specifications given in absolute pressure
units.
Residence Time
The RPlug model assumes a cylindrical geometry. The length, diameter, and
number of tubes are specified. The process fluid is assumed to move through
the tubes, and the coolant is assumed to flow on the outside of the tubes.
The total reactor volume cannot be specified, but the aspect ratio
(length/diameter) has no influence on the model predictions. Thus, the
diameter can be set to 1.12838 units, which corresponds to an area of 1.0000
units2 . With this area, the length in units and volume in units3 have the same
numerical value, thus the specified length is equal to the volume.
The phase volumes cannot be specified independently. Instead, the RPlug
model assumes that the phases move through the reactor without slipping
past each other. This assumption is valid for situations where one phase is
dispersed as droplets or bubbles in a second, continuous phase, such as dew
in a vapor phase or small gas bubbles in a liquid phase. This assumption is
not valid for multiphase plug flow reactors with controlled levels.
With this assumption in place, the reactor residence time is equal to the
residence time of each phase present in the reactor. The residence time is
calculated by numerical integration.
One work-around for the no-slip assumption is to write a user kinetic
subroutine (or a step-growth mass-transfer routine) which calls the flash
model directly. Then, specify the reactor as liquid-only and set the diameter
to the hydraulic diameter of the reactor.
Calculating Residence Time
Equation to Calculate Residence Time in RPlug:
z=L
D 2 N dz
=
4 F
z=0 z j f j,z v j,z
Where:
= Reactor residence time
D = Tube diameter
N = Number of tubes
Z = Axial position in reactor of length L
Fz = Total molar flow rate of process stream at axial location z
Enthalpy 105 (SI units) x total mass flow The larger of:
Enthalpy at 2
Cutoff
Component Mole The scaling factor at z = 0 to 1.0 is set to The scaling factor at z = z + z is
Flows 0.1 x total mass flow set to the larger of:
Component mass flow at z
Cutoff
Scaling factors are updated at
each step
Class 2 Attributes The scaling factor at z = 0 to 1.0 is set to The scaling factor at z = z + z is
the larger of: set to the larger of:
Attribute value in inlet stream Attribute value at z
(Attribute scaling factor from the TBS Cutoff
table) x (mole flow rate of the attributed Scaling factors are updated at
component in the inlet) each step
(Cutoff) x (total mole flow rate at the
inlet) x (Attribute scaling factor from the
TBS table)
Scaling factors are held constant
The static scaling method uses a constant set of scaling factors throughout
the reactor. The dynamic scaling method updates the scaling factors based on
the previously converged step. The scaling factors are never set lower than
the specified minimum scale factor.
The static scaling method may result in faster integration for many types of
problems, but there are potential numerical problems when using this
method. Consider an irreversible reaction A B in a plug-flow reactor in
which component B is not present in the feed. The scaling factor for
component A will be set very large and the scaling factor for B will be set
to the minimum scaling factor. This will result in relatively loose tolerance for
the mass balance in A and tight tolerance for the mass balance in B.
Further, as the reaction approaches completion the component B will have a
large flow rate but a small scaling factor. This makes the conservation
equation for B difficult to solve, which will result in small integration steps.
Consider the same situation with dynamic scaling. The initial scaling factors
are the same as the static case. With each new step, however, the scaling
factors are updated to the variable values from the previous step. This keeps
the scaled variables close to one throughout the integration. For example:
Solver cannot converge Try reducing the initial step size by orders of magnitude from the
for initial step default ( 10-2 ) to 10-8 . If the problem persists, try increasing the cutoff
parameter from 10-10 to 10-5 . If the problem still persists, verify the
values and units of the rate constants in the kinetic model. Verify the
heat-transfer coefficient if applicable. Verify the temperature,
composition, and flow rates of the feed streams. Check the history file
diagnostics for unusually high reaction rates.
Integration error: non- This problem is usually related to infeasible reaction kinetics. If using a
negativity violation. user kinetic routine, verify the code, otherwise, a zeroth-order reactant
may be completely consumed. Check the history file diagnostics; look
for the component flow rate or attribute element which has a value of
zero and a negative rate of change.
Integration error: Try increasing the cutoff parameter from 10-10 to 10-5 . If the problem
maximum number of persists, try different combinations of scaling method and corrector
steps is reached method. As a last resort, try increasing the number of steps to 5000. If
the problem still continues, search for errors in the kinetics; check the
diagnostics for unreasonable reaction rates.
Integration error: Tighten the flash tolerance to a value below the corrector tolerance.
corrector tolerance Loosen the integration tolerance to 1 10-3 . Increase the corrector
cannot be achieved tolerance ratio to 0.2, 0.3, 0.5. If the problem continues, verify the
kinetics and heat-transfer parameters. Check history diagnostics.
Flash failures appear This may be a physical property problem; it may reflect overly-tight
during the integration flash tolerances, loosen the local and/or global flash tolerance levels or
increase the maximum number of flash iterations.
RBatch
RBatch is a rigorous model for batch and semi-batch reactors. Any number of
continuous feed streams can be specified in addition to a batch charge
stream. Optionally, a vapor vent may be considered. The RBatch model does
not have a vent condenser option; Aspen Custom Modeler is required to
rigorously model batch polymerization reactors with vent condensers or
overhead columns.
The RBatch model assumes feed and product accumulator holding tanks with
continuous outlets. The accumulator concept provides a bridge between the
continuous steady-state modeling environment in Aspen Plus and the
inherently dynamic nature of batch reactors. The conversion between
continuous streams and discreet charges and dynamic product accumulations
is controlled by specified cycle times and continuous feed stream profiles
specified in the reactor.
Temperature
RBatch allows many options for specifying the reactor duty or temperature, as
summarized here:
Type Specifications Calculations
K
t
d ( Tt Tt s )
Qt = M treactor K ( Tt Tt s ) + ( Tt Tt s ) dt + KD
I 0
dt
Where:
Qt = Instantaneous heat duty (J/sec)
t = Time (sec)
K = Proportional gain (J/kg-K)
I = Integral time (sec)
D = Derivative time (sec)
By default, the proportional gain is 2500 J/kg-K, which results in very tight
control at the expense of excessive simulation time. The speed of the model
can be increased by reducing the gain (try a value of 25 J/kg-K).
Pressure
If the reactor volume is not specified, the RBatch model assumes the reactor
operates as a closed system with a variable volume. The pressure at the
reactor is specified as constant value or as a time-varying profile.
If the reactor volume is specified, and there is a vent stream attached to the
reactor, the flow rate of the vent stream is determined from the specified
pressure or pressure profile. The vent flow is positive when the calculated
reactor pressure exceeds the specified reactor pressure.
K
t
d ( Pt Pt s )
Ft = K ( Pt Pt ) + ( Pt Pt )dt + KD
s s
I 0 dt
Where:
Ft = Instantaneous flow rate (kmol/sec)
Reactor Volume
If the reactor pressure is not specified, then RBatch will predict the reactor
pressure based on a specified reactor volume. The pressure will be
manipulated by a trial-and-error algorithm to satisfy the specified volume.
If pressure and volume are both specified, you must either attach a vent
stream to the reactor or attach a continuous make-up stream and pressure
controller to the reactor.
Residence Time
The residence time of the reactor is controlled by user-specified stop criteria.
You can specify whether RBatch should halt the reaction when the stop
criterion variable is approached from above or below. If several stop criteria
are specified, RBatch stops at the first stop criteria it reaches.
In addition to stop criteria, you must specify a maximum time for the reactor.
This prevents runaway calculations in the event that none of the stop criteria
are feasible.
The stop criteria may include one or more of the following:
A maximum reaction time
A maximum or minimum component mole or mass fraction in the reactor
Batch Operations
RBatch can represent batch or semi-batch reactors, depending on what
streams are connected to it in the flowsheet. If a vent stream or time-varying
continuous feed stream is connected to the RBatch block, then the model
operates in semi-batch mode.
The batch reactor model is interfaced into the Aspen Plus continuous flow,
steady-state modeling environment through the concept of holding tanks, as
shown here:
Cycle Time
RBatch is a dynamic batch reactor model that is interfaced into the Aspen Plus
continuous steady-state modeling environment. The interface requires
converting batch charges and accumulator inventories into continuous stream
flow rates. The cycle time is used to convert the batch charge flow rate into
the initial reactor inventory. The cycle time is also used to convert the vent
accumulator inventory and the reactor inventory into vent and reactor
product streams.
For example, assuming a reactor has a cycle time of two hours and that no
continuous feed streams are specified, then:
If the batch charge stream is set to 50 kg/hour, the initial reactor
inventory is 100 kg.
If at the end of the reaction cycle, the vent accumulator contains 30 kg of
material, the time-averaged continuous vent stream flow rate is 15 kg/hr.
The composition of the time-averaged vent stream will be the same as the
final composition in the vent accumulator.
The final reactor inventory will be 70 kg, and the time-averaged reactor
product flow rate will be 35 kg/hr.
RBatch allows you to specify a feed time and down time instead of the cycle
time. In this case, the time-averaged batch charge stream is divided by the
feed time to calculate the initial batch inventory. The time-averaged product
flow rates are based on the cycle time, which is calculated from the sum of
the feed time, the down time, and the reaction time. This option is not
recommended unless it is used to correct the mass balance for the influence
of time-varying continuous feed streams.
Enthalpy 105 (SI units) x mass holdup Enthalpy at previous time step
Component Mass The scaling factor for each component The scaling factor at t = t + t is set to the
Inventory In inventory equation is set to: larger of:
Reactor and Vent 0.1 * (mass of batch charge stream) Component mass flow at t
Accumulator
Scaling factors are held constant Cutoff
Scaling factors are updated at each step
Class 2 Attribute The scaling factor of each component The scaling factor at t = t + t is set to the
Inventory in attribute is set to: larger of:
Reactor and Vent (Attribute scaling factor from the TBS Attribute inventory at time = t
Accumulator table) x (cycle time) (this is the attribute Cutoff
inventory at time = 0)
Scaling factors are updated at each step
Scaling factors are held constant
Solver cannot converge for Try reducing the initial step size by orders of magnitude from the
initial step default ( 10-1 ) to 10-8 . If the problem persists, try increasing the cutoff
parameter from 10-10 to 10-5 . If the problem still persists, verify the
values and units of the rate constants in the kinetic model. Verify the
heat-transfer coefficient if applicable. Verify the temperature,
composition, and flow rates of the feed streams. Check the history
file diagnostics for unusually high reaction rates.
Integration error: non- This problem is usually related to infeasible reaction kinetics. If using
negativity violation. a user kinetic routine, verify the code, otherwise, a zeroth-order
reactant may be completely consumed. Check the history file
diagnostics; look for the component flow rate or attribute element
that has a value of zero and a negative rate of change.
Integration error: maximum Try increasing the cutoff parameter from 10-10 to 10-5 . If the problem
number of steps is reached persists, try different combinations of scaling method and corrector
method. As a last resort, try increasing the number of steps to 5000.
If the problem still continues, search for errors in the kinetics; check
the diagnostics for unreasonable reaction rates.
Integration error: corrector Tighten the flash tolerance to a value below the corrector tolerance.
tolerance cannot be Loosen the integration tolerance to 1 10-3 . Increase the corrector
achieved tolerance ratio to 0.2, 0.3, 0.5. If the problem continues, verify the
kinetics and heat-transfer parameters. Check history diagnostics.
Flash failures appear during This may be a physical property problem; it may reflect overly-tight
the integration flash tolerances, loosen the local and/or global flash tolerance levels
or increase the maximum number of flash iterations.
Reactor converges but an Set the cycle time instead of the feed time.
error message says that the Check the molecular weights of each reactant and product.
mass-balance does not close
Verify that reaction stoichiometry is correct.
Dupl All attributes in feed stream are copied to each outlet stream.
FSplit Class 2 attributes divide in proportion to flow rate of attributed component. Class 0
SSplit attributes are recalculated for each outlet stream.
Sep Fout
Equation to calculate outlet stream attributes: Aout = A
Sep2 Fin in
F = Flow rate of attributed component (in = mixed feed, out = outlet)
A = Class-2 component attribute value (in = mixed feed, out = outlet)
RadFrac Component attribute conservation equations are included in this model at the tray-by-
tray level. The class-2 attributes are calculated at each tray by the following equation:
Fout
Aout = A
Fin in
F = Flow rate of attributed component (in = mixed feed to tray, out = outlet from tray)
A = Class-2 component attribute value (in = mixed feed to tray, out = outlet from
tray)
The RadFrac model does not allow polymer reaction kinetics.
MultiFrac / These unit operation blocks do not consider component attributes. Polymers must be
BatchFrac converted to oligomer components if polymer fractionation is to be considered in these
models.
Reactor Models
RStoic If user specified attributes in the COMP-ATTR form, they are used for the product
RYield stream. Otherwise, class 2 attributes divide in proportion to the flow rate of the
attributed component. Class 0 attributes are recalculated for each outlet stream.
Fout
Equation to calculate outlet stream attributes: Aout = A
Fin in
F = Flow rate of attributed component (in = mixed feed, out = outlet)
A = Class-2 component attribute value (in = mixed feed, out = outlet)
* This also applies to any block that allows multiple feed streams and uses an implied mixer to
calculate the net feed stream.
References
Chan, W.-M., Gloor, P. E., & Hamielec, A. E. (1993). A Kinetic Model for Olefin
Polymerization in High-Pressure Autoclave Reactors. AIChE J., 39, No. 1.
Chaudhari, R. V., & Shah, Y. T. (1986). Recent Advances in Slurry Reactors,
Concepts and Design of Chemical Reactors. S.A. Whitaker & A. Cassano
(Eds.). Switzerland: Gordon and Breach Science Publishers.
Henderson, J. N., & Bouton, T. C. (Eds.). (1979). Polymerization Reactors and
Processes. ACS Symp. Ser.
Rodriguez, F. (1996). Principles of Polymer Systems. New York: Taylor &
Francis.
Trambouze, P., van Landeghem, H., & Wauquier, J. P. (1988). Chemical
Reactors: Design/Engineering/Operation. Paris: Editions Technips.
Walas, S. M. (1988). Chemical Process Equipment Selection and Design.
Boston: Butterworths.
Literature Review
Before you regress process data, it is a good idea to collect information about
the process. Sources of data include in-house lab data, databanks, trade
journals, conference notes, polymer handbooks, on-line electronic databases,
experimental designs, and so on.
The open and in-house process literature may contain a wealth of information
about key model parameters. Further, these sources may provide additional
sources of fundamental data which can be used to independently evaluate
model parameters.
Simulation studies described in trade journals are an excellent source of
insight and know-how related to model development. These studies
frequently point out which assumptions are valid and which parameters are
important. In addition, these papers may elucidate reaction mechanisms or
physical phenomena that should be considered in a rigorous process model.
Trend Analysis
Use the preliminary model to carry out trend evaluation studies. The
sensitivity feature can be used to examine the influence of process variables
on the model predictions. Compare these trends against process data. If the
predicted trends are not consistent, adjust the appropriate model parameters
to improve the match. For example, if the predicted slope of the monomer
conversion versus temperature curve is less than the measured slope, the
activation energy of the polymerization reaction may be too low.
Use the sensitivity tool to examine the influence of the model parameters on
the model predictions and to determine which parameters are important in
Model Refinement
The Data-Fit tool is the best choice for refining the fit between the model
predictions and the process data, especially when several sets of data are
available. Data-Fit can adjust several model parameters simultaneously,
capturing subtle interactions among the parameters to get the best overall
match between the process data and model predictions.
When the model predictions cannot match the process data, the assumptions
in the model may be too broad. Perhaps the process is limited by heat- or
mass-transfer, or a reactor is not ideally mixed. Maybe there are additional
side reactions that should be considered in the model, or the rate expression
needs to be modified to account for some unusual aspect of reaction kinetics.
These issues can be addressed during the model refinement process by
adding new layers of detail to the model. Avoid adding more detail than
necessary, however, because model fitting is a process of diminishing returns.
Model refinement is an open-ended process. The model parameters can be
tuned more accurately as more data become available from the process. Bad
data points are easier to spot when there are more sets of data to compare.
It is impossible for a simulation model to match process data perfectly. There
are several sources of error that lead to differences between the model
results and process data, including:
Variations in process operating conditions due to disturbances, excursions
from steady state, control system actions, etc.
Imperfect calibration of flow meters, level controllers, etc.
Analytical error in lab measurements
Simplifications and assumptions in the model, such as ideal mixing,
isothermal and isobaric vessels, phase equilibrium, etc.
Errors in the model parameters.
* The pressure variable is treated as a pressure drop if the specified value is non-
positive.
** Specify location (RPlug) or stage number (RadFrac / MulitFrac)
*** Basis can be MOLE, MASS, or STDVOL - the variable specified in the data set
must match the variable specified in the column .
Some measured data, such as polymer melt index and intrinsic viscosity, are
not predicted by the standard property sets in Aspen Polymers. The best way
to include these properties in a data regression is to write a user Prop-Set
property subroutine. Each user property can be linked to a property set.
Property sets can be accessed as stream-property variables.
If you are fitting component attribute or user Prop-Set property profiles, you
must treat the measured variables as point data for the reactor outlet stream.
Use the reactor length or stop-time as an additional point data. Each profile
point must be treated as a separate data case in the data set.
If some results data are missing from one or more sets of profile data, they
can be left blank on the input forms. The model will estimate the values of
these results and tabulate them after the regression run.
Using this expression, the net rate constant, knet , is sensitive to the activation
energy, Eact . If the activation energy is adjusted a little bit, a large
adjustment must be made to the pre-exponential factor to offset this
difference. In other words, the activation energy controls the magnitude of
the reaction rate as well as the temperature sensitivity of the reaction rate.
A better approach is to use the modified Arrehnius expression:
Eact 1 1
R T Tref
knet = ko exp
The parameter Tref is a reference temperature that typically represents the
middle of the temperature range used to estimate the activation energy.
Using this formula, the net rate constant, knet , remains constant at the
reference temperature regardless of the value of the activation energy. With
this approach, the pre-exponential factor, ko , controls the magnitude of the
reaction rate at the reference temperature. The activation energy, Eact ,
controls the temperature sensitivity of the rate constant. This makes it much
easier to fit the model.
DATA-SET DS-1
DEFINE CAT MASS-FLOW STREAM=CATALYST SUBSTREAM=MIXED COMPONENT=CAT
DEFINE TEMP BLOCK-VAR BLOCK=CSTR1 SENTENCE=PARAM VARIABLE=TEMP
DEFINE VISC STREAM-PROP STREAM=PRODUCT PROPERTY=INT-VISC
DEFINE CONV STREAM-PROP STREAM=PRODUCT PROPERTY=CONVERSN
USE STD-DEV 0.001 0.1 0.002 0.0050 /
DATA 0.025 290.0 0.844 0.8550 /
DATA 0.023 295.0 0.842 0.8700 /
DATA 0.055 280.0 0.850 0.9050 /
DATA 0.033 292.0 0.835 0.9000
STEP-GROWTH MYMODEL
RATE-CON 1 PRE-EXP=9.67D14 ACT-ENERGY=41.0
RATE-CON 2 PRE-EXP=3.25D0 ACT-ENERGY=0.0
etc
CALCULATOR INITIAL
DEFINE P1 PARAMETER 1
DEFINE P2 PARAMETER 2
P1 = 1.0D0
P2 = 1.0D0
EXECUTE FIRST
CALCULATOR ADJUST
DEFINE P1 PARAMETER 1
DEFINE P2 PARAMETER 2
DEFINE EXP1 REACT-VAR REACTION=MYMODEL VAR=PRE-EXP SENT=RATE-CON ID1=1
DEFINE EXP2 REACT-VAR REACTION=MYMODEL VAR=PRE-EXP SENT=RATE-CON ID2=2
C specify base case pre-exponential factors for side rxn 1 and 2
F BASE1 = 9.67D14
F BASE2 = 3.25D0
C calculate pre-exponential factors using correction factors
C manipulated by the data regression block
F EXP1 = BASE1 * P1
F EXP2 = BASE2 * P2
READ-VARS P1 P2
WRITE-VARS EXP1 EXP2
Note: For more information on user models, see your Aspen Plus User Models
documentation.
Stream Processing
In order to perform its calculations the user model must be able to read and
process the Aspen Plus stream structure. The stream structure is documented
in Aspen Plus User Models. Example 1 shows a USER2 model routine.
Note: The data in the streams coming in and out of the model are stored in
SI units.
There are several utilities available for stream processing. These perform
functions such as finding the number of stream variables, i.e. the size of the
stream vector, copying one stream to another, finding the total number of
substreams, and finding specific substreams within a stream. Several stream
handling utilities are documented in Appendix C of this User Guide.
Diagnostics
Throughout the simulation calculations, a user model may call the Aspen Plus
error handler to issue diagnostic messages ranging from fatal errors to
warnings and information. The error handler is documented in Aspen Plus
Note: The data coming in and out of the model are stored in SI units.
C------------------------------------------------------------------------
SUBROUTINE USRKIP (SOUT, NSUBS, IDXSUB, ITYPE, NINT,
2 INT, NREAL, REAL, IDS, NPO,
3 NBOPST, NIWORK, IWORK, NWORK, WORK,
4 NC, NR, STOIC, RATES, FLUXM,
5 FLUXS, XCURR, NTCAT, RATCAT, NTSSAT,
C------------------------------------------------------------------
C GET REACTING PHASE SPECIFIC MOLAR VOLUME, SVOL ASSUMING IT IS
C LIQUID
C
CALL SHS_CPACK (SOUT, NCK, IDX, X, TOTFLO)
CALL PPMON_VOLL (
+ TEMP, PRES, X, NCK, IDX, NBOPST, 4, 1, SVOL, DV, KER)
VFLOW1 = SLIQRX
C
C
C GET VOLUME OF REACTING PHASE, VFLOW
C
VFLOW = SVOL * SOUT(NCK+1)
C
C-----------------------------------------------------------------
C
DO 50 I = 1, NC
CONC(I) = XX(I)/SVOL
50 CONTINUE
IF(LZMOM .GT. 0 .AND. VFLOW .GT. RGLOM_RMIN)
ZMOM=SOUT(LZMOM+1)/VFLOW
C------------------------------------------------------------------
C INITIALIZE THE RATES FOR COMPONENTS TO ZERO
C
DO 100 I = 1, NC
RATES(I) = 0D0
100 CONTINUE
C
C------------------------------------------------------------------
C LOAD REACTION RATE CONSTANTS FROM THE REALR
DO 200 I = 1, NR
AK(I) = REALR(I)
200 CONTINUE
C
C------------------------------------------------------------------
C CALCULATE REACTION RATES FOR COMPONENTS
C
DO 300 I = 1, NC
DO 310 J = 1, NC
M = COMPUTE CORRECT INDEX
RATES(I) = RATES(I) - AK(M) * CONC(I)*CONC(J)*VFLOW
300 CONTINUE
C
C
C CALCULATE RATES FOR CLASS-2 ATTRIBUTE EXAMPLE
C------------------------------------------------------------------
DO 400 I = 1, NTCAT
RATCAT(I) = 0D0
400 CONTINUE
C
C INITIALIZE ATTRIBUTES OF INTEREST IN THIS WAY
C FOR ARRAY ATTRIBUTES THIS GIVES FIRST LOCATION IN ARRAY
C RACAT(LZMOM - (NC+9) + 1) = 0
RETURN
END
Note: The data coming in and out of the model are stored in SI units.
C----------------------------------------------------------------------
SUBROUTINE HL2U (T ,P ,Z ,N ,IDX ,
1 IRW ,IIW ,KCALC ,KOP ,NDS ,
2 KDIAG ,QMX ,DQMX ,KER )
C
C----------------------------------------------------------------------
C HV2U IS A USER MIXTURE ENTHALPY SUBROUTINE
C
C THIS USER SUBROUTINE CALCULATES THE LIQUID ENTHALPY OF A BINARY
C MIXTURE CONTAINING ONE POLYMER AND ONE SOLVENT.
C
C
C NAME OF MODULE: HL2U
C
C
IMPLICIT NONE
C
DIMENSION Z(N), IDX(N), KOP(10)
DIMENSION D(15)
References
Aspen Plus User Models. Cambridge, MA: Aspen Technology, Inc.
Aspen Plus System Management. Cambridge, MA: Aspen Technology, Inc.
This section discusses the tools available for applying Aspen Polymers
(formerly known as Aspen Polymers Plus) features to solve real-life problems.
The topics covered include:
Example Applications for a Simulation Model, 366
Application Tools Available in Aspen Polymers, 367
Model Variable Accessing, 369
CALCULATOR
Calculator blocks provide a mechanism for you to incorporate Fortran
statements or Microsoft Excel spreadsheets into the flowsheet calculations.
This can be used to calculate and set input variables based on special user
DESIGN-SPEC
Design-Spec blocks allow you to set a process variable that is normally
calculated during the simulation. For each specification, you must identify
which process variable can be adjusted to meet that specification. For this
reason, Design-Spec blocks can be used as feedback controllers.
To use this block you must specify which model variables must be fixed, what
values they must be fixed at, and which model input variables can be
manipulated. You can include Fortran statements in Design-Spec blocks.
An example use of a Design-Spec block would be to set a maximum amount
for impurities in a product stream.
SENSITIVITY
Sensitivity blocks provide a mechanism for you to analyze the effect of
operating variables, which you select on the process. This block generates a
matrix of manipulated variables versus sampled variables. If there is more
than one manipulated variable, the sensitivity analysis is performed for each
combination of manipulated variables. It is recommended that you use
multiple Sensitivity blocks if you do not want to combine the manipulated
variables.
To use this block you must specify which are the manipulated variables, which
are the sampled variables, and how they must be tabulated. You can include
Fortran statements in Sensitivity blocks.
An example use of a Sensitivity block would be to determine the effect of
reactor temperature or pressure on the polymer product properties.
CASE-STUDY
Case-Study blocks provide another mechanism for you to analyze the effect of
operating conditions on process variables. They allow you to make several
runs in series for the entire flowsheet. Since a report is generated for the
whole flowsheet for each case, you do not need to specify output variables to
be sampled.
OPTIMIZATION
Optimization blocks provide a mechanism for you to minimize or maximize an
objective function calculated using key process variables. To define the
objective function you would use Fortran statements.
To use this block you must define the objective function, specify manipulated
variables, and define constraints, if any.
An example use of Optimization would be to find the optimal reactor
temperature to meet polymer product property specifications while
minimizing reaction medium viscosity.
Notes:
1. Component attributes may be accessed in several ways. They may be
accessed through STREAM-VEC or through SUBSTRM-VEC. In this case,
users are responsible for locating the desired attribute and attribute
element within the stream or substream vector. See the table that follows
for the MIXED substream vector structure.
2. Component attributes may also be accessed with COMPATTR-VAR. With
COMPATTR-VAR, users must provide the element number for attributes
having more than one element. See the Polymer Structural Properties
section of Chapter 2 to find out the dimensions of polymer component
attributes. If the attribute is dimensioned by number of polymer segments,
NSEGS, (e.g. SFLOW, or SFRAC polymer attributes), the ordering of
elements follows the order in which the list of polymer segments was
specified (See the Component Classification section of Chapter 2). For
component attributes dimensioned by number of catalytic sites, each
element represents a site number, i.e. site no. 1, no. 2, etc. For two-
dimensional component attributes dimensioned by number of segments
and number of catalytic sites (NSEGS*NSITES), the first dimension is
NSEG, therefore, the ordering of elements is as follows: the list of specified
segments is repeated for each site beginning with site no. 1.
3. Component attributes may also be accessed with COMPATTR-VEC. In this
case, users are not required to provide an element number since the whole
component attribute is returned as a vector having one or more elements.
The ordering of elements within the attribute vector follows the description
given in Note 2.
4. COMPATTR-VAR and COMPATTR-VEC are equivalent for component
attributes having only one element.
5. REACT-VAR may be used to access kinetic constant parameters for reaction
kinetic models, including free-radical, step-growth and Ziegler-Natta. The
type of information required to access these parameters is model
dependent. For free-radical, the reaction type (INIT-DEC, for example),
and the reacting species are required, in addition to the name of the
parameter to be accessed. The same is true for Ziegler-Natta which also
requires a catalyst site type number. For step-growth, a reaction number is
required. For the standard Aspen Plus reaction models, a reaction number,
and/or substream identifier may be needed to locate the parameters.
value1
Values for component attribute 2 of component 1
(polymer or other attributed component)
valuencat1
value1
Values for component attribute 1 of component 2
(polymer or other attributed component)
valuencat1
References
Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc.
Convergence and Optimization in Aspen Plus, Course notes. Cambridge, MA:
Aspen Technology, Inc.
Installation Procedure
Refer to the Aspen Engineering Suite Installation Guide, Aspen Polymers
chapter for information on how to install Aspen Polymers on your system.
Configuration Tips
Startup Files
The information needed to launch the main Aspen Plus application window is
recorded in startup files. These files define the type of simulation, default
settings for the user interface, hosts for the simulation engine, run settings,
etc. One type of startup file is used to define defaults for the type of
simulation. This is the simulation template.
Simulation Templates
Simulation templates are available to help you get started setting up your
model. These templates typically contain options such as unit sets, physical
property method selection, and Table File Format (TFF) selection for stream
result tables. Polymer simulation templates are available. You can create your
own personal template to allow faster definition of a new simulation model.
User Fortran
User Fortran Templates
There are several ways for you to customize your models by adding
calculations in Fortran. The End-Use Properties section of Chapter 2 described
how to setup a user Prop-Set for calculating end-use properties. Chapter 4
described how to setup user unit operation models, user kinetic models, and
user property models. Templates are available for your use in creating the
Fortran files used in these features. You will find these templates in the
following location:
Version Location
Windows %asptop%\user
Troubleshooting Guide
Following are tips to help you diagnose and resolve problems you may run
into while setting up or running Aspen Polymers.
The polymer input forms The installation was not complete. You must locate your installation CD and do
cannot be found on the an incremental installation of Aspen
GUI. Polymers. Select Aspen Polymers from the
product list and chose the subcomponents
button to select the Aspen Polymers steady
state installation option.
Aspen Polymers is installed but Enable Aspen Polymers. From the Tools
not enabled. menu, select Options. On the Startup tab
there is a box entitled Enable forms for
layered products. Make sure you select
Aspen Polymers
A file created without You visited the polymer record You must enable Aspen Polymers (From the
using polymer features while creating the file, then later Tools menu, Select Options, click on the
appears incomplete in switched off Aspen Polymers. Startup tab). In the Data Browser, select
the components record. Polymers (Polymers will appear as
incomplete), right mouse click, select Delete.
Windows crashes during An invalid operation was Usually, when you crash, a backup file is
input specifications. performed either by the Aspen created. Startup Aspen Plus again, then you
Plus program or by another should be able to recover your file. If the
program running simultaneously. invalid operation was caused by Aspen Plus,
repeat the input steps that lead to the crash,
verify that it is reproducible, and submit the
problem to Technical Support.
Windows crashes during The simulation engine Export an input summary. Run the input
simulation calculations. encountered an error that could summary alone, then examine the run
not be transferred to the GUI. history for simulation errors. Change the
input specifications associated with the error
and rerun.
Aspen Plus ran out of resources to Free-up some disk space and run again.
create run files. This can happen Also, consult the Aspen Plus System
especially for large simulations. Management reference manual. An entire
You may see error messages section is devoted to managing virtual
referring to the amount of virtual memory on Win95/98 and WinNT.
memory available.
Aspen Plus ran out of memory to Make some disk space available or increase
load dynamic link libraries. the amount of memory available to the
application, then run again.
Windows crashes after Aspen Plus could not load the If you are running on a remote hosts, there
simulation is complete. simulation results. may have been a communication failure at
the end of the simulation calculations. You
can submit the run again or you can
manually load the results file (.SUM) from
the remote host.
If you are running on a local PC host, Aspen
Plus may have run out of memory to load
the results. Make some disk space available
or increase the amount of memory available
to the application and run again.
During simulation The application could not find If the license error message refers to "Feature 10".
calculations an error a valid free license to complete This means that you do not have a license for Aspen
message occurs for a the simulation. Plus itself. If you are using a licensed installation,
license failure. then this could be a temporary license failure. This
can happen for multi-user sites, or if you are using a
license manager located on a network. In that case,
you simply need to try again later.
If you are using an installation with a single
activator, then your license key file may be
corrupted, the port where the activator is plugged in
could be damaged, or the activator could be
damaged. To correct your license key files, perform
a license key installation again. If the problem is
your activator, contact Technical Support to have it
replaced.
If the license error message refers to another
feature number, you may still have run into a
temporary license failure (see above). In that case,
try again. If this was not a temporary license failure,
then you created a simulation file which uses
features for which you are not licensed. If the
message refers to "Feature 15", then you are trying
to use Aspen Polymers without a valid license. Other
feature numbers refer to specific add-on products.
You must contact AspenTech to obtain a valid Aspen
Polymers license.
A message box See "Windows crashes during See "Windows crashes during simulation
comes up stating simulation calculations" under calculations" under User Interface Problems. See
that an error User Interface Problems. See also "After one run a subsequent run following an
occurred in the also "After one run a input change crashes" later in this section.
Aspen Plus engine. subsequent run following an
input change crashes" later in
this section.
A run history Aspen Plus ran out of See "Windows crashes during simulation
message appears resources to load dynamic link calculations" under User Interface Problems.
referring to a libraries.
dynamic load module
error.
You are referencing user Compile the user Fortran and place it in your run
Fortran and do not have the directory.
compiled object file in your
working directory. The working
directory is the location from
which you opened an existing
file. If you created a file from a
template or opened an existing
file from a floppy or a write
protected area (e.g. \xmp or
\app) the working directory is
as specified in Tools Options
Startup.
A run history You ran out of virtual memory See the Aspen Plus System Management, which
message appears space to load the run files. discusses virtual memory management.
which refers to
"Virtual Memory
Exhausted".
After one run a The problem size has changed Usually after the crash you should be able to recover
subsequent run as a result of the input or for your file and run with the input change. To prevent
following an input other reasons Aspen Plus this from happening for the same run, reinitialize the
change crashes. unsuccessfully tried to reuse simulation before making repeated runs. This is still
the previous run data space. a problem that should be reported to Technical
Usually an error message Support.
appears which states that a
"Fatal error has been
encountered".
References
Aspen Engineering Suite Installation Guide for Windows. Cambridge, MA:
Aspen Technology, Inc.
Aspen Plus System Management. Cambridge, MA: Aspen Technology, Inc.
Aspen Plus User Guide. Cambridge, MA: Aspen Technology, Inc.
POLYMER Databank
POLYMER contains property parameters for polymers.
Note that a generic polymer component is available in the databank for
custom designed polymers.
MW =
MWSEG
NSEG
For the generic polymer component MW is set to 1.
ABS Acrylonitrile-butadiene-styrene
BR-1 Poly(butadiene)
CA-1 Cellulose-acetate
Cellulose Cellulose
Chitosan Chitosan
CPE Chlorinated-Poly(ethylene)
CTA Cellulose-triacetate
Dextran Dextran
EVA Ethylene-vinyl-acetate
EEA Ethylene-ethyl-acrylate
EPR Ethylene-propylene
HDPE High-density-Poly(ethylene)
Heparin Heparin
Hyaluronic Hyaluronic-Acid
I-PB Isotactic-Poly(1-butene)
I-PMMA Isotactic-Poly(methyl-methacryl)
I-PP Isotactic-Poly(propylene)
Keratan Keratan-Sulfate
LDPE Low-density-poly(ethylene)
LLDPE Linear-low-density-poly(ethylene)
NBR Nitrile-butadiene-rubber
NYLON6 Nylon-6
NYLON66 Nylon-66
PAA Poly(acrylic-acid)
P(ACA&S) Poly(acrylamide-styrene)
PALA Poly(alanine)
PAMIDE Poly(amide)
PAMS Poly(alpha-methylstyrene)
P(AMS&AN) Poly(a-methylstyrene-AN)
PAN Poly(acrylonitrile)
PARA Poly(acrylamide)
PARG Poly(arginine)
PASN Poly(asparagine)
PASP Poly(aspartic-acid)
PB-1 Poly(1-butene)
PBA Poly(n-butyl-acrylate)
PBMA Poly(n-butyl-methacrylate)
P(BMA&S) Poly(n-butyl-methac-styrene)
PBS-1 Poly(butadiene-styrene)
PBT Poly(butylene-terephthalate)
PC-1 Poly(carbonate)
P(C&DMS) Poly(carbonate-dimet-siloxane)
PCHMA Poly(cyclohexyl-methacrylate)
PCYS Poly(cysteine)
PD-1 Poly(decene-1)
PDMA Poly(decyl-methacrylate)
PDMS Poly(dimethylsiloxane)
P(DMS&S) Poly(dimethylsiloxane-styrene)
PE Poly(ethylene)
PEA Poly(ethyl-acrylate)
PEEK Poly(ether-ether-ketone)
PEG Poly(ethylene-glycol)
P(EG&PG) Poly(eth-glycol-prop-glycol)
PEMA Poly(ethyl-methacrylate)
PEO Poly(ethylene-oxide)
P(EO&POX) Poly(eth-oxide-prop-oxide)
P(E&P) Poly(ethylene-propylene)
PET Poly(ethylene-terephthalate)
P(E&VAC) Poly(ethylene-vinyl-acetate)
PGLN Poly(glutamine)
PGLU Poly(glutamic-acid)
PGLY Poly(glycine)
PH Poly(heptene-1)
PHA Poly(n-hexyl-acrylate)
PHENOXY Phenoxy
PHIS Poly(histidine)
PHMA Poly(n-hexyl-methacrylate)
PI Poly(imide)
PIB Poly(isobutylene)
PIBMA Poly(isobutyl-methacrylate)
PILE Poly(isoleucine)
PIP-1 Poly(isoprene)
PLEU Poly(leucine)
PLYS Poly(lysine)
PMA Poly(methyl-acrylate)
P(MAA&MMA) Poly(methac-acid-met-methac)
P(MAA&S) Poly(methac-acid-styrene)
P(MAA&VAC) Poly(methac-acid-vin-acetate)
PMET Poly(methionine)
PMMA Poly(methyl-methacrylate)
PMMS Poly(m-methylstyrene)
PMP Poly(4-methyl-1-pentene)
PMVPD Poly(2-methyl-5-vinylpyridine)
PNA Poly(sodium-acrylate)
POCS Poly(o-chlorostyrene)
POE Poly(oxyethylene)
POLYMER Generic polymer component
POM Poly(oxymethylene)
POMS Poly(o-methylstyrene)
POP Poly(oxypropylene)
PP Poly(propylene)
PPA Poly(n-propyl-acrylate)
PPBRS Poly(p-bromostyrene)
PPEMA Poly(n-pentyl-methacrylate)
PPG Poly(propylene-glycol)
PPHE Poly(phenylalanine)
PPO Poly(phenylene-oxide)
PPMA Poly(n-propyl-methacrylate)
PPMOS Poly(p-methoxystyrene)
PPMS Poly(p-methylstyrene)
PPOX Poly(propylene-oxide)
PPRO Poly(proline)
PPS Poly(phenylene-sulfide)
PS-1 Poly(styrene)
PSBMA Poly(sec-butyl-methacrylate)
PSER Poly(serine)
PSF Poly(sulfone)
P(S&VP) Poly(sytrene-vinylpyrrolidone)
P(S&VPD) Poly(styrene-4-vinylpyridine)
PT-1 Poly(tetrahydrofuran)
PTFE Poly(tetrafluoroethylene)
PTHR Poly(threonine)
PTRP Poly(tryptophan)
PTYR Poly(tyrosine)
PU-1 Poly(urethane-fiber)
PVA Poly(vinyl-alcohol)
PVAC Poly(vinyl-acetate)
P(VAC&VAL) Poly(vin-acetate-vin-alcohol)
PVAL Poly(valine)
PVAM Poly(vinyl-amine)
PVC Poly(vinyl-chloride)
PVCAC Poly(vin-chloride-vin-acetate)
PVDC Poly(vinylidene-chloride)
PVDF Poly(vinylidene-fluoride)
PVF Poly(vinyl-fluoride)
PVI Poly(vinyl-isobutyl-ether)
PVME Poly(vinyl-methyl-ether)
PVO Poly(vinylpropionate)
PVP Poly(vinylpyrrolidone)
PVPD Poly(4-vinyl-pyridine)
SAN Styrene-acrylonitrile
SBR Styrene-butadiene-rubber
UF Urea-formaldehyde
SEGMENT Databank
SEGMENT contains property parameters for polymer segments.
Note that a special nomenclature was devised to identify polymer segments.
The segment name consists of the name of the monomer from which it
originates, followed by a label to identify it as a repeat unit (-R) or an end
group (-E). In cases where several molecular structures are possible, a
numeric subscript is used to differentiate the isomers. A similar convention is
used for assigning component aliases.
O
CO-R Carbonyl-R
C
C2H2-R-1 cis-Vinylene-R
C2H2-R-2 trans-Vinylene-R
CH CH
C2H3O-E-2 Vinyl-alcohol-E
OH
CH CH
C2H4N-E Vinylamine-E-1
NH2
O
C2H4NO-E Glycine-E-1
NH2 CH2 C
O
C2H4NO2-E Glycine-E-2 NH CH2 C
OH
CH2 CH
C2H4O-R-3 Vinyl-alcohol-R
OH
CH2 CH
C2H5N-R Vinylamine-R
NH2
CH2 CH2
C2H5O-E-1 Ethylene-oxide-E-1
OH
CH2 CH2
C2H6N-E Ethyleneamine-E
NH2
CH3
C2H6OSi-R Dimethyl siloxane-R Si O
CH3
CH3
C2H7OSi-E Dimethyl siloxane-E Si OH
CH3
O O
C3H2O2-R Malonic -acid-R
CCH2C
CH CH
C3H2O2Na-E Sodium acrylate-E-1 C
O ONa
CH2 CH
C3H3N-R Acrylonitrile-R
C N
CH CH
C3H3NO-R Acrylamide-R-1 C
O NH
CH CH
C3H3O2-E Acrylic acid-E-1 C
O OH
CH2 CH
C3H3O2Na-R Sodium-acrylate-R C
O ONa
O O
C3H303-E Malonic-acid-E
CCH2COH
CH CH
C3H4NO-E Acrylamide-E-1 C
O NH2
CH2 CH
C3H4NO-B Acrylamide-B C
O NH
O
N C
C3H4N2O-B Urea-formaldehyde-R
N CH2
CH2
CH2 CH
C3H4O2-R Acrylic-acid-R C
O OH
CH2 CH2
C3H4O2Na-E Sodium-acrylate-E-2 C
O ONa
CH CH
C3H5-E Propylene-E-1
CH3
CH2 CH2
C3H5NO-R-1 Acrylamide-R-2 C
O NH
CH2 CH
C3H5NO-R-2 Acrylamide-R-3 C
O NH2
O
C3H5NO-R-3 Alanine-R NH CH C
CH3
O
NH CH C
C3H5NOS-R Cysteine-R
CH2
SH
O
NH CH C
C3H5NO2-R Serine-R
CH2
OH
CH2 CH2
C3H5O2-E Acrylic-acid-E-2 C
O OH
CH2 CH
C3H6-R Propylene-R
CH3
CH2 CH2
C3H6NO-E-1 Acrylamide-E-2 C
O NH2
O
C3H6NO-E-2 Alanine-E-1 NH2 CH C
CH3
O
NH2 CH C
C3H6NOS-E Cysteine-E-1
CH2
SH
O
C3H6NO2-E-1 Alanine-E-2 NH CH C
CH3 OH
O
NH2 CH C
C3H6NO2-E-2 Serine-E-1
CH2
OH
O
NH CH C
C3H6NO2S-E Cysteine-E-2
CH2 OH
SH
O
NH CH C
C3H6NO3-E Serine-E-2
CH2 OH
OH
O CH2 CH
C3H6O-R-1 Oxypropylene-R
CH3
CH2 CH O
C3H6O-R-2 Propylene-oxide-R
CH3
CH2 CH
C3H6O-R-3 Vinyl-methyl-ether-R O
CH3
O CH2 CH O
C3H6O2-R Propylene-glycol-R
CH3
C3H6O2-R-1 1,3-Propanediol-R ~O(CH2)3O~
OCHCH2O
C3H6O2-R-2 1,2-Propanediol-R
CH3
CH2 CH2
C3H7-E Propylene-E-2
CH3
HO CH2 CH
C3H7O-E-1 Oxypropylene-E
CH3
CH2 CH OH
C3H7O-E-2 Propylene-oxide-E
CH3
C3H7O-E-i i-Propanol-E ~OCH(CH3)2
C3H7O-E-n n-Propanol-E ~O(CH2)2CH3
O CH2 CH OH
C3H7O2-E Propylene-glycol-E
CH3
C3H7O2-E-1 1,3-Propanediol-E ~O(CH2)3OH
OCHCH2OH
C3H7O2-E-P 1,2-Propanediol-E-P
CH3
OCH2CHCH3
C3H7O2-E-S 1,2-Propanediol-E-S
OH
O O
C C
C4H2O2-R-cis Maleic-acid-R
C C
H H
O
H C
C4H2O2-R-tra Fumaric-acid-R C C
C H
O
O O
C COH
C4H3O3-E-cis Maleic-acid-E
C C
H H
O
H COH
C4H3O3-E-tra Fumaric-acid-E C C
C H
O
O O
C4H4O2-R Succinic-acid-R
C(CH2)2C
O
NH CH C
C4H5NO3-R Aspartic-acid-R CH2
C
O OH
C CH2
C4H5O2-E-1 Methyl-acrylate-E-1 C
O OCH3
CH3
C4H5O2-E-2 Methyl-acrylic-acid-E-1
CH C
C
O OH
CH CH
C4H5O2-E-3 Vinyl-acetate-E-1 O
C CH3
O
O O
C4H5O3-E Succinic-acid-E
C(CH2)2COH
CH2 CH
C4H6-R-2 Butadiene-R-2
CH CH2
O
NH2 CH C
C4H6NO3-E Aspartic-acid-E-1 CH2
C
O OH
O
NH CH C
OH
C4H6NO4-E Aspartic-acid-E-2 CH2
C
O OH
O
NH CH C
C4H6N2O2-R Asparagine-R CH2
C
O NH2
CH2 CH
C4H6O2-R-1 Methyl-acrylate-R C
O O CH3
CH3
CH2 C
C4H6O2-R-2 Methyl acrylic-acid-R
C
O OH
CH2 CH
C4H6O2-R-3 Vinyl-acetate-R O
C CH3
O
CH CH
C4H7-E-1 1-Butene-E
C2H5
CH3
C4H7-E-2 Isobutylene-E CH C
CH3
O
NH CH C
C4H7NO2-R Threonine-R CHOH
CH3
O
NH2 CH C
C4H7N2O2-E Asparagine-E-1 CH2
C
O NH2
O
NH CH C
C4H7N2O3-E Asparagine-E-2 OH
CH2
C
O NH2
CH2 CH2
C4H7O2-E-1 Methyl-acrylate-E-2 C
O O CH3
CH3
C4H7O2-E-2 Methyl-acrylic-acid-E-2
CH2 CH
C
O OH
CH3
C4H7O2-E-3 Methyl-acrylic-acid-E-3
C CH3
C
O OH
CH2 CH2
C4H7O2-E-4 Vinyl-acetate-E-2 C
O O CH3
CH2 CH
C4H8-R-1 1-Butene-R
C2H5
CH3
C4H8-R-2 Isobutylene-R CH2 C
CH3
O
NH2 CH C
C4H8NO2-E Threonine-E-1
CHOH
CH3
O
NH CH C
C4H8NO3-E Threonine-E-2
OH
CHOH
CH3
O O
C5H6O2-R Glutaric-acid-R
C(CH2)3C
O
C5H7NO-R Proline-R C
N
O
NH CH C
C5H7NO3-R Glutamic-acid-R C2H4
C
O OH
CH3
C5H7O2-E-1 Methyl-methacrylate-E-1
CH C
C
O O CH3
CH CH
C5H7O2-E-2 Ethyl-acrylate-E-1 C
O O C2H5
CH CH
C5H7O2-E-3 Vinyl-propionate-E-1 O
C C2H5
O
O O
C5H7O3-E Glutaric-acid-E
C(CH2)3COH
CH2 C CH CH2
C5H8-R Isoprene-R
CH3
O
C5H8NO-E Proline-E-1 C
HN
O
C5H8NO2-E Proline-E-2 C OH
N
O
NH2 CH C
C5H8NO3-E Glutamic-acid-E-1 C2H4
C
O OH
O
NH CH C
C5H8NO4-E Glutamic-acid-E-2 C2H4 OH
C
O OH
O
NH CH C
C5H8N2O2-R-1 Glutamine-R C2H4
C
O NH2
O O
C5H8N2O2-R-2 Trimethylene-diisocyanate-R C C
NH C3H6 NH
CH3
C CH2
C5H8O2-R-1 Methyl-methacrylate-R
C
O OCH3
CH2 CH
C5H8O2-R-2 Ethyl-acrylate-R C
O O C2H5
CH2 CH
C5H8O2-R-3 Vinyl-propionate-R O
C C2H5
O
CH CH
C5H9-E 1-Pentene-E-1
C3H7
O
NH CH C
C5H9NO-R Valine-R
CH
CH3 CH3
O
NH CH C
C5H9NOS-R Methionine-R C2H4
S
CH3
O
NH2 CH C
C5H9N2O2-E Glutamine-E-1 C2H4
C
O NH2
C5H9N2O3-E Glutamine-E-2
CH3
CH2 CH
C5H9O2-E-1 Methyl-methacrylate-E-2
C
O O CH3
CH3
C CH3
C5H9O2-E-2 Methyl-methacrylate-E-3
C
O OCH3
CH2 CH2
C5H9O2-E-3 Ethyl-acrylate-E-2 C
O O C2H5
CH2 CH2
C5H9O2-E-4 Vinyl-propionate-E-2 O
C C2H5
O
CH2 CH
C5H10-R 1-Pentene-R
C3H7
C5H10NO-E Valine-E-1
O
NH2 CH C
C5H10NOS-E Methionine-E-1 C2H4
S
CH3
O
NH CH C
C5H10NO2-E Valine-E-2 OH
CH
CH3 CH3
O
NH CH C
C5H10NO2S-E Methionine-E-2 OH
C2H4
S
CH3
C6H4S-R Phenylene-sulfide-R S
C6H5O-E Phenol-E O
C6H5S-E-1 Phenylene-sulfide-E-1 S
C6H5S-E-2 Phenylene-sulfide-E-2 SH
NH NH
C6H6N2-R-M m-Phenylene-diamine-R
NH NH
C6H6N2-R-O o-Phenylene-diamine-R
C6H6N2-R-P p-Phenylene-diamine-R NH NH
NH NH2
C6H7N2-E-M m-Phenylene-diamine-E
NH NH2
C6H7N2-E-O o-Phenylene-diamine-E
C6H7N3O-R Histidine-R
CH CH O
C6H8NO-E Vinylpyrrolidnone-E-1 N C
C6H8N3O-E Histidine-E-1
C6H8N3O2-E Histidine-E-2
O O
C6H8O2-R Adipic-acid-R
C (CH2)4 C
CH2 CH
O
C6H9NO-R Vinylpyrrolidnone-R N C
CH C CH3
C6H9O2-E-1 Ethyl-methacrylate-E-3 C
O O C2H5
CH CH
C6H9O2-E-2 n-Propyl-acrylate-E-1 C
O O C3H7
O O
C6H9O3-E Adipic-acid-E
C (CH2)4 C OH
CH2 CH
CH2
C6H10-R 1,4-Hexadiene-R CH
CH
CH3
CH2 CH2
O
C6H10NO-E Vinylpyrrolidnone-E-3 N C
CH3
C6H10O2-R-1 Ethyl-methacrylate-R-1
CH2 C
C
O O C2H5
CH2 CH
C6H10O2-R-2 n-Propyl-acrylate-R C
O O C3H7
CH2OH
C6H10O3-R Amylose-R O
O
CH2OH
O
C6H10O5-R-1 Cellulose-R O
OH OH
O CH2
O
C6H10O5-R-2 Dextran-R HO
OH OH
CH CH
C6H11-E-1 4-Methyl-1-pentene-E-1 CH3
CH2 CH
CH3
CH CH
C6H11-E-2 1-Hexane-E-1
C4H9
C6H11NO-R-1 Caprolactam-R
O
NH (CH2)5 C
O
NH CH C
C6H11NO-R-2 Isoleucine-R
CH C2H5
CH3
O
NH CH C
C6H11NO-R-3 Leucine-R CH2
CH CH3
CH3
CH CH
CH3
C6H11O-E Vinyl-isobutyl-ether-E-1
O
CH2 CH
CH3
CH3
CH2 CH
C6H11O2-E-1 Ethyl-methacrylate-E-1
C
O O C2H5
CH3
C6H11O2-E-2 Ethyl-methacrylate-E-2
CH3 C
C
O O C2H5
CH2 CH2
C6H11O2-E-3 n-Propyl-acrylate-E-2 C
O O C3H7
CH2OH
C6H11O3-E Amylose-E C O
HO
CH2OH
O
C6H11O5-E Cellulose-E-1 HO
OH OH
CH2OH
O
C6H11O6-E-1 Cellulose-E-2 O OH
OH OH
CH2 O
O
C6H11O6-E-2 Dextran-E-2 HO OH
OH OH
CH2 CH
C6H12-R-1 1-Hexane-R
C4H9
CH2 CH CH3
C6H12-R-2 4-Methyl-1-pentene-R CH2 CH
CH3
O
C6H12NO-E-1 Caprolactam-E-1
NH2 (CH2)5 C
O
NH2 CH C
C6H12NO-E-2 Isoleucine-E-1
CH
CH3 C2H5
O
NH2 CH C
C6H12NO-E-3 Leucine-E-1 CH3
CH2
CH
CH3
O
C6H12NO2-E-1 Caprolactam-E-2 NH (CH2)5 C
OH
O
NH CH C
C6H12NO2-E-2 Isoleucine-E-2 OH
CH
CH3 C2H5
O
NH CH C
C6H12NO2-E-3 Leucine-E-2
OH
CH2
CH CH3
CH3
O
C6H12N2O-R Lysine-R NH CH C
C4H8 NH2
O
NH CH C
CH2
CH2
C6H12N4O-R Arginine-R
CH2
NH
C NH
NH2
CH2 CH
CH3
C6H12O-R Vinyl-isobutyl-ether-R O CH2 CH
CH3
CH3 CH CH3
C6H13-E-2 4-Methyl-1-pentene-E-3 CH2 CH
CH3
CH3 CH
C6H13-E-3 1-Hexane-E-2
C4H9
O
C6H13N2O-E Lysine-E-1 NH2 CH C
C4H8 NH2
O
C6H13N2O2-E Lysine-E-2
NH CH C
OH
C4H8 NH2
O
NH2 CH C
CH2
CH2
C6H13N4O-E Arginine-E-1
CH2
NH
C NH
NH2
O
NH CH C OH
CH2
CH2
C6H13N4O2-E Arginine-E-2
CH2
NH
C NH
NH2
CH2 CH2
C6H13O-E Vinyl-isobutyl-ether-E-2 O CH3
CH2 CH
CH3
O
C7H5O2-E Phenylcarbonate-E C
O
CH CH
C7H6N-E 4-Vinyl-pyridine-E-1
CH2 CH
C7H7N-R 4-Vinyl-pyridine-R
CH2 CH2
C7H8N-E 4-Vinyl-pyridine-E-2
N
O O
C7H10O2-R Pimelic-acid-R
C(CH2)5C
CH CH
C7H11O2-E-1 n-Butyl-acrylate-E-1 C
O O C4H9
CH3
CH C
C7H11O2-E-2 n-Propyl-methacrylate-E-1
C
O O C3H7
O O
C7H11O3-E Pimelic-acid-E
C(CH2)5COH
CH2 CH
C7H12O2-R-1 n-Butyl-acrylate-R C
O O C4H9
CH3
CH2 C
C7H12O2-R-2 n-Propyl-methacrylate-R
C
O O C3H7
CH CH
C7H13-E 1-Heptene-E-1
C5H11
CH2 CH2
C7H13O2-E-1 n-Butyl-acrylate-E-2 C
O O C4H9
CH3
CH2 CH
C7H13O2-E-2 n-Propyl-methacrylate-E-2
C
O O C3H7
CH3
CH3 C
C7H13O2-E-3 n-Propyl-methacrylate-E-3
C
O O C3H7
CH2 CH
C7H14-R 1-Heptene-R
C5H11
CH2 CH2
C7H15-E-1 1-Heptene-E-2
C5H11
CH3 CH
C7H15-E-2 1-Heptene-E-3
C5H11
O O
C8H4O2-R Terephthalate-R
C C
O
C
C8H4O2-R-1 Phthalate-R O
C
O C O
C8H4O2-R-2 Isophthalate-R
C
O O
C8H5O3-E Terephthalic-acid-E
C C OH
O
C
C8H5O3-E-1 Phthalic-acid-E O
C OH
O C O
C8H5O3-E-2 Isophthalic acid-E
C OH
CH CH
C8H6Br-E p-Bromostyrene-E-1
Br
CH CH
C8H6Cl-E-1 o-Chlorostyrene-E-1 Cl
CH CH
C8H6Cl-E-2 p-Chlorostyrene-E-1
Cl
CH CH
C8H7-E Styrene-E-1
CH2 CH
C8H7Br-R p-Bromostyrene-R
Br
CH2 CH
C8H7Cl-R-1 o-Chlorostyrene-R Cl
CH2 CH
C8H7Cl-R-2 p-Chlorostyrene-R
Cl
CH2 CH
C8H8-R Styrene-R
CH2 CH2
C8H8Br-E p-Bromostyrene-E-2
Br
CH2 CH2
C8H8Cl-E-1 o-Chlorostyrene-E-2 Cl
CH2 CH2
C8H8Cl-E-2 p-Chlorostyrene-E-2
Cl
CH CH
C8H8N-E 2-Methyl-5-vinylpyridine-E-1
N
CH3
CH3
C8H8O-R Phenylene-oxide-R O
CH3
CH2 CH2
C8H9-E Styrene-E-2
CH2 CH
C8H9N-R 2-Methyl-5-vinylpyridine-R
N
CH3
CH2 CH2
C8H10N-E 2-Methyl-5-vinylpyridine-E-2
N
CH3
O O
C8H12O2-R Suberic-acid-R
C(CH2)6C
O
CH2 O C CH3
C8H12O6-R Cellulose-acetate-R O
O
OH OH
CH3
CH C
C8H13O2-E-1 n-Butyl-methacrylate-E-1
C
O O C4H9
CH3
CH C
C8H13O2-E-2 Isobutyl-methacrylate-E-1 CH3
C
O O CH2 CH CH3
CH3
CH C
C8H13O2-E-3 sec-Butyl-methacrylate-E-1 CH3
C
O O CH C2H5
O O
C8H13O3-E Suberic-acid-E
C(CH2)6COH
O
CH2 O C CH3
C8H13O6-E Cellulose-acetate-E O
OH
OH OH
O O
C8H14N2O2-R Hexamethylene-diisocyanate-R
C NH (CH2)6 NH C
CH3
C8H14O2-R-1 n-Butyl-methacrylate-R
CH2 C
C
O O C4H9
CH3
C8H14O2-R-2 Isobutyl-methacrylate-R
CH2 C
CH3
C
O O CH2 CH CH3
CH3
C8H14O2-R-3 sec-Butyl-methacrylate-R
CH2 C
CH3
C
O O CH C2H5
CH CH
C8H15-E 1-Octene-E-1
C6H13
CH3
CH2 CH
C8H15O2-E-1 n-Butyl-methacrylate-E-2
C
O O C4H9
CH3
C8H15O2-E-2 n-Butyl-methacrylate-E-3
CH3 C
C
O O C4H9
CH3
CH2 CH
C8H15O2-E-3 Isobutyl-methacrylate-E-2 C CH3
O O CH2 CH
CH3
CH3
CH3 C
C8H15O2-E-4 Isobutyl-methacrylate-E-3
C CH3
O O CH2 CH
CH3
CH3
C8H15O2-E-5 sec-Butyl-methacrylate-E-2
CH2 CH
CH3
C
O O CH C2H5
CH3
C8H15O2-E-6 sec-Butyl-methacrylate-E-3
CH3 C
C CH3
O O CH C2H5
CH2 CH
C8H16-R 1-Octene-R
C 6H13
CH2 CH2
C8H17-E-1 1-Octene-E-2
C 6H13
CH3 CH
C8H17-E-2 1-Octene-E-3
C6H13
O O
C9H7O3-E Dimethyl-terephthalate-E
C C O CH3
CH3
CH C
C9H9-E-1 Alpha-Methylstyrene-E-1
CH CH
C9H9-E-2 m-Methylstyrene-E-1
CH3
CH CH
C9H9-E-3 o-Methylstyrene-E-1 CH3
CH CH
C9H9-E-4 p-Methylstyrene-E-1
CH3
O
NH CH C
C9H9NO-R Phenylalanine-R CH2
O
NH CH C
CH2
C9H9NO2-R Tyrosine-R
OH
CH CH
C9H9O-E p-Methoxystyrene-E-1
OCH3
CH3
CH2 C
C9H10-R-1 alpha-Methylstyrene-R
CH2 CH
C9H10-R-2 m-Methylstyrene-R
CH3
CH2 CH
C9H10-R-3 o-Methylstyrene-R CH3
CH2 CH
C9H10-R-4 p-Methylstyrene-R
CH3
O
NH2 CH C
C9H10NO-E Phenylalanine-E-1 CH2
O
NH CH C
C9H10NO2-E-1 Phenylalanine-E-2 CH2 OH
O
NH2 CH C
CH2
C9H10NO2-E-2 Tyrosine-E-1
OH
O
NH CH C
CH2 OH
C9H10NO3-E Tyrosine-E-2
OH
CH2 CH
C9H10O-R p-Methoxystyrene-R
OCH3
CH3
CH2 CH
C9H11-E-1 alpha-Methylstyrene-E-2
CH3
CH3 C
C9H11-E-2 alpha-Methylstyrene-E-3
CH2 CH2
C9H11-E-3 m-Methylstyrene-E-2
CH3
CH2 CH2
C9H11-E-4 o-Methylstyrene-E-2 CH3
CH2 CH2
C9H11-E-5 p-Methylstyrene-E-2
CH3
CH2 CH2
C9H11O-E p-Methoxystyrene-E-2
OCH3
CH CH
CH2
C9H12-R Ethylidene-norbornene-R CH CH
CH2 C
CH CH3
O O
C9H14O2-R Azelaic-acid-R
C(CH2)7C
CH CH
C9H15O2-E-1 n-Hexyl-acrylate-E-1 C
O O C6H13
CH3
CH C
C9H15O2-E-2 n-Pentyl-methacrylate-E-1
C
O O C5H11
O O
C9H15O3-E Azelaic-acid-E
C(CH2)7COH
CH2 CH
C9H16O2-R-1 n-Hexyl-acrylate-R C
O O C6H13
C9H16O2-R-2 n-Pentyl-methacrylate-R
CH CH
C9H17-E 1-Nonene-E-1
C7H15
CH2 CH2
C9H17O2-E-1 n-Hexyl-acrylate-E-2 C
O O C6H13
CH3
C9H17O2-E-2 n-Pentyl-methacrylate-E-2
CH2 CH
C
O O C5H11
CH3
C9H17O2-E-3 n-Pentyl-methacrylate-E-3
CH3 C
C
O O C5H11
CH2 CH
C9H18-R 1-Nonene-R
C 7H15
CH2 CH2
C9H19-E-1 1-Nonene-E-2
C7H15
CH3 CH
C9H19-E-2 1-Nonene-E-3
C 7H15
CH CH
CH
CH2 CH
C10H12-R Dicyclopentadiene-R CH CH
CH2 CH
CH
CH3
CH C
C10H15O2-E Cyclohexyl-methacrylate-E-1
C
O O
CH3
CH2 C
C10H16O2-R Cyclohexyl-methacrylate-R
C
O O
O O
C10H16O2-R-1 Sebacic-acid-R
C(CH2)8C
CH3
CH2 CH
C10H17O2-E-1 Cyclohexyl-methacrylate-E-2
C
O O
CH3
CH3 C
C10H17O2-E-2 Cyclohexyl-methacrylate-E-3
C
O O
CH3
CH C
C10H17O2-E-3 n-Hexyl-methacrylate-E-1
C
O O C6H13
O O
C10H17O3-E Sebacic-acid-E
C(CH2)8COH
CH3
CH2 C
C10H18O2-R n-Hexyl-methacrylate-R
C
O O C6H13
CH CH
C10H19-E 1-Decene-E-1
C8H17
CH3
CH2 CH
C10H19O2-E-1 n-Hexyl-methacrylate-E-2
C
O O C6H13
CH3
CH3 C
C10H19O2-E-2 n-Hexyl-methacrylate-E-3
C
O O C6H13
CH2 CH
C10H20-R 1-Decene-R
C8H17
CH2 CH2
C10H21-E-1 1-Decene-E-2
C8H17
CH3 CH
C10H21-E-2 1-Decene-E-3
C8H17
O
NH CH C
C11H10N2O-R Tryptophan-R CH2
O
NH2 CH C
C11H11N2O-E Tryptophan-E-1 CH2
O
NH CH C
OH
C11H11N2O2-E Tryptophan-E-2 CH2
CH CH
C11H21-E 1-Undecene-E-1
C9H19
CH2 CH
C11H22-R 1-Undecene-R
C9H19
CH2 CH2
C11H23-E-1 1-Undecene-E-2
C9H19
CH3 CH
C11H23-E-2 1-Undecene-E-3
C9H19
C12H6O2-R 2,6-Napthalene-diacid-R
C12H7O3-E 2,6-Napthalene-diacid-E
O
CH2 O C CH3
O
C12H16O8-R Cellulose-triacetate-R
O
O O
CH3 C O O C CH3
O
CH2 O C CH3
C12H17O8-E Cellulose-triacetate-E O
HO
O O
CH3 C O O C CH3
CH2OH OH NH2
O
C12H22N2O8-R Chitosan-R O O
O
OH NH2 CH2OH
CH CH
C12H23-E 1-Dodecene-E-1
C10H21
CH2OH OH NH2
O
C12H23N2O8-E Chitosan-E-1 O OH
O
OH NH2 CH2OH
CH2OH OH NH2
O
C12H23N2O9-E Chitosan-E-2 HO O O
O
OH NH2 CH2OH
CH2 CH
C12H24-R 1-Dodecene-R
C10H21
CH2 CH2
C12H25-E-1 1-Dodecene-E-2
C10H21
CH3 CH
C12H25-E-2 1-Dodecene-E-3
C10H21
C13H9O3-E 2,6-Napthalene-dimethylester-E
CH2OH CH2OH
O O
C14H23NO10-R Heparin-R HO O
O
O OH OH NH C CH3
CH2OH CH2OH
O O
C14H24NO10-E Heparin-E-1 HO O
O
OH OH OH NH C CH3
CH2OH CH2OH
O O
C14H24NO11-E Heparin-E-2 HO O OH
O
O OH OH NH C CH3
CH3
CH C
C14H25O2-E Decyl-methacrylate-E-1
C
O O C10H21
CH3
CH2 C
C14H26O2-R Decyl-methacrylate-R
C
O O C10H21
CH3
C14H27O2-E-1 Decyl-methacrylate-E-2 CH2 CH
C
O O C10H21
CH3
C14H27O2-E-2 Decylmethacrylate-E-3
CH3 C
C
O O C10H21
CH3
C15H14O2-R Bisphenol-A-R O C O
CH3
CH3
C15H15O2-E Bisphenol-A-E O C OH
CH3
Solvent Dependency
Decomposition rates are lowest in solvents that act as radical scavengers,
such as poly chlorinated organic compounds (e.g., TCE). Initiators used for
bulk-phase vinyl chloride polymerizations are typically in these types of
Concentration Dependency
At high initiator concentrations there is an induced initiation effect. Primary
radicals attack and split un-decomposed initiator molecules. This reduces the
measured half-life time and efficiency of the initiator. All of the data reported
in the following table are based on measurements at relatively low initiator
concentrations (0.2 molar or less). Although the standard decomposition rate
expressions do not account for induced initiator, the user may modify the rate
expression using a gel effect term.
Temperature Dependency
Initiator decomposition rates are reported in several formats including rate
constants, half-life times at specified temperatures, and half-life temperatures
at specified times. These data are all related to each other through the
following equations:
E E1
k Tref = A exp kT = kTref exp 1
RT R T Tref
ref
ln(0.5) E
kT = T60 =
t 1 ,T ln(0.5)
2 R ln
3600 A
Where:
A = Pre-exponential factor (1/sec)
These equations were applied to the published raw data to allow the rate
constants to be published in a concise format here.
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
ABAH 2,2-azo-bis(2- Vazo 56 (DuPont) C8H20N6Cl2 271.19264 2997-92-4 3.3436E-05 6.44E+14 29.4 0.12300 110.5 73.7 55.9 Water DuPont
amidinopropane) V-50 (Wako Chem) HCl HN NH HCl
dihydrochloride N N
H 2N NH2
VAZO68 4,4-azo-bis Vazo 68 (DuPont) C12H22N2O4 258.31776 2638-94-0 7.3642E-06 5.12E+12 27.2 0.11380 132.7 88.7 68.0 Water DuPont
(4-cyanovaleric acid) HOOC
N N
COOH
VA61 2,2-azo-bis[2-(2- VA-061 (Wako Chem) C12H22N6 250.34712 20858-12-2 1.3404E-03 1.00E+15 27.2 0.11400 78.4 45.0 28.9 Acidic water Wako
imidazolin-2-yl)propane] N N
N N
N HN
H
VA86 2,2-Azobis[2-methyl-N-(2- VA-086 C12H24N4O4 288.34712 61551-69-7 6.7869E-06 7.95E+14 30.6 0.12800 123.9 86.0 67.7 Water Wako
hydroxyethyl)propionamide] O O
N N
HOH 2CH 2C NH HN CH2 CH2OH
VAZO44 2,2-azo-bis(N,N- Vazo 44 (DuPont) C12H24Cl2N6 323.26840 27776-21-2 1.3564E-04 8.10E+12 25.6 0.10700 103.3 63.0 44.0 Water DuPont
dimethylene VA-44 (WakoChem) N N
isobutyramidine) N N 2HCl
dihydrochloride
N HN
H
VA46B 2,2-azo-bis[2-(2- VA-046B (Wako Chem) C12H30N6O10S2 482.53664 20858-12-2 1.4388E-03 1.18E+17 30.4 0.12700 75.9 46.0 31.4 Water Wako
imidazolin-2-yl)propane N N
disulfate dihydrate H2 SO4
N N
N H2 O
HN
H
VA41 2,2-azo-bis[2-(5-methyl- VA-041 (WakoChem) C14H26Cl2N6 349.30628 n/a 2.7035E-04 2.53E+15 28.9 0.12100 91.3 57.4 41.0 Water Wako
2-imidazolin-2-yl)propane] N N
dihydrochloride
N N
N N
H H
HCl HCl
VA58 2,2-azobis[2-(3,4,5,6- VA-058 (WakoChem) C14H28Cl2N6 351.32216 102834-39-0 2.5342E-05 1.44E+15 30.1 0.12600 111.8 75.5 58.0 Water Wako
tetrahydropyrimidin-2- N N
yl)propane] dihydrochloride N N 2HCl
NH HN
VA57 2,2-azobis[N-(2- VA-057 (WakoChem) C14H34N6O8 414.45960 n/a 2.8824E-05 5.56E+14 29.4 0.12300 112.0 74.9 57.0 Water Wako
carboxyethyl)-2- HN NH
HOO C N N CO OH 4 H 2O
methylpropionamidine] HN NH
tetrahydrate
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
VA85 2,2-Azobis{2-methyl-N-[2- VA-085 (Wako Chem) C16H32N4O4 344.45464 n/a 7.8450E-07 6.41E+13 30.4 0.12700 148.2 105.4 85.0 Water Wako
(1-hydroxybuthyl)] O O
propionamide} H 3CH 2 C N N CH2 CH3
NH HN
HOH2 C CH2 OH
VA60 2,2-azo-bis{2-[1-(2- VA-060 (Wako Chem) C16H32Cl2N6O2 411.37472 11858-13-0 1.9254E-05 9.56E+15 31.5 0.13200 111.7 76.9 60.0 Water Wako
hydroxyethyl)-2-imidazolin- N N
2-yl]propane} N N 2HCl
dihydrochloride
N N
CH 2 CH 2 OH CH 2 CH 2 OH
V30 1-cyano-1-methyl- V-30 (Wako Chem) C5H8N4O 140.14488 10288-28-5 4.4161E-08 1.86E+15 34.5 0.14430 164.9 123.9 104.0 Toluene Wako
ethylazofomamide CN
N N CONH2
AIBN 2,2'-azo-bis-isobutyronitrile Vazo 64 (DuPont) C8H12N4 164.21024 78-67-1 1.0464E-05 2.74E+15 31.1 0.13023 118.3 82.0 64.4 Chlorobenzene AkzoNobel
Perkadox AIBN
(AkzoNobel) NC N N CN
AMBN 2,2'-azo-bis(2- Vazo 67 (DuPont) C10H16N4 192.26400 13472-08-7 8.4357E-06 1.38E+15 30.8 0.12893 121.2 84.0 66.0 Chlorobenzene AkzoNobel
methylbutyronitrile) Perkadox AMBN CN CN
(AkzoNobel)
V-59 (Wako Chem) C 2H5 N N C 2H 5
V601 dimethyl 2,2'-azobis (2- V-601 (Wako Chem) C10H18N2O4 230.26400 2589-57-3 8.5556E-06 6.99E+14 30.4 0.12700 122.1 84.3 66.0 Toluene Wako
methylpropionate) O O
H 3CO N N OCH3
ACCN 1,1-azo-di-(hexa Vazo 88 (DuPont) C14H20N4 244.33976 2094-98-6 5.4449E-07 1.07E+16 34.0 0.14219 140.2 103.0 84.9 Chlorobenzene AkzoNobel
hydrobenzenenonitrile) Perkadox ACCN NC
(AkzoNobel)
V-40 (Wako Chem) N N
CN
AMVN 2,2'-azo-bis(2,4-dimethyl Vazo 52 (DuPont) C14H24N4 248.37152 4419-11-8 1.0349E-04 1.78E+14 27.8 0.11630 102.1 65.0 47.2 Toluene DuPont
valeronitrile) V-65 (Wako Chem)
VF096 2,2'-azo-bis[N-(2- VF-096 (Wako Chem) C14H24N4O2 280.37032 129136-92-1 1.5480E-07 4.67E+14 32.7 0.13700 157.8 116.1 96.0 Toluene Wako
propenyl)-2- O O
methylpropionamide]
N N
NH HN
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
AMOMVN 2,2'-azo-bis(4-methoxy- V-70 (Wako Chem) C16H28N4O2 308.42408 15545-97-8 1.1718E-03 1.26E+15 27.5 0.11500 79.4 46.1 30.0 Toluene Wako
2,4-dimethyl valeronitrile) CN CN
H 3CO H 2C N N CH 2 OCH3
VAM110 2,2'-azo-bis(N-butyl-2- Vam-100 (Wako Chem) C16H32N4O2 312.45584 n/a 2.3941E-08 4.40E+14 33.9 0.14200 174.2 130.9 110.0 Toluene Wako
methylpropionamide) O O
N N
C 4 H9 NH HN C 4 H 9
VAM111 2,2'-azo-bis(N-cyclohexyl- Vam-110 (Wako Chem) C20H36N4O2 364.53160 n/a 3.4427E-08 1.71E+13 31.5 0.13200 181.3 133.7 111.0 Toluene Wako
2-methylpropionamide) O O
N N
NH HN
Diacyl Peroxides
PP dipropionyl peroxide C6H10O4 146.14300 3248-28-0 4.3006E-05 1.14E+15 30.5 0.12760 119.1 81.9 63.9 Benzene Polymer
O Handbook
O
O
O
SAP succinic acid peroxide Luperox SAP (Atofina) C8H10O8 234.16260 123-23-9 8.7924E-06 4.89E+10 24.0 0.10043 142.3 91.0 67.4 Acetone Atofina
SUCP-70-W (Degussa) O O
HO O
O OH
O O
IBP diisobutyryl peroxide Trigonox 187-C30 C8H14O2 142.19796 3437-84-1 2.7220E-03 3.42E+14 26.1 0.10906 72.7 39.0 22.8 Chlorobenzene AkzoNobel
(AkzoNobel) O
O
O
O
BP dibenzoyl peroxide Luperox AFR40 (Atofina) C14H10O4 242.23100 94-36-0 3.8607E-06 3.40E+14 30.4 0.12721 130.3 91.0 72.1 Benzene Atofina
O O
O O
DCLBP bis(2,4-dichlorobenzoyl) DCLBP (Degussa) C16H6Cl2O4 333.12664 133-14-2 4.2163E-05 3.95E+14 28.9 0.12100 109.1 72.0 54.1 Benzene Degussa
peroxide O O
Cl Cl
O O
Cl Cl
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
OMBP bis(ortho-methylbenzoyl) Perkadox 20 (Akzo C16H14O4 270.28476 3034-79-5 1.5072E-05 6.85E+13 28.4 0.11900 120.9 81.0 61.9 Benzene Degussa
peroxide Nobel) O O
OMBP (Degussa)
O O
PMBP bis(para-methylbenzoyl) PMBP (Degussa) C16H14O4 270.28476 895-95-2 5.1895E-06 2.06E+14 29.9 0.12500 128.6 89.0 70.0 Benzene Degussa
peroxide O O
O O
OP dioctanoyl peroxide Trigonox SE-8 C16H30O4 286.41180 762-16-3 1.3761E-05 2.36E+15 30.8 0.12905 116.3 80.0 62.4 Chlorobenzene AkzoNobel
(AkzoNobel) O
O (CH2) 6CH 3
H 3C(CH2) 6 O
O
INP bis(3,5,5- Trigonox 36 C18H34O4 314.46556 3851-87-4 2.0300E-05 2.70E+15 30.7 0.12835 112.8 77.0 59.6 Chlorobenzene AkzoNobel
trimethylhexanoyl) peroxide (AkzoNobel) O O
Luperox 219 (AtoFina) O O
DP didecanoyl peroxide Luperox DEC (Atofina) C20H38O4 342.51932 762-12-9 1.4646E-05 8.34E+14 30.1 0.12600 117.2 80.0 62.0 Benzene Degussa
Perkadox SE-10 O
(AkzoNobel)
O C 9H19
C 9H 19 O
O
LP dilauroyl peroxide Luperox LP (Atofina) C24H46O4 398.62684 105-74-8 1.7414E-05 3.84E+14 29.5 0.12337 116.9 79.0 60.8 Chlorobenzene AkzoNobel
Laurox (AkzoNobel) O
O C 11H23
C 11H 23 O
O
Peroxycarbonates
BPIC tert-butylperoxy isopropyl Trigonox BPIC C8H16O4 176.21264 2372-21-6 7.0005E-08 2.44E+16 35.9 0.15015 154.9 117.0 98.5 Chlorobenzene AkzoNobel
carbonate O
O O O
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
IPPC diisopropyl IPPC (Degussa) C8H16O6 208.21144 105-64-6 1.6931E-04 7.70E+14 28.4 0.11900 96.3 61.0 44.0 Benzene Degussa
peroxydicarbonate O
O O
O O
O
NPPC di-n-propyl Luperox 221 (AtoFina) C8H16O6 208.21144 16066-38-9 1.4752E-04 3.56E+15 29.5 0.12362 96.1 62.0 45.5 Chlorobenzene AkzoNobel
peroxydicarbonate Trigonox NPP-CK85 O
(AkzoNobel)
O O
O O
O
SBPC di-secbutyl Luperox 225 (AtoFina) C10H16O6 232.23344 19910-65-7 1.2919E-04 3.38E+15 29.6 0.12385 97.2 63.0 46.4 Chlorobenzene AkzoNobel
peroxydicarbonate Trigonox SBP O
(AkzoNobel)
O O
O O
O
TBPIC tert-butylperoxy- Trigonox BPIC (Akzo) C11H20O6 248.27620 2372-21-6 7.0005E-08 2.44E+16 35.9 0.15015 154.9 117.0 98.5 Chlorobenzene AkzoNobel
isopropylcarbonate Luperox TBIC (AtoFina) O
TBPIC (Degussa)
O
O O
TBPEHC tert-butylperoxy 2- Trigonox 117 C13H26O4 246.34704 12/4/3443 6.4441E-08 3.95E+16 36.3 0.15172 154.4 117.0 98.7 Chlorobenzene AkzoNobel
ethylhexyl carbonate (AkzoNobel) C 4H9
Luperox TBEC (AtoFina)
O O
O C 2H 5
O
CHPC dicyclohexyl CHPC (Degussa) C14H22O6 286.32508 1561-49-5 1.9626E-04 3.30E+16 30.8 0.12900 91.9 59.9 44.2 Chlorobenzene AkzoNobel
peroxydicarbonate O (Polymer
Handbook)
O O
O O
O
TAPEHC tert-amylperoxy 2- Trigonox 131 C14H28O4 260.37392 70833-40-8 1.2326E-07 2.29E+16 35.5 0.14841 150.5 113.0 94.7 Chlorobenzene AkzoNobel
ethylhexyl carbonate (AkzoNobel) C 2H5
Luperox TAEC (AtoFina) C 2H 5
O O
C 4H 9 O
O
EHPC di(2-ethylhexyl) Luperox 223 (AtoFina) C18H34O6 346.46436 16111-62-9 1.1396E-04 1.80E+15 29.3 0.12245 98.9 64.0 47.1 Chlorobenzene AkzoNobel
peroxydicarbonate Trigonox EHP O
(AkzoNobel) O O
O O
O
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
BCHPC Di(4-tert-butylcyclohexyl) Perkadox 16 C22H38O6 398.54012 15520-11-3 1.1205E-04 7.34E+15 30.2 0.12639 97.7 64.0 47.6 Chlorobenzene AkzoNobel
peroxydicarbonate (AkzoNobel)
O O
O
O
O O
MYPC Dimyristyl Perkadox 26 C30H58O6 514.78692 53220-22-7 9.9164E-05 3.06E+15 29.7 0.12430 99.5 65.0 48.3 Chlorobenzene AkzoNobel
peroxydicarbonate (AkzoNobel) O
C 14H 29 O O C H
O O 14 29
O
CEPC dicetyl peroxydicarbonate Perkadox 24 C34H66O6 570.89444 26322-14-5 9.9270E-05 2.85E+15 29.7 0.12410 99.6 65.0 48.2 Chlorobenzene AkzoNobel
(AkzoNobel) O
C 16H 33 O O C H
O O 16 33
O
Alkyl Peroxides
DTBP di-tert-butyl peroxide Trigonox B (AkzoNobel) C8H18O2 146.22972 110-05-4 3.7905E-09 4.36E+15 36.7 0.15346 182.9 141.0 120.7 Chlorobenzene AkzoNobel
Luperox DI (AtoFina)
O O
DTAP di-tert-amyl peroxide Trigonox 201 C10H22O2 174.28348 10508-09-5 2.1965E-08 3.99E+15 35.5 0.14835 168.7 128.0 108.3 Chlorobenzene AkzoNobel
(AkzoNobel)
Luperox DTA (AtoFina)
O O
BCUP tert-butylcumyl peroxide Trigonox T (AkzoNobel) C13H20O2 208.30060 3457-61-2 1.0091E-08 1.12E+15 35.1 0.14698 178.8 136.0 115.3 Chlorobenzene AkzoNobel
BCUP (Degussa)
O O
DCUP dicumyl peroxide Perkadox BC C18H22O2 270.37148 80-43-3 1.0731E-08 9.28E+15 36.5 0.15267 172.2 132.0 112.4 Chlorobenzene AkzoNobel
(AkzoNobel)
Luperox 500 (AtoFina)
O O
DTBCP di-tert-butyl cumyl peroxide C26H38O2 382.58652 3.6200E-09 3.05E+15 36.5 0.15260 184.4 142.0 121.4 Toluene Warson
(1980)
O O
Hydroperoxides
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
TBHP tert-butyl hydroperoxide Trigonox A (AkzoNobel) C4H10O2 90.12220 75-91-2 2.1276E-12 3.09E+17 44.5 0.18600 226.9 185.0 164.4 Chlorobenzene AkzoNobel
Luperox TBH (AtoFina)
TBHP (Degussa)
O OH
TAHP tert-amyl hydroperoxide Trigonox TAHP (Akzo) C5H12O2 104.14908 3425-61-4 6.2470E-09 6.14E+07 24.4 0.10200 234.1 190.0 153.0 Chlorobenzene AkzoNobel
TAHP (AtoFina)
C2 H 5 O OH
TMBHP 1,1,3,3-tetramethylbutyl Trigonox TMBH C8H18O2 146.22972 5809-08-5 9.0052E-11 9.13E+18 44.2 0.18500 172.7 153.0 135.0 Chlorobenzene AkzoNobel
hydroperoxide (AkzoNobel) O OH
CUHP cumene hydroperoxide Trigonox K (AkzoNobel) C9H12O2 152.19308 80-15-9 1.8527E-09 1.13E+12 31.7 0.13256 221.8 166.0 139.8 Chlorobenzene AkzoNobel
Luperox CU (AtoFina)
CUHP (Degussa)
O OH
IPCHP isopropylcumyl Trigonox M (AkzoNobel) C12H18O2 194.27372 26762-93-6 5.6157E-09 2.28E+12 31.4 0.13144 207.1 154.0 129.0 Chlorobenzene AkzoNobel
hydroperoxide
O OH
Peroxyesters
TBPA tert-butyl peroxyacetate Trigonox F (AkzoNobel) C6H12O3 132.15948 107-71-1 5.7708E-08 1.51E+16 35.7 0.14936 157.5 119.0 100.2 Chlorobenzene AkzoNobel
Luperox 7 (AtoFina) O
O
O
TAPA tert-amyl peroxyacetate Trigonox 133 C7H14O3 146.18636 690-83-5 2.5042E-07 1.53E+17 36.3 0.15171 141.3 106.0 88.7 Chlorobenzene AkzoNobel
(AkzoNobel) O
Luperox 555 (AtoFina)
C 2H 5 O O
TBPIB tert-butyl peroxyisobutyrate Trigonox 41 C8H16O3 160.21324 109-13-7 1.3027E-06 2.02E+15 32.3 0.13516 136.3 98.0 79.5 Chlorobenzene AkzoNobel
(AkzoNobel) O
O
O
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
TBPPI tert-butyl peroxypivalate Trigonox 25 C9H18O3 174.24012 927-07-1 2.8161E-05 6.72E+14 29.5 0.12359 111.9 75.0 57.2 Chlorobenzene AkzoNobel
(AkzoNobel) O
Luperox 11 (AtoFina)
TBPPI (Degussa) O O
TBPEA tert-butyl Trigonox 27 C10H20O3 188.26700 2550-33-6 2.4603E-06 2.52E+15 32.0 0.13400 130.6 93.0 74.8 Chlorobenzene AkzoNobel
peroxydiethylacetate (AkzoNobel) O
O O
TAPPI tert-amyl peroxypivalate Trigonox 125 C10H20O3 188.26700 29240-17-3 3.8733E-05 4.16E+15 30.5 0.12776 107.0 72.0 55.0 Chlorobenzene AkzoNobel
(AkzoNobel) O
Luperox 554 (AtoFina)
TAPPI (Degussa) O O C 2 H5
TBPB tert-butyl peroxybenzoate Triganox C (AkzoNobel) C11H14O3 194.23036 614-45-9 3.5920E-08 2.10E+16 36.2 0.15159 160.5 122.0 103.2 Chlorobenzene AkzoNobel
Luperox P (AtoFina) O
TBPB (Degussa)
O
O
TBPN7 tert-butyl Trigonox 257 C11H22O3 202.29388 110-05-4 8.0391E-05 2.17E+14 28.1 0.11756 104.2 67.0 49.1 Chlorobenzene AkzoNobel
peroxyneoheptanoate (AkzoNobel) O
O O C 3 H7
TAPB tert-amyl peroxybenzoate Trigonox 127 C12H16O3 208.25724 4511-39-1 7.3536E-08 8.27E+15 35.1 0.14702 157.0 118.0 99.0 Chlorobenzene AkzoNobel
(AkzoNobel) O
Luperox TAP (AtoFina)
TAPB (Degussa) O
O
C 2 H5
TBPEH tert-butylperoxy-2- Trigonox 21 C12H24O3 216.32076 3006-82-4 4.1442E-06 1.59E+14 29.8 0.12490 131.1 91.0 71.7 Chlorobenzene AkzoNobel
ethylhexanoate (AkzoNobel) O
Luperox 26 (AtoFina)
O C 4 H9
O
C 2H 5
TMBPPI 1,1,3,3-tetramethylbutyl Trigonox 425 C13H26O3 230.34764 22288-41-1 9.0908E-05 2.41E+14 28.1 0.11750 103.0 66.0 48.2 Chlorobenzene AkzoNobel
peroxypivalate (AkzoNobel) O
O
O
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
TAPEH tert-amyl peroxy-2- Trigonox C13H26O3 230.34764 686-31-7 3.3205E-06 1.72E+15 31.6 0.13211 128.7 91.0 72.7 Chlorobenzene AkzoNobel
ethylhexanoate 121(AkzoNobel) O
Luperox 575 (AtoFina)
TAPEH (Degussa) O C4H 9
O
C 2H 5
C 2 H5
TBPIN tert-butylperoxy-3,5,5- Trigonox 42S C13H26O3 230.34764 13122-18-4 1.6062E-07 1.90E+15 33.6 0.14078 154.0 114.0 94.6 Chlorobenzene AkzoNobel
trimethyl-hexanoate (AkzoNobel)
O
O
O
TBPND tert-butyl Trigonox 23 C14H28O3 244.37452 26748-41-4 1.1742E-04 1.49E+14 27.6 0.11547 101.2 64.0 46.2 Chlorobenzene AkzoNobel
peroxyneodecanoate (AkzoNobel) O C 2 H5
Luperox 10 (AtoFina)
TBPND (Degussa) O O C 4 H9
C 2 H5
DMHBPEH 1,1-dimethyl-3- Luperox 665 (AtoFina) C14H28O4 260.37392 95732-35-7 1.0997E-05 3.49E+13 28.2 0.11800 125.0 84.0 64.4 TCE AtoFina
hydroxybutyl peroxy-2- C2H 5
ethylhexanoate OH
O
C 4H 9 O
O
TAPND tert-amyl Trigonox 123 C15H30O3 258.40140 68299-16-1 1.7016E-04 1.46E+14 27.3 0.11438 97.9 61.0 43.3 Chlorobenzene AkzoNobel
peroxyneodecanoate (AkzoNobel) O C 2H 5
Luperox 546 (AtoFina)
C 2 H5 O O C 4H 9
C 2H 5
CUPN7 cumyl peroxyneoheptanoate Trigonox 197 C16H24O3 264.36476 130097-36-8 2.4772E-04 3.27E+14 27.6 0.11557 93.8 58.0 40.8 Chlorobenzene AkzoNobel
(AkzoNobel) O
Luperox 288 (AtoFina)
O O C C2 H 5
C 2H 5
TMBPEH 1,1,3,3-tetramethylbutyl Trigonox 421 C16H32O3 272.42828 22288-43-3 6.0205E-06 1.55E+14 29.6 0.12380 127.8 88.0 68.9 Chlorobenzene AkzoNobel
peroxy-2-ethylhexanoate (AkzoNobel) O
C 4H 9 O
O
C2 H 5
DMHBPND 1,1-dimethyl-3- Luperox 610 (AtoFina) C16H32O4 288.42768 95718-78-8 4.0233E-04 1.14E+14 26.6 0.11131 90.4 54.0 36.6 a- AtoFina
hydroxybutyl C2 H 5 methylstyrene
peroxyneodecanoate C 4H 9 OH
O
O
C 2H 5
O
ID Long Name Trade Name(s) Formula / Molecular Structure MW CAS No kref (1/s) A (1/sec) kcal/mol GJ/kmol 1 min 1 hr 10 hr Solvent Source
TMBPND 1,1,3,3,-tetramethylbutyl Triganox 423 C18H36O3 300.48204 51240-95-0 2.8151E-04 4.02E+14 27.7 0.11579 92.5 57.0 39.9 Chlorobenzene AkzoNobel
peroxyneodecanoate (AkzoNobel) C2H 5
C 4H 9
O
O
C 2H 5
O
CUPND cumyl peroxyneodecanoate Trigonox 99 C19H30O3 306.44540 26748-47-0 3.1832E-04 2.95E+14 27.4 0.11459 91.7 56.0 38.8 Chlorobenzene AkzoNobel
(AkzoNobel) O C 2H 5
Luperox 188 (AtoFina)
CUPND (Degussa) O O C4 H 9
C 2H 5
C-C Initiators
DMDPB 2,3-dimethyl-2,3- Perkadox 30 C18H22O2 270.37148 1889-67-4 6.1389E-18 7.57E+18 55.0 0.23019 304.5 259.0 236.4 Chlorobenzene AkzoNobel
diphenylbutane (AkzoNobel)
Sulfonyl Peroxides
ACHSP acetyl Lupersol 228Z (AtoFina) C8H14O5S 222.26216 3179-56-4 7.3692E-04 7.27E+17 32.0 0.13390 80.1 51.0 36.6 Toluene Warson
cyclohexanesulphonyl O O (1980)
peroxide
S O O
O
This appendix describes the input and output arguments for various Fortran
utilities useful for writing user kinetic subroutines. For each utility a list of
variables in the argument list is given along with their I/O status, their type,
and a brief description. These utilities are available to you in addition to those
documented in the Aspen Plus User Models reference manual.
The utilities documented in this appendix are:
Component Attribute Handling Utilities
VOLL
Utility Description
This utility finds a component attribute element ID given the attribute ID and
the element number.
Argument List
SUBROUTINE SHS_CAELID ( IDCAT, IELEM, IDCAEL )
CAID
Utility Description
This utility finds a component attribute ID given the component sequence
number, the attribute type number, and the substream structure.
Argument List
SUBROUTINE SHS_CAID ( ISSCNC, NCSEQ, J, IDCAT )
CAMIX
Utility Description
This is the component attribute mixing utility. It mixes the attributes from two
inlet streams into an outlet stream.
Argument List
SUBROUTINE SHS_CAMIX ( IP, SS1, SS2, SSO )
INTEGER IP
REAL*8 SS1(1), SS2(1), SS0(1)
IP=1 !'Conventional substream'
.
CASPLT
Utility Description
This is the component attribute splitting utility. It calculates the attribute
values in a product stream for a given feed stream.
Argument List
SUBROUTINE SHS_CASPLT ( FEED, PROD, NSUBS, IDXSUB, ITYPE )
CASPSS
Utility Description
This is the component attribute splitting utility for substreams. It calculates
the attribute values in a product substream for a given feed substream.
Argument List
SUBROUTINE SHS_CASPSS ( FEED, PROD, ITYPE )
INTEGER ITYPE(1)
REAL*8 FEED(1), PROD(1)
ITYPE(1)=1 !'Conventional'
.
.
.
CALL SHS_CASPSS ( FEED, PROD, ITYPE )
CAUPDT
Utility Description
This utility calculates class zero component attribute values in a product
stream based on class 2 component attributes.
Argument List
COPYCA
Utility Description
This utility copies all attribute values from one stream into another stream of
the same type.
Argument List
GETCRY
Utility Description
This utility returns the crystallinity of a list of components.
GETDPN
Utility Description
This utility returns the number average degree of polymerization.
Argument List
GETMWN
Utility Description
This utility calculates the true molecular weight of a polymer, from the degree
of polymerization and the average segment molecular weight.
Argument List
Utility Description
This utility returns the weight-average molecular weight vector for all of the
polymer components present. For standard components, the component
molecular weight is returned.
Argument List
REAL*8 MWW
INTEGER NCNC, NCP, IDXI
NCNC=1 !'Conventional substream'
NCP=1 !'Only one component (polymer)'
IDXI=2 !'Polymer is 2nd component'
.
.
.
CALL POLY_GETMWW( NCNC, NCP, IDXI, MWW )
GETPDI
Utility Description
This utility returns the polydispersity index for all components listed in the
IDX array. For standard components, the PDI is set equal to the value of the
POLPDI parameter.
Argument List
GETSMF
Utility Description
This utility returns the segment mole fractions for the specified polymer or
oligomer component.
Argument List
GETSWF
Utility Description
This utility returns the segment weight (mass) fractions for the specified
polymer or oligomer component.
Argument List
Utility Description
This utility finds the offset of a component attribute from the beginning of the
substream given the structure of the substream, the component sequence
number and the attribute type number.
Argument List
LCATT
Utility Description
This utility finds the offset of a component attribute from the substream given
the structure of the substream, attributed component sequence number and
the attribute ID.
Argument List
NCAVAR
Utility Description
This utility finds the number of elements in a component attribute given the
attribute type index, the component index, and the substream type.
Argument List
Utility Description
This utility packs a list of conventional components into an output vector that
contains components whose mole fraction is greater than a minimum value
XMIN.
Argument List
Utility Description
This utility is used to retrieve parameter values from the plex.
Argument List
C
INTEGER TC, I
.
.
.
TC(I)=DMS_IFCMNC('TC')+I
ISCAT
Utility Description
This utility determines whether a component is a catalyst.
Argument List
INTEGER ICOMP
LOGICAL PPUTL_ISCAT
ISINI
Utility Description
This utility determines whether a component is an ionic initiator.
Argument List
INTEGER ICOMP
LOGICAL PPUTL_ISINI
ICOMP=2 !
.
.
.
If ( PPUTL_ISINI( ICOMP ) ) then...
ISOLIG
Utility Description
This utility determines whether a component is an oligomer.
Argument List
INTEGER ICOMP
LOGICAL SHS_ISOLIG
ICOMP=3 !
.
.
.
If ( SHS_ISOLIG( ICOMP ) ) then...
ISPOLY
Utility Description
This utility determines whether a component is a polymer.
Argument List
INTEGER ICOMP
LOGICAL SHS_ISPOLY
ICOMP=2 !
.
..
If ( ISPOLY( ICOMP ) ) then...
ISSEG
Utility Description
This utility determines whether a component is a segment.
Argument List
INTEGER ICOMP
LOGICAL PPUTL_ISSEG
ICOMP=5 !
.
.
.
If ( PPUTL_ISSEG( ICOMP ) ) then...
SCPACK
Utility Description
This utility packs lists of conventional component flow rates from several
phases into an output array which contains mole fractions of components that
are present in at least one of the phases.
Argument List
XATOWT
Utility Description
This utility returns the true weight fractions for all of the components present.
Argument List
XATOXT
Utility Description
This utility returns the true mole fractions for all of the components present.
Argument List
Utility Description
This utility returns the substream type number from the stream class
descriptor bead.
Argument List
INTEGER I, SHS_IPTYPE
INTEGR LD !'Use LOCATS utility model to obtain LD'
I=1 !'Substream 1'
.
.
.
N = SHS_IPTYPE (LD, I)
LOCATS
Utility Description
This utility finds the integer and real plex addresses of a stream, the stream
class bead location and bead number, given the stream bead number.
Argument List
Utility Description
This utility finds the offset of a substream from the beginning of a stream
structure.
Argument List
INTEGER I, SHS_LPHASE
INTEGER LD !'Use LOCATS utility to obtain LD'
I=1
.
.
.
N = SHS_LPHASE (LD, I)
NPHASE
Utility Description
This utility finds the number of substreams from the stream class descriptor
bead.
Argument List
INTEGER SHS_NPHASE
INTEGER !'Use LOCATS utility model to obtain LD'
.
.
.
N = SHS_NPHASE (LD)
NSVAR
Utility Description
This utility returns the number of stream variables.
Argument List
INTEGER SHS_NSVAR
INTEGER LD !'Use LOCATS utility model to obtain LD'
.
.
.
N = SHS_NSVAR (LD)
SSCOPY
Utility Description
This utility copies substream information from one stream to another.
Argument List
Other Utilities
VOLL
Utility Description
This utility calculates the mixture molar volume of liquid.
Argument List
Specifying Components
This section describes the input language for specifying components.
Naming Components
Following is the input language used to name components.
Input Language for Components
Specifying Component
Attributes
This section describes the input language for specifying component
attributes..
STREAM sid
SUBSTREAM ssid keyword=value
basis-FLOW cid flow / . . .
basis-FRAC cid frac / . . .
COMP-ATTR cname cattrname (value-list) / . . .
STREAM FEED
SUBSTREAM MIXED TEMP=70 PRES=1
MASS-FLOW STY 13.5 /ACN 7.27 /XYLENE 79 /SAN 0.1E-5/INI1 0.23
COMP-ATTR SAN DPN (3000) /
DPW (6000) /
PDI (2) /
MWN (312450) /
MWW (624900) /
ZMOM (0.39E-10) /
FMOM (1.17E-7) /
SMOM (7.02E-4) /
SFLOW (0.55E-7 0.55E-7) /
SFRAC (0.5 0.5) /
LSFLOW (0. 0.) /
LEFLOW (0. 0.)
ATTR-SCALING
SCALING COMP=comp-id ATTR=attr-id
SCALE-FACTOR=scale UPPER-BOUND=upper
ATTR-SCALING
SCALING PP LSEFLOW SCALE=1E-008 UPPER=1.E35
SCALING PP LZMOM SCALE=1E-008 UPPER=1.E35
SCALING PP LSZMOM SCALE=1E-008 UPPER=1.E35
SCALING TICL4 CVSFLOW SCALE=1E-008 UPPER=1.E35
SCALING TICL4 CPSFLOW SCALE=1E-008 UPPER=1.E35
Requesting Distribution
Calculations
See Specifying Component Characterization Inputs on page 461.
Optional Keywords:
COMPS PHASE UNITS TEMP PRES
Keyword: SUBROUTINE
Use the USER-PROPERTY paragraph to define the property. This property can
be referenced in the Prop-Set paragraph in the same way as built-in
properties. You must supply a Fortran subroutine to calculate the value of the
user Prop-Set properties.
userpropid User property set ID. This property must be different from
built-in properties. (See Aspen Physical Property System
Physical Property Data documentation.)
SUBROUTINE Name of user-supplied subroutine for calculating the
property. For details on writing the user-supplied subroutine,
see Aspen Plus User Models reference manual.
FLASH FLASH=NO Does not flash the stream before the
user-supplied subroutine is called
(Default)
FLASH= Does not flash the stream for total
NOCOMPOSITE stream properties (When PHASE=T in the
Prop-Set paragraph), but flashes for any
other phase specification
FLASH=YES Always flashes stream before the user-
supplied subroutine is called
UNIT-TYPE Units keyword for the property. If not entered, unit
conversion is not performed on property values returned from
the user-supplied subroutine.
Optional keywords:
FREE-WATER SOLU-WATER HENRY-COMPS
HENRY-COMPS henryid cid-list
HENRY-COMPS HC INI1
PROPERTIES POLYNRTL HENRY-COMPS=HC
PROP-DATA
IN-UNITS SI
PROP-LIST PLXANT / TB
PVAL HOPOLY -40.0 0 0 0 0 0 0 0 1D3 / 2000.0
PVAL COPOLY -40.0 0 0 0 0 0 0 0 1D3 / 2000.0
PROP-DATA
IN-UNITS SI
PROP-LIST MW
PVAL HOPOLY 1.0
PVAL COPOLY 1.0
PVAL ABSEG 192.17
PVAL ASEG 76.09
PVAL BSEG 116.08
PROP-DATA
IN-UNITS SI
PROP-LIST DHCONM / DHSUB / TMVK / TGVK
PVAL HOPOLY -3.64261D4 / 8.84633D4 / 1.0 / 0.0
PVAL COPOLY -3.64261D4 / 8.84633D4 / 1.0 / 0.0
PROP-DATA
IN-UNITS SI
PROP-LIST GMRENB / GMRENC
BPVAL MCH ASEG -92.0 / 0.2
BPVAL ASEG MCH 430.0 / 0.2
ESTIMATE [option]
STRUCTURES
method SEG-id groupno nooccur / groupno nooccur /...
The main keywords for specifying property parameter estimation inputs are
the ESTIMATE and the STRUCTURES paragraphs. A brief description of the
input language for these paragraphs follows. For more detailed information
please refer to the Aspen Physical Property System Physical Property Data
documentation.
option Option=ALL Estimate all missing parameters (default)
method Polymer property estimation method name
SEG-id Segment ID defined in the component list
groupno Functional group number (group IDs listed in Appendix B of
Volume 2 of this User Guide)
nooccur Number of occurrences of the group
ESTIMATE ALL
STRUCTURES
VANKREV ABSEG 115 1 ;-(C6H4)-
VANKREV BSEG 151 2 / 100 2 ; -COO-CH2-CH2-
COO-
VANKREV ABSEG 115 1 / 151 2 / 100 2 ;-(C6H4)-COO-CH2-CH2-
COO-
Specifying Step-Growth
Polymerization Kinetics
Following is the input language for the STEP-GROWTH REACTIONS paragraph.
Input Language for Step-Growth Polymerization
The keywords for specifying rate constant parameters for the built-in
reactions, and for specifying user reactions are described here.
Input Language Description for Step-Growth Polymerization
Specifying Free-Radical
Polymerization Kinetics
Following is the input language for the FREE-RAD REACTIONS paragraph. The
reaction keywords and rate coefficient parameters for free-radical
polymerization are given. Users may select a subset of the built-in reactions
for a given simulation.
Specifying Emulsion
Polymerization Kinetics
Following is the input language for the EMULSION REACTIONS paragraph.
Users are able to select the phases in which the reactions are occurring and
also define the kinetics of particle absorption, desorption, and termination.
Input Language for Emulsion Polymerization
Specifying Ziegler-Natta
Polymerization Kinetics
Following is the input language for the part of the polymerization REACTIONS
paragraph specific to Ziegler-Natta kinetics. Ziegler-Natta inputs may be used
to define the reaction kinetics for a wide variety of homo- and co-polymers
produced by catalyzed polymerization, including HDPE. A subset of the built-in
kinetics can be defined for a simulation by including the reaction keywords for
the desired reactions and specifying the rate coefficient parameters for these
SPECIES POLYMER=polymerid
STOIC reactionno compid coef / ...
RATE-CON reactionno pre-exp act-energy [t-exp] [TREF=ref-temp] &
[CATALYST=cid CAT-ORDER=value] [USER-RC=userid] / ...
POWLAW-EXP reactionno compid exponent /
[ASSIGN reactionno [ACTIVITY=value] RC-SETS=setno-list]
SUBROUTINE RATECON=rcname MASSTRANS=mtname
USER-VECS NINTRC=nintrc NREALRC=nrealc NINTMT=nintmt NREALMT=nrealmt &
NIWORKRC=niwork NWORKRC=nwork NIWORKMT=niwork NWORKMT=nwork &
NURC=nurc
INTRC value-list
REALRC value-list
INTMT value-list
REALMT value-list
Specifying Segment-Based
Polymer Modification Reactions
The input language for the SEGMENT-BAS REACTIONS paragraph is described
here.
Input Language for Segment-Based Polymer Modification Reactions
( C )k e
ij R T Tref
rate = j j oi
References
Aspen Physical Property System Physical Property Data. Cambridge, MA:
Aspen Technology, Inc.
Aspen Plus User Models. Cambridge, MA: Aspen Technology, Inc.
522 Index
emulsion model 195219 site-based aggregate polymers
end-use properties 72 42, 49
features 5, 913 site-based bulk polymers 48
files 373 site-based live polymers 41, 49
flowsheets 284 site-based polymers 39
fortran utilities 43559 specifying conventional
free-radical polymerization component 464
model 15994 user 45
input language 460520 variables for data regression 338
installation 373 Ziegler-Natta 44
ionic model 24155 Average properties 5657
key parameters 334
kinetic rate constant parameters B
42134
model definition 12 Backbone modifications 260
polyester technology package 91 Batch reactors 322
property approach 56 BatchFrac
reaction models 82 attribute handling 329
segment approach 27 Beta-scission 179
segment-based reaction model Bifunctional initiator decomposition
25681 167
steady-state features 285 Bifunctional initiators 170, 171
steady-state modeling 28285 Bimodal distributions 54
step-growth polymerization Bivariate distributions 53
model 85158 Block length 34
templates 373 Branch formation 261
troubleshooting 37477 Branching
unit operation models 286330 degree of 32
unit operations 285 free-radical polymerization 188
user models 83, 35165 frequency 34
user subroutines 13651, 265 number of chains 34
76 reactions 235
Ziegler-Natta model 22040 Broyden solver 303
Aspen PolyQuest 92 Bulk
AspenTech support 3 free-radical polymerization 159
AspenTech Support Center 3 94
Association reactions 248 polymer chain 165
Attributes See also Component polymer chain length moment
attributes equation 183
aggregate polymers 39, 48 polymerization 160
bulk polymers 46 Bulk polymerization 82
calculation methods 46 Butadiene 195
catalyst 44 Butyl acrylate 195
fortran utilities 43648 Butyl methacrylate 195
handling in unit operations 328
initialization scheme 4650 C
initializing in streams 465
CAELID 436
input language 43648
CAID 436
live polymers 38, 48
Calculator block 367
polymers 3536
CAMIX 437
required 43, 46
Case study block 368
scale factors 50
CASPLT 438
scaling 466
Index 523
CASPSS 438 precipitation 82
Catalyst sites solution 82
inhibited 226 suspension 82
propagation 226 Characterizing
types 226 approach 19
vacant 226 components 10, 12, 27
Catalysts Chlorinated polyethylene 256
poisoning 235 Chloroprene 195
preactivation 232 Class 0 component attributes 33,
site activation 232 45, 328
types 22124 Class 1 component attributes 33
Ziegler-Natta 24, 221 Class 2 component attributes 33,
Ziegler-Natta reactions 225 4546, 305, 328
Catalyzed initiation reaction 169 CMC See Critical micelle
Categorizing polymers 19 concentration
CAUPDT 439 Cocatalysts
Chain poisoning 235
initiation for ionic 247 Combination reactions 100, 261
initiation for Ziegler-Natta 232 Component attributes
scission 260 about 19
termination 249 aggregate polymer 33
Chain length available 3544
average properties 57 calculation methods 46
distribution 20, 34, 5758, 62 categories 34
first moment 46 class 0 33, 45
instantaneous weight distribution class 0 treatment in unit
60 operations 328
instanteous number-average 61 class 1 33
weight-average 61 class 2 33, 4546, 305
zeroth moment 46 class 2 treatment in unit
Chain size 53 operations 328
Chain transfer classes 33
dormant polymer formation 249 composite 34
ionic reactions 249 copolymer composition 32
spontaneous 234, 249 degree of branching 32
to agent 233, 249 degree of cross-linking 32
to cocatalysts 234 degree of polymerization 23, 32
to electron donor 234 emulsion polymerization 214
to hydrogen 234 for aggregate polymers 39, 48
to monomer 175, 234, 249 for blocks 51
to polymer 177 for bulk polymers 46
to small molecules 174, 233 for catalysts 33, 44
to solvent 174, 233 for composite aggregate
to transfer agent 174 polymers 35
Chain-growth polymerization for composite live polymers 34
bulk 82 for composite polymers 34
commercial polymers 81 for ionic initiators 32, 44
comparison to step-growth 79 for live polymers 38, 48
emulsion 82 for polymer properties 32
overview 80 for polymers 3435, 3536
524 Index
for site-based aggregate conventional 22
polymers 35, 42, 49 databanks 378420
for site-based bulk polymers 48 defining 12
for site-based live polymers 35, defining types 28
41, 49 fortran utilities 352, 43648,
for site-based polymers 35, 39 44854
43 input language 46064
for site-based species 44 ionic initiators 24
for streams 51 naming 28, 460
for structural properties 32 oligomers 23
for Ziegler-Natta catalysts 32 POLYMER databank 37882,
free-radical polymerization 187 37982
initialization 46, 51 polymers 22
initialization scheme 46 pure component databank 378
input language 43648 segment approach 27
ionic polymerization 252 SEGMENT databank 383420
live polymer 33 segments 24
molecular architecture 32 site-based 24
molecular weight 32 specifying 27
required 43, 46 specifying catalysts 46164
scale factors 50 specifying oligomers 46164
segment composition 32 specifying polymers 46164
segment-based reaction model specifying step-growth 153
264 Composition 8
sequence length 32 Condensation polymerization 78,
specifying 5152 122
specifying conventional 51 Condensation reactions 99
specifying conventional Configuring
attributes 464 Aspen Polymers 37273
specifying scale factors 52 Consumption of radicals 5960
specifying scaling factors 466 Continuous polymerization 88
step-growth polymerization 120 Conventional components 22
structural properties tracked 23 Conventional species 259
types 34 Convergence
unit operation model treatment for RCSTR 300
32830 improving 50
user-specified 45 initialization options (RCSTR)
Ziegler-Natta 44 306
Ziegler-Natta polymerization 236 parameter tuning 346
Component databanks RBatch troubleshooting 32427
about 25 RCSTR troubleshooting 3079
for initiators 26 RPlug troubleshooting 31519
for PC-SAFT 26 scaling factors (RBatch) 324
for polymers 11, 26 scaling factors (RCSTR) 304
for POLYPCSF 26 scaling factors (RPlug) 315
for pure components 25 solver method (RBatch) 326
for segments 11, 26 solver method (RPlug) 317
selecting 28 step size (RBatch) 326
Components step size (RPlug) 317
adding reacting 150 troubleshooting data regression
catalysts 24 34547
categories 2125 Conversion
characterizing 12 energy balance 303
Index 525
Copolymer applications 331
density 75 data collection 333
Copolymerization 61 data review 332
free-radical 15994 data verification 333
ionic 24155 features 285
ionic propagation 248 literature search 332, 333
user input for ionic model 246 model development 332, 335
user input for Ziegler-Natta model refinement 333, 336
model 231 parameters 33435
Ziegler-Natta 22040 preliminary fit 332, 33435
Copolymers 16 procedure 33236
COPYCA 440 trend analysis 333, 335
Coupling reactions 250 Data regression See also Data
CPACK 448 fitting
CPE See Chlorinated polyethylene activation energy 348
Critical micelle concentration 197 base-case model 337
Cross linking 261 choosing parameters 347
Cross-link formation 181 convergence problems 34547
Cross-linking 32, 34 data sets 337
Crystalline polymers 16 defining cases 337, 343
Crystallinity 8 entering data 337
Custom entering operating conditions
prop-sets 73 337
Custom models See User models, flowsheet variables 36971
See User models fortran blocks 339
customer support 3 interpreting results 34445
Cycle time 323 manipulating variables 339
Cyclodepolymerization reactions point data 341
100 procedure 33236, 33650,
33650
D profile data 342
Prop-Sets 339
DAMP-FAC 303 scaling fitted parameters 348
Damping factor 303 sensitivity studies 347
Data sequencing cases 344
collection 333 standard deviation 343
defining regression cases 343 troubleshooting 34547
fitting 33132 tuning 346
interpreting regression results Databanks
344 component 25, 378420
literature search 332, 333 functional group 11
point 337 INITIATOR 26
profile 337 PC-SAFT 26
regression 33132 polymer 11
review 332 POLYMER 26, 37882
sequencing regression cases 344 POLYPCSF 26
trend analysis 333, 335 pure component 25, 378
verification 333 segment 11
Data fitting See also Data SEGMENT 26, 382420
regression selecting 28
526 Index
Dead polymer 34 moment equation 18384
Dead polymer chain 165 moments 5657
Dead sites 44 particle size 21214
Dead zones 300, 313 plotting data 67, 68
Defining plug flow reactors 63
additional simulation options 13 polymer 62
components 12 procedure 65
feed streams 13 specifying calculations 6668
flowsheet options 12 specifying characteristics 66
global simulation options 12 streams 64
polymerization kinetics 13 structural property 5369
property models 13 tracking 62
regression cases 343 verification 65
UOS model operating conditions Distribution calculations
13 specifying input language 467
Degree of Dupl
branching 32, 53 about 28890
cross-linking 32 attribute handling 328
polymerization 32, 55 Duty
Density in RBatch 319
as polymer property 8 in RCSTR 297
function 5657 in RPlug 309
of copolymer 75 Dyads 34
Depolymerization 260 free-radical rate equation 184
Design-spec block 368 Dynamic models 10, 13
Desorption 209
Developing E
models 12
Direct esterification 86 EB-LOOP 303
Displaying e-bulletins 3
distribution data for reactors 67 Editing
distribution data for streams 67 emulsion reactions 217
distribution data tables 67 free-radical reactions 191
Disproportionation 176 ionic reactions 253
Distillation models segment-based reactions 279
about 293 user step-growth reactions 155
available 287 Ziegler-Natta reactions 239
RadFrac 293 Elastomers 16
Distribution Electrophilic reactions 97
average properties and moments Emulsion polymerization
5657 absorption 209
calcuations 467 accessing model 215
chain length 62 activated initiation 207
copolymerization 61 adding reactions 217
displaying data table 67 applications 195
displaying for reactors 67 aqueous phase 204
displaying for streams 67 assigning rate constants 217
functions 54, 56 attributes 214
GPC 64, 65 built-in reaction listing 216
in process models 56 chain growth 82
kinetic reactors 62 desorption 209
method of instantaneous editing reactions 217
properties 5861
Index 527
homogeneous nucleation 200 melt index 75
202 melt index ratio 76
industrial processes 196 relationship to structure 72
input language 49399 selecting 76
kinetics 196211, 207 zero-shear viscosity 74
kinetics scheme (figure) 200 Energy balance conversion 303
latex 198 Entering
latex reactions 203 point data 341
micellar nucleation 197200 profile data 342
model 195219 standard deviations 343
model assumptions 211 Equilibrium
model features 21114 for ionic polymerization 250
monomer partitioning 21112 for Ziegler-Natta polymerization
nomenclature 204 235
nucleation time 199 phase 184
particle growth 197, 202 reactions with counter-ion 248
particle number 199 reactor models 296
particle phase 206 Equilibrium models
particle size distribution 21214 RGibbs 296
population balance equation 213 RYield 296
products produced 196 Esterification
properties calculated 214 batch process 90
radical balance 2037 direct 86
rate constant 210 operating conditions 89
rate of particle formation 202 results 88
reactions 200 secondary 87
redox initiation 208 Estimating
seed process 202 property parameters 473
Smith-Ewart theory 207 Ethylene
specifying calculation options process types 222
218 Ethylene-propylene 221, 224
specifying gel-effect 218 Exchange reactions 248
specifying model 215
specifying particle growth F
parameters 219
specifying phase partitioning 218 Features 5, 913
specifying reacting species 216 Feed streams
stage I (seed) 198 defining 13
stage II (growth) 198, 202 with polymers 23, 46
stage III (finishing) 198 Files
user profiles 214 startup 373
End group reformation reactions Fitting
100 activation energy 348
End-use properties choosing parameters 347
about 7076 Flash2
adding a Prop-Set 76 about 290
calculating 73, 76 attribute handling 329
density of copolymer 75 input variables 339
input language 46870 results variables 339
intrinsic viscosity 74 Flash3
528 Index
about 290 linking 374
attribute handling 329 monitors 352
input variables 339 templates 374
results variables 339 utilities 352, 43559
Flowsheeting options 11 Fortran blocks
Flowsheets in data regression 339
basic unit operation models 286 to enforce assumptions 339
calculation procedure 367 to manipulate process variables
calculator block 367 340
case studies 368 to scale paramters 349
design-spec block 368 Fortran utilities
distillation models 287, 293 CAELID 436
Dupl block 28890 CAID 436
equilibrium reactor models 296 CAMIX 437
Flash2 block 290 CASPLT 438
Flash3 block 290 CASPSS 438
fractionation models 287 CAUPDT 439
FSplit block 291 component handling 352
Heater block 291 COPYCA 440
incorporating spreadsheets 367 CPACK 448
kinetic reactor models 296327 for component attributes 43648
mass-balance reactor models for components 44854
29496 for mixture molar volume 458
Mixer block 291 for streams 45459
model configuration tools 367 GETCRY 440
69 GETDPI 443
Mult block 291 GETDPN 441
optimization 369 GETMWN 442
Pipe block 292 GETMWW 443
polymer process 284 GETSMF 444
process studies 36769 GETSWF 445
Pump block 292 IFCMNC 449
RadFrac block 293 IPTYPE 454
RBatch block 31927 ISCAT 449
RCSTR block 296309 ISINI 450
reactor models 288, 294 ISOLIG 450
REquil block 296 ISPOLY 451
RGibbs block 296 ISSEG 451
RPlug block 30919 LCAOFF 446
RStoic block 294 LCATT 446
RYield block 295 LOCATS 455
sensitivity study 368 LPHASE 456
Sep block 293 NCAVAR 447
Sep2 block 293 NPHASE 456
setting fixed variables 368 NSVAR 457
steady-state 28285 SCPACK 452
stream manipulators 286 SSCOPY 457
unit operation models 286330 stream handling 352
variables 36971 VOLL 458
variables for data regression XATOWT 453
36971 XATOXT 453
Fortran Fractionation models 287
arguments 43559 Free-radical iniators
Index 529
decomposition rate parameters solution 160
42123 specifying calculation options
Free-radical polymerization 192
accessing model 189 specifying gel-effect 192
adding reactions 191 specifying model 190
applications 159 specifying reacting species 190
beta-scission reactions 179 specifying reactions 191
bifunctonal initiator specifying user profiles 193
decomposition reaction 170, structural properties 188
171 termination reactions 17475
branching 188 user profile properties 188
built-in reaction listing 190 Frequency function 5657
bulk 160 FSplit
bulk polymer chain length about 291
moment equation 183 attribute handling 328
calculation method 182 Functional group databank 11
catalyzed initiation reaction 169
chain transfer reactions 174 G
dyads 184
editing reactions 191 Gas-phase process 222
gel effect 166 Gear integrator 315, 324
gel effect 18486 Gel effect
induced initiation reaction 169 built-in correlations 185
industrial processes 160 free-radical 166
initiation reactions 167 free-radical polymerization 184
initiator decomposition reaction 86
168 specifying 192, 218
input language 48293 user specified correlations 186
kinetics 16179 user subroutine arguments 186
kinetics nomenclature 162 Gel effect subroutine
kinetics scheme (figure) 161 free-radical 166
live polymer chain length Gel permeation chromatography 64
moment equation 183 Generation of radicals 59
model 15994 GETCRY 440
model assumptions 18287 GETDPI 443
model features 18287 GETDPN 441
modifying the rate expression GETMWN 442
166 GETMWW 443
moment-property relationship GETSMF 444
equation 187 GETSWF 445
parameters 18789 Glycol recovery 87
pendent double bond GPC 64
polymerization 181
phase equilibrium 184 H
propagation reactions 172
HDPE See High density
properties calculated 18789
polyethylene
quasi-steady-state
Heat exchangers 299
approximation 184
Heater
rate constant 166
about 291
reactions 161
attribute handling 329
530 Index
help desk 3 ionic 44, 243
Heterogeneous catalysts 221 reaction for catalyzed 169
High density polyethylene reaction for decomposition 168
about 220 reaction for induced 169
processes 222 redox 208
High impact polypropylene 224 INITIATOR databank
HIPP See High impact about 26
polypropylene Initiators
Hold-up databank 26
in RCSTR 297 free-radical 42123
Homogeneous catalysts 221 ionic 24
Homogeneous nucleation Injection ports 314
particle formation 197 Input language
process 200202 attribute scaling factors 466
rate of particle formation 202 catalysts 46164
Homopolymers 15 component attributes 43648
components 46064
I conventional component
attributes 464
IFCMNC 449 distribution calculations 467
INCL-COMPS 150 emulsion 49399
Induced initiation reaction 169 end-use properties 46870
Industrial applications for Aspen Polymers 460520
polymer production steps 282 free-radical 48293
84 ionic 51017
polymer production steps oligomers 46164
(figure) 282 physical properties 47074
Industrial processes polymers 46164
emulsion polymerization 196 property data 471
free-radical polymerization 160 property methods 470
ionic polymerization 242 property parameter estimation
model uses 366 473
segment-based reaction model prop-set 46870
257 segment-based reactions 51721
step-growth polymerization 86 step-growth 47482
Ziegler-Natta polymerization 221 streams 465
Inhibited sites 226 Ziegler-Natta 499509
Inhibition Input variables
catalyst sites 44, 234 Flash2 339
Initators Flash3 339
for ionic polymerization 246 MultiFrac 339
Initialization RadFrac 339
hybrid option 307 RBatch 338
integration option 306 RCSTR 338
options for RCSTR 306 RPlug 339
solver option 306 standard deviations 343
Initiation Installing
activated 207 Aspen Polymers 373
catalyzed 167 Instantaneous
decomposition rate 167 number-average 61
free-radical 168, 170, 171 properties 56, 5861, 62
free-radical polymerization 167 weight chain length 6061
induced 167 Interfacial processes 82
Index 531
Intermolecular reactions 99 ISSEG 451
Intramolecular reactions 99
Intrinsic viscosity 74 K
Ionic initiator 24
Ionic initiators Kinetic models
component attributes 32 RBatch 31927
properties tracked 44 RCSTR 296309
Ionic polymerization RPlug 30919
accessing model 252 Kinetics
active species formation 246 data fitting 33132
adding reactions 253 decomposition rate parameters
aggregation 248 42123
applications 241 defining polymerization 13
assigning rate constants 254 emulsion (input language) 493
association 248 99
built-in reaction listing 253 emulsion polymerization 196
chain initiation 247 211, 207
chain termination 249 free-radical (input language)
chain transfer 249 48293
comparison to other addition free-radical polymerization 161
processes 242 79
copolymerization steps 246, 248 ionic (input language) 51017
coupling 250 ionic polymerization 24250
editing reactions 253 mechanisms 10
equilibrium with counter-ion 248 melt polycarbonate 11820
exchange 248 multi-site 63
industrial processes 242 nylon reactions 10718
initiator attributes 243 parameter influence on 334
initiator types 246 polyester reactions 1017
input language 51017 polymerization 78
kinetics scheme 24250 rate constant parameters 421
kinetics scheme (figure) 244 34
model 24155 reactor models 296327
model assumptions 25051 segment-based reaction model
model features 25051 261
nomenclature 245 single-site 63
phase equilibria 250 specifying emulsion 21519
polymers tracked 243 specifying free-radical 18993
propagation 247 specifying ionic 25254
properties calculated 25152 specifying step-growth 5152
rate calculations 250 specifying step-growth (input
rate constants 246 language) 47482
reactions 244 specifying Ziegler-Natta 23739
specifying model 252 step-growth polymerization 97
specifying reacting species 252 120
IPTYPE 454 user fortran arguments 43559
ISCAT 449 user models 35761
ISINI 450 user subroutine (example) 358
ISOLIG 450 user subroutines 145
ISPOLY 451
532 Index
Ziegler-Natta (input language) processes 81
499509 Metallocene catalysts 221
Ziegler-Natta polymerization Method of instantaneous properties
22535 56, 5861, 62
Method of moments 56, 182
L Methylmethacrylate 195
Micellar nucleation 197200
Latex MIXED
definition 198 substream variables 370
number of particles per liter 199 Mixer
reactions 203 about 291
LCAOFF 446 attribute handling 329
LCATT 446 Mixing
Linear condensation polymers 55 non-ideal in RCSTR 298
Linear low density polyethylene non-ideal in RPlug 312
about 220 Modeling
processes 222, 223 applications 85, 159, 195, 220,
Linking 241, 256
fortran 374 data fitting 285, 33132
Liquid enthalpy enforcing assumptions 339
user subroutine (example) 363 features 285
Liquid process 223 nylon 9296
Live nylon-6,6 112
polymer chain 165 polycarbonates 9697
polymer chain length moment polyesters 8692
equation 183 polymer phase change 295
Live polymer 33, 34 polymer processes 284
LLDPE See Linear low density steady-state 28285
polyethylene tools 285
Local work arrays 151, 275 unit operations 285, 286330
LOCATS 455 Models
Low density polyethylene 160 accessing variables 36971
Low molecular weight polymer 55 analysis tools 36769
LPHASE 456 application tools 36671
base case 337
M calculations for user models
35257
Mass balance 303
defining 12
Mass-balance models
developing 332, 335
RStoic 294
parameter fitting 33435
RYield 295
possible uses 366
Material streams 46
process studies 36769
MB-LOOP 303
refining 333, 336
Melt index 8, 75
structure for user models 351
Melt index ratio 76
trend analysis 333, 335
Melt polycarbonate
unit operation 11
rate constants 119
user 35165
reaction components 118
USER2 routine 354
reaction kinetics 11820
Molar volume
step-growth reactions 119
fortran utilities 458
Melt-phase
Molecular structure
nylon-6,6 processes 118
SEGMENT databank 383420
polymerization 96
Molecular weight
Index 533
as component attribute 32 period 198
distribution 8, 56 time 198
number-average 75 time (equation) 199
weight-average 34, 75 Nucleophilic reactions
Moment equations about 97
bulk polymer 183 nomenclature 99
general 182 Number average
live polymer 183 chain length distribution 61
relationship to properties 187 degree of polymerization 55
Moments of chain length Number-average
distribution degree of polymerization 34
first 38, 46 Nylon
Monomers aqueous salt solutions 94
corresponding segment formulas melt-phase polymerization 96
123 production process 9296
definition 15 salt preparation 94
functional groups 125 Nylon-6
partitioning 21112 production process 92
purification 283 rate constants 109
synthesis 28384, 283 reaction components 108
Most-probable distribution 55, 110, reaction kinetics 107
116, 127 step-growth reactions 108
Mult user-specified reactions 109
about 291 Nylon-6,6
attribute handling 329 melt-phase polymerization 118
MultiFrac modeling approaches 112
attribute handling 329 production process 94
input variables 339 rate constants 114, 115
results variables 339 reaction components 112
Multimodal distributions 54 reaction kinetics 111
step-growth reactions 113
N user-specified reactions 116
NCAVAR 447
O
Newton solver 303
Nomenclature Occupied sites 44
for emulsion model 204 Oligomers
for free-radical model 162 as components 23
for ionic model 245 definition 15
for segment-based reaction fractionation 126
model 262 segments 24
for step-growth model 99 specifying 30
for Ziegler-Natta model 229 Optimization 369
POLYMER databank 37982 Orienticity 34
SEGMENT databank 382
NPHASE 456 P
NSVAR 457
Nucleation Packed vectors 151, 275
homogeneous 197, 200202 Parameters
micellar 197200 data fitting 33132
decomposition rate 42123
534 Index
estimating property 473 Polybutylene terephthalate 91
fitting 332, 33435 Polycarbonates
for free-radical polymerization aliphatic 85
18789 aromatic 85
influence of kinetics 334 production process 9697
integer 151, 275 reaction kinetics 11820
kinetic rate constant 42134 Polydispersity
POLYMER property 378 index 61
real 151, 275 Polyesters
scaling 348 assigning rate constants 104
SEGMENT property 382 polyester technology package 91
to manipulate process variables production process 85, 8692
340 reaction components 102
tuning for data regression 346 reaction kinetics 1017
Particle growth side reactions 105
in emulsion polymerization 202 step-growth reactions 103
specifying parameters 219 user-specified reactions 106
PBT See Polybutylene Polyethylene
terephthalate chlorinated 256
PC-SAFT low density 160
databank 26 Polyethylene naphthalate 91
PC-SAFT databank Polyethylene terephthalate
about 26 batch processes 8991
PEN See Polyethylene naphthalate continuous step-growth
Pendent double bond polymerization 8689
polymerization 181 solid-state models 92
PET See Polyethylene terephthalate Polyisobutylene 241, 256
Phase equilibria Polymer chain
ionic polymerization 250 bulk 165
step-growth polymerization 122 dead 165
Ziegler-Natta polymerization 235 definition 165
Phase equilibrium live 165
free-radical polymerization 184 POLYMER databank
Phase partitioning about 11, 26, 378
specifying 218 components 37982
Physical properties nomenclature 37982
calculations in user models 356 Polymerization
fitting parameters 33435 addition 78
input language 47074 bulk 82
user models 36165 chain-growth 79, 80
user subroutine (example) 363 condensation 78
Pipe 292 condensation polymerization 122
Plant data fitting 33132 continuous 88
Plot degree of 32
distribution data 67, 68 emulsion 82, 195219
PMMA See Polymethyl free-radical 15994
methacrylate interfacial 82
Point data ionic 24155
about 337 kinetics 10, 13, 78
entering 341 manufacturing step 284
Polyamides 86 melt phase 81
Polybutadiene 241 precipitation 82
Polybutene 241 process overview 67
Index 535
process types 81 ionic properties calculated 251
reaction types 78 52
reactions 78 ladder 16
solid-state 81 linear 16
solution 82 linear condensation 55
step-growth 79, 80, 85158 linear low density polyethylene
suspension 82 220
Ziegler-Natta 22040 live 33, 34
Polymers live polymer chain length
acrylic acid 195 moment equation 183
addition 55 low density polyethylene 160
aggregate 33, 34 low molecular weight 55
aliphatic polycarbonates 85 mass 120, 264
amorphous 16 method of instantaneous
aromatic polycarbonates 85 properties 56, 58, 62
as components 23 method of moments 56
average properties and moments methylmethacrylate 195
5657 mole fraction 263
branched 16 monomer purification 283
bulk polymer chain length monomer synthesis 28384, 283
moment equation 183 network 16
butadiene 195 nomenclature 37982
butyl acrylate 195 phase change 295
butyl methacrylate 195 polyamides 86
by chemical structure 18 polybutadiene 241
by physical structure 16 polybutene 241
by property 17 polyesters 85
chain-growth 81 polyisobutylene 241, 256
characterizing 19 polymerization step 284
chlorinated polyethylene 256 polymethyl methacrylate 160,
chloroprene 195 256
component attribute sets 3435 polyoxides 241
component attributes 32, 34 polypropylene 221
component characterization 10 polystyrene 159, 160, 241
crystalline 16 polyurethanes 86
data fitting procedure 33236 polyvinyl acetate 159
data regression procedure 336 polyvinyl alcohol 160, 256
50 polyvinyl chloride 159
dead 34 processing 67
definition 6 processing step 284
elastomers 16 production rate 60
emulsion properties calculated production steps 28284
214 properties 19
end-use properties 7076 properties tracked 34
ethylene-propylene 221 property distributions 5369
free-radical properties calculated property parameters 378
18789 prop-sets 71
high density polyethylene 220 purification 28384
high-impact polystyrene 159 reacting 257
recovery 9, 284
536 Index
segment-based properties dynamic 10, 13
calculated 264 features 285
segments 24, 382 flowsheets for polymer processes
separation 9, 284 284
specifying 29 issues for polymers 79
star 16 steady-state 10, 13, 28285
step-growth 80 tools 285
structural properties 23 unit operations 285
structure 15 Processing
structure of 1519 polymers 284
styrene 195 Profile data
synthesis 284 about 337
tetrafluroethylene 195 data sets 342
thermoplastics 16 entering 342
thermosets 16 RBatch 342
tracking structural properties 32 RPlug 342
vinyl chloride 195 Propagation
vinylacetate 195 depolymerization 260
Ziegler-Natta properties free-radical polymerization 172
calculated 236 ionic polymerization 247
Polymethyl methacrylate 160, 256 segment-based reaction model
Polyoxides 241 261
POLYPCSF sites 226
databank 26 Ziegler-Natta polymerization 233
POLYPCSF databank Properties
about 26 average polymer 5657
Polypropylene branching 23
about 221 chain size 53
process types 223 composition 8
Polypropylene terephthalate 91 copolymer composition 23, 53
Polystyrene 159, 160, 241 copolymerization 61
Polyurethanes 86 crystallinity/density 8
Polyvinyl acetate 159 degree of branching 53
Polyvinyl alcohol 160, 256 degree of polymerization 23
Polyvinyl chloride 159 density of copolymer 75
Population balance end-use 7076
equation for emulsion estimating parameters 473
polymerization 213 for polymers 56
equation for free-radical input language 47074
polymerization 182 intrinsic viscosity 74
Potential sites 44 melt index 8, 75
Power-law reaction model See melt index ratio 76
Segment-based reaction method of instantaneous 58
model:about molecular structure 23
PPT See Polyproylene terephthalate molecular weight 23
Precipitation polymerization 82 molecular weight 8
Pressure moments of molecular weight
drop 297, 310 distribution 23
in RBatch 320 particle size 53
in RCSTR 297 polymer structural 32, 53
in RPlug 310 prop-set 71
Process modeling segment composition 23
data fitting 285 specifying data 471
Index 537
viscosity 8 absorption 206
zero-shear viscosity 74 balance 2037
Property distributions consumption of 5960
bimodal 54 depletion 204
bivariate 53 desorption 206
most-probable 55 generation 204
multimodal 54 generation of 59
Schulz-Flory 54 rate of production 204
Stockmayer bivariate 56 termination 206
structural 5369 Random scission 100
types 53 Rate constant parameters
unimodal 54 data-fitting 285
Property methods Rate constants
input language 470 assigning to emulsion reactions
Property parameter databanks 11 217
Property set See also Prop-Sets assigning to ionic reactions 254
Prop-Sets assigning to step-growth
adding 76 reactions 154, 156
custom 73 assigning to Ziegler-Natta
defining 71 reactions 239
for data regression 339 data fitting 331
for polymers 71 emulsion 210
properties 71 for melt polycarbonate 119
uses 71 for model generated reactions
Propylene 131
processes 223, 224 for nylon-6 109
Pseudocondensation reactions 99 for nylon-6,6 114, 115
Pump 292 for polyesters 104
Pure components for user-specified reactions 135,
databank 25, 378 280
Purification free-radical 166
monomer 283 ionic 246
process step 28384 kinetic parameters 42134
PVA See Polyvinyl alcohol segment-based 261
specifying for segment-based
Q power-law reactions 279
specifying for step-growth user
QSSA See Quasi-steady-state reactions 155
approximation step-growth 149
Quasi-steady-state approximation user subroutines 140, 270
184 Ziegler-Natta 231
Rate expression
R step-growth 129, 134
RBatch
RadFrac
about 31927
about 293
attribute handling 330
attribute handling 329
batch reactors 322
input variables 339
common problems 327
results variables 339
cycle time 323
Radiation initiation reaction 169
duty 319
Radicals
538 Index
dynamic scaling 324 specifying for step-growth 156
hybrid scaling options 325 Reacting polymers 257
input variables 338 Reaction models
pressure 320 Aspen Plus 83, 35157
profile data 342 available 35157
residence time 321 basic unit operation 286
results variables 338 built-in 82
scaling options 324 custom 83
semi-batch reactors 322 distillation 287, 293
solver method 326 Dupl 28890
specifying user profiles 193 equilibrium 296
static scaling options 324 Flash2 290
step size 326 Flash3 290
streams 322 fractionation 287
temperature 319 FSplit 291
troubleshooting convergence generic 83
32427 Heater 291
volume 321 kinetic 296327
RCSTR mass-balance 29496
about 296309 Mixer 291
algorithm 300 Mult 291
attribute handling 330 Pipe 292
calculation loops 301 Pump 292
calculation table 301 RadFrac 293
common problems 308 RBatch 31927
component scaling 305 RCSTR 296309
condensed phases 297 reactor 288, 294
convergence 300 REquil 296
duty 297 RGibbs 296
effective hold-up 297 RPlug 30919
external heat exchanger 299 RStoic 294
horizontal partition 298 RYield 295
hybrid initialization 307 Sep 293
initialization options 306 Sep2 293
input variables 338 stream manipulators 286
integration initialization 306 treatment of component
multiphase 297 attributes 32830
non-ideal mixing 298 Reactions
pressure 297 active species 246
residence time 297 adding emulsion 217
results variables 338 adding free-radical 191
scaling options 304 adding ionic 253
single-phases 297 adding segment-based 279
solver initialization 306 adding user 155
substream scaling 305 adding Ziegler-Natta 238
temperature 297 addition 99
troubleshooting convergence aggregation 248
3079 assigning emulsion rate
vertical partition 299 constants 217
with dead zone 300 assigning ionic rate constants
Reacting phase 254
specifying for segment-based assigning step-growth rate
power-law model 277 constants 154
Index 539
assigning user rate constants homogeneous nucleation 200
156 including user 154
assigning Ziegler-Natta rate induced initiation 167, 169
constants 239 Inhibition 177
association 248 initiator decomposition 167, 168
backbone 260 intermolecular 99
beta-scission 179 intramolecular 99
bifunctional initiator ionic polymerization 244
decomposition 170, 171 latex 203
branching (segment-based) 261 melt polycarbonate kinetics 118
branching (Ziegler-Natta) 235 20
catalyst preactivation 232 micellar nucleation 197
catalyst site activation 232 micellar nucleation (figure) 198
catalyzed initiation 167, 169 modification See Segment-based
chain initiation (free-radical 167 reaction model
chain initiation (ionic) 247 nucleophilic 97
chain initiation (Ziegler-Natta) nylon-6 kinetics 107
232 nylon-6,6 kinetics 111
chain scission 260 particle growth 202
chain termination (free-radical) polyester kinetics 1017
17475 polymerization 78
chain termination (ionic) 249 propagation (free-radical) 172
chain transfer (free-radical) 174 propagation (ionic) 247
chain transfer (ionic) 249 propagation (segment-based)
chain transfer (Ziegler-Natta) 261
233 propagation (Ziegler-Natta) 233
chain-growth 80 pseudocondensation 99
classifying 78 radiation initiation 169
cocatalyst poisoning 235 radical balance 203
combination 100, 261 rearrangement 100
condensation 99 reverse condensation 99
conventional species 259 ring addition 100
coupling 250 ring closing 100
cross linking 261 ring opening 100
cyclodepolymerization 100 side group 260
depolymerization 260 site deactivation 234
editing emulsion 217 site inhibition 234
editing free-radical 191 specifying segment-based 276
editing ionic 253 80
editing segment-based 279 specifying user rate constants
editing user 155 155
editing Ziegler-Natta 239 spontaneous initiation 169
electrophilic 97 step-growth 80
emulsion polymerization 200 step-growth functional groups
end group reformation 100 124
equilibrium with counter-ion 248 step-growth polymerization 100
exchange 248 step-growth rate constants 154
for step-growth polymerization supplied by emulsion model 211
122 14
free-radical polymerization 161
540 Index
supplied by free-radical model with injection ports 314
18287 Rearrangement reactions 100
supplied by ionic model 250 Recovery/separation 9, 284
supplied by segment-based Redox initiation 208
model 264 Regression See Data regression
supplied by step-growth model Reports
12934 for user models 357
supplied by Ziegler-Natta model step-growth options 156
236 REquil
terminal double bond 235 about 296
termination (free-radical) 174 attribute handling 330
75 Residence time
termination (ionic) 249 RBatch 321
thermal initiation 169 RCSTR 297
types affecting catalyst states RPlug 311
225 Results variables
user-specified step-growth 134 Flash2 339
36 Flash3 339
viewing emulsion 216 MultiFrac 339
viewing free-radical 190 RadFrac 339
viewing ionic 253 RBatch 338
viewing segment-based 278 RCSTR 338
viewing step-growth 153 RPlug 339
viewing Ziegler-Natta 238 standard deviations 343
Ziegler-Natta polymerization 227 Reverse condensation reactions 99
Reactor models Rgibbs
about 294 about 296
available 288 RGibbs
data sets 342 attribute handling 330
equilibrium 296 Ring addition reactions 100
input variables 338 Ring closing reactions 100
kinetic 296327 Ring opening reactions 100
mass-balance 29496 Routines
results variables 338 USER2 354
Reactors RPlug
condensed phase RCSTR 297 about 30919
convergence problems for attribute handling 330
RBatch 32427 common problems 318
convergence problems for RCSTR duty 309
3079 dynamic scaling 315
convergence problems for RPlug hybrid scaling 317
31519 input variables 339
displaying distribution data 67 multiphase 312
distribution 62 non-ideal mixing 312
horizontal partition 298 pressure 310
multiphase RCSTR 297 profile data 342
multiphase RPlug 312 residence time 311
RCSTR algorithm 300 results variables 339
single-phase RCSTR 297 scaling options 315
vertical partition 299 solver method 317
with dead zones 300, 313 specifying user profiles 193
with external heat exchanger static scaling options 315
299 step size 317
Index 541
temperature 309 including user rate constant
troubleshooting convergence subroutine 280
31519 Segment-based power-law model
with dead zone 313 specifying reacting phase 277
with injection ports 314 user subroutines 26576
Rstoic Segment-based reaction model
about 294 about 25681
RStoic accessing 276
attribute handling 329 adding reaction schemes 278
Ryield adding reactions 279
about 295 applications 256
RYield assumptions 263
attribute handling 329 backbone modifications 260
branch formation 261
S chain scission 260
combination 261
Salt conventional species 259
aqueous solutions 94 cross linking 261
preparation 94 depolymerization 260
Scale factors editing reactions 279
about 50 features 263
specifying 52 including user basis subroutine
Scaling 281
factors 466 industrial processes 257
Scaling factors input language 51721
component (RCSTR) 305 kinetics 261
dynamic (RBatch) 324 mole fraction conversion 263
dynamic (RPlug) 315 nomenclature 262
hybrid (RBatch) 325 propagation 261
hybrid (RPlug) 317 properties calculated 264
RBatch 324 rate calculations 264
RCSTR 304 rate constants 261
RPlug 315 reaction categories 25863
static (RBatch) 324 reactions allowed 25863
static (RPlug) 315 side group modifications 260
substream (RCSTR) 305 specifying model 276
Schulz-Flory distribution 54 specifying pre-exponential units
Scission 100, 260 279
SCPACK 452 specifying rate constants 279
Secondary esterification 87 specifying reaction settings 277
Seed process 202 Segments
Segment approach 27 composition 15, 32
SEGMENT databank copolymers 16
about 11, 26, 382 definition 24
components 383420 homopolymers 15
nomenclature 382 methodology in Aspen Polymers
Segment flow 34 27
Segment fraction 34 mole fraction 263
Segment-based model molecular structure 383420
assigning rate constants 280 nomenclature 382
542 Index
property parameters 382 components (input language)
sequence 15 46064
specifying 29 conventional component
structure 15 attributes 51, 464
types 24 data fit 33236
Semi-batch reactors 322 data regression 33650
Semi-crystalline copolymer density databanks 28
75 distribution calculations 6668
Sensitivity blocks 368 distribution calculations (input
Sep language) 467
about 293 distribution characteristics 66
attribute handling 328 emulsion calculation options 218
Sep2 emulsion kinetics 21519
about 293 emulsion kinetics (input
attribute handling 328 language) 49399
Separation/recovery 9, 284 emulsion model 215
Side group modifications 260 emulsion rate constants 217
Simulations emulsion reacting species 216
dynamic 10 end-use properties 76
templates 373 end-use properties (input
Site activation 232 language) 46870
Site deactivation 234 feed streams 13
Site inhibition 234 fixed process variables 368
Site-based components flowsheet options 12
about 24 free-radical calculation options
attributes 44 192
specifying 30 free-radical kinetics 18993
Slurry process 222, 223 free-radical kinetics (input
Smith-Ewart theory 207 language) 48293
Solid-state models 92 free-radical model 190
Solid-state processes 81 free-radical reacting species 190
Solution polymerization 82, 160 gel-effect 192, 218
Solution process 222 global simulation options 12
Solution processes 82 ionic kinetics 25254
Solver methods ionic kinetics (input language)
RBatch 326 51017
RPlug 317 ionic model 252
Specifying ionic rate constants 254
additional simulation options 13 ionic reacting species 252
Aspen Polymers options 37273 oligomers 30, 46164
attribute scaling factors (input particle growth parameters 219
language) 466 phase partitioning 218
catalysts 46164 physical properties (input
component attributes 5152 language) 47074
component attributes (input point data 341
language) 43648 polymerization kinetics 13
component attributes in blocks polymers 29, 46164
51 pre-exponential units 157, 279
component attributes in streams profile data 342
51 property data 471
component names 460 property models 13
components 12, 27 reacting phase 277
regression cases 343
Index 543
scale factors 52 flowsheeting 28285
segment-based reaction model tools 285
276 unit operation 286330
segment-based reaction rate unit operations 285
constants 279 Step-growth polymerization
segment-based reaction scheme accessing model 152
278 adding user reactions 155
segment-based reaction settings addition processes 257
277 applications 85
segment-based reactions 27680 Aspen PolyQuest 92
segment-based reactions (input assigning rate constants 131,
language) 51721 135, 154, 156
segments 29 batch PET 8991
site-based components 30 built-in reaction listing 153
standard deviations 343 commercial polymers 80
step-growth components 153 comparison to chain-growth 79
step-growth kinetics 5152 continuous PET 8689
step-growth kinetics (input editing user reactions 155
language) 47482 electrophilic reactions 97
step-growth model 152 functional groups 124, 125
step-growth rate constants 154, including user basis subroutine
155, 156 157
step-growth reacting phase 156 including user kinetic subroutine
step-growth report options 156 157
stream attributes 465 including user rate constant
UOS model operating conditions subroutine 157
13 including user reactions 154
user models 35165 industrial processes 86
user profiles 193 input language 47482
user step-growth reactions 154 interfacial 82
Ziegler-Natta kinetics 23739 kinetics 97120
Ziegler-Natta kinetics (input melt phase 81
language) 499509 melt polycarbonate reaction
Ziegler-Natta model 237 kinetics 11820
Ziegler-Natta rate constants 239 model 85158
Ziegler-Natta reacting species model features 12023
237 model predictions 120
Spontaneous initiation reaction 169 model structure 12351
Spreadsheets model-generated reactions 129
incorporating in flowsheets 367 34
SSCOPY 457 nomenclature 99
SSplit nucleophilic reactions 97
attribute handling 328 nylon 9296
Standard deviations 343 nylon-6 reaction kinetics 107
Starting nylon-6,6 reaction kinetics 111
Aspen Polymers 37273 oligomer fractionation 126
Startup files 373 overview 80
Steady-state models PBT 91
data fitting 285 PEN 91
features 285 phase equilibria 122
544 Index
polycarbonates 9697 of polymers 1519, 19, 23
polyester reaction kinetics 1017 of segments 15, 24
polyester technology package 91 propertyend-use relationship 72
polyesters 8692 Styrene 195
PPT 91 Subroutines
rate constants 118, 129, 149 fortran arguments 43559
rate constants example 149 including user basis 157, 281
rate expression 129, 134 including user kinetic 157
reacting groups 123 including user rate constant 157,
reacting species 123, 126 280
reaction mechanism 122 local work arrays 151, 275
reaction stoichiometry 128 updating component list 150
reactions 100 user 13651, 26576
solid-state 81 user basis 136, 263, 266
solid-state models 92 user forms 152
solution 82 user gel effect 186
specifying components 153 user kinetic (example) 358
specifying model 152 user kinetics 145
specifying pre-exponential units user property (example) 363
157 user rate constant 140, 270
specifying rate constants 154, support, technical 3
155 Suspension polymerization 82
specifying reacting phase 156 Synthesis
specifying report options 156 monomer 283
specifying subroutines 157 polymer 284
user reactions 134
user subroutines 13651 T
Stockmayer bivariate distribution
56 tacticity 34
Stoichiometry TDB See Terminal double bond
step-growth 128 technical support 3
Streams Temperature
continuous batch charge 322 in RBatch 319
defining feed 13 in RCSTR 297
displaying distribution data 67 in RPlug 309
distributions 64 Templates
fortran utilities 45459 custom 373
initializing attributes 465 fortran 374
manipulating 286 simulation 373
MIXED variables 370 Terminal double bond reactions
processing in user models 353 235
RBatch 322 terminal double bonds 34
time-averaged continuous Terminal models
reactor product 323 free-radical 165
time-averaged continuous vent Ziegler-Natta 231
product 323 Terminal monomer loss 100
time-varying continuous feed Termination
323 between chain radicals 177
variables for data regression 338 bimolecular 177
Structure by combination 176
of components 22 disproportionation 176
of monomers 15 free-radical polymerization 174
of oligomers 15, 23 75
Index 545
inhibition 177 property calculations 356
Tetrafluroethylene 195 Pump 292
Thermal initiation reaction 169 RadFrac 293
Thermoplastics 16 RBatch 31927
Thermosets 16 RCSTR 296309
Tips reactor models 288, 294
configuration 373 reports 357
data regression 34547 REquil 296
Transesterification 88 results variables 338
Trommsdorff effect 185 RGibbs 296
Troubleshooting RPlug 30919
Aspen Polymers 37477 RStoic 294
convergence (RBatch) 32427 RYield 295
convergence (RCSTR) 3079 Sep 293
convergence (RPlug) 31519 Sep2 293
data regression convergence steady-state models 286330
34547 stream processing 353
diagnostic messages 356 treatment of component
RBatch common problems 327 attributes 32830
RCSTR common problems 308 user model calculations 35257
RPlug common problems 318 user model structure 351
simulation engine 376 user models 35157
user interface 374 variables for data regression 338
USER 351, 357
U User attributes
properties tracked 45
Unimodal distributions 54 User fortran
Unit operation models 11 arguments 43559
Unit operations linking 374
Aspen Plus models 35157 templates 374
available models 35157 User models
basic models 286 about 35165
calculations 356 calculations 35257
diagnostics 356 component list 150
distillation models 287, 293 diagnostics calculations 356
Dupl 28890 integer parameters 151, 275
equilibrium reactor models 296 kinetic 35761
features 285 packed vectors 151, 275
Flash2 290 physical property 36165
Flash3 290 property calculations 356
fractionation models 287 real parameters 151, 275
FSplit 291 reports 357
Heater 291 stream processing 353
input variables 338 structure 351
kinetic reactor models 296327 unit operation 35157
mass-balance reactor models unit operation calculations 356
29496 USER block 351
Mixer 291 USER2 block 351
Mult 291 User profiles
Pipe 292 for emulsion polymerization 214
546 Index
specifying 193 in RBatch 321
User prop-sets 73
User reactions W
adding step-growth 155
assigning rate constants for web site, technical support 3
step-growth 156 Weight average
editing step-growth 155 chain length 61
for polyesters 106 degree of polymerization 55
nylon-6 109
nylon-6,6 116 X
specifying rate constants for
XATOWT 453
step-growth 155
XATOXT 453
specifying step-growth 154
step-growth polymerization 134
36 Z
User routines Z-average
fortran linking 374 degree of polymerization 55
User subroutines Z-average degree of
segment-based power-law model polymerization 34
26576 Zero-shear viscosity 74
step-growth polymerization 136 Ziegler-Natta
51 component attributes 44
USER2 Ziegler-Natta catalysts
about 351 about 24
model routine 354 attributes 44
component attributes 32
V dead sites 44
inhibited sites 44
Vacant sites 44, 226
occupied sites 44
Variables
potential sites 44
accessing flowsheet 36971
properties tracked 44
indirect manipulation 339
specifying 24
input 338, 341, 342
vacant sites 44
results 338, 341, 342
Ziegler-Natta polymerization
standard deviations 343
accessing model 237
Vectors
adding reactions 238
packed 151, 275
applications 220
Viewing
assigning rate constants 239
emulsion reactions 216
built-in reaction listing 238
flowsheet variables 36971
catalyst preactivation 232
free-radical reactions 190
catalyst reactions 225
ionic reactions 253
catalyst site activation 232
segment-based reactions 278
catalyst states 225
step-growth reactions 153
catalyst types 221
Ziegler-Natta reactions 238
chain initiation 232
Vinyl chloride 195
chain transfer to small molecules
Vinylacetate 195
233
Viscosity
cocatalyst poisoning 235
as polymer property 8
copolymerization steps 231
intrinsic 74
editing reactions 239
zero-shear 74
ethylene processes 222
VOLL 458
gas-phase process 222, 223
Volume
industrial processes 221
Index 547
input language 499509
kinetics scheme 22535
kinetics scheme (figure) 227
liquid process 223
model 22040
model assumptions 235
model features 235
nomenclature 229
phase equilibria 235
polyethylene processes 222
polypropylene process types 223
propagation 233
properties calculated 236
propylene processes 223, 224
rate calculations 236
rate constants 231
rate expressions 231
reactions 227
site deactivation 234
site inhibition 234
site types 226
slurry process 222, 223
solution process 222
specifying model 237
specifying reacting species 237
steps 230
terminal double bond 235
548 Index