Introduction To The Physical

Chemistry Of Polymer
Lecture 1
 Introduction to polymers
Poly = many, mer = unit, many units
Polymer science is relatively a new branch of science . It deals with chemistry
physics and mechanical properties of macromolecule .
Macromolecule are involved in all human aspect ; the human body itself is
made from proteins a polymer (made of poly amino acid ). Cellulose an
Important natural material essential for the existence of man since the down
of history, is the complicated polymer structure.
Beyond the many natural polymer , the man made polymers ore now for
human development . It is impossible to imagine modern life without all the
different types of synthetic textile materials (polyester , polyamide………..)
: In this course we will discuss the following
Types of polymer -1
Step polymerization -2
Addition free radical polymerization -3
Addition ionic polymerization -4
Copolymerization -5
Molecular weights of polymer -6
Elucidation of the structure of polymer -7
 Definitions
Polymer –is a large molecule consisting of a number of repeating
units with molecular weight typically several thousand or
higher

Repeating unit – is the fundamental recurring unit of a polymer

Monomer - is the smaller molecule(s) that are used to prepare a

polymer

Oligomer –is a molecule consisting of reaction of several repeat

units of a monomer but not large enough to be consider a
polymer (dimer , trimer, tetramer, . . .)

Degree of polymerization - number of repeating units

Nomenclature of polymer
Based on monomer source -1
The addition polymer is often named according to the monomer that was
used to form it
Example : poly( vinyl chloride ) PVC is made from vinyl chloride
-CH2-CH(Cl)-

If “ X “ is a single word the name of polymer is written out

directly
-ex. polystyrene -CH2-CH(Ph)

Poly X

If “ X “ consists of two or more words parentheses should be

used
-ex , poly (vinyl acetate ) -CH2-CH(OCOCH3)

Based on polymer structure -2

The most common method for condensation polymers since the polymer
contains different functional groups than the monomer
 Classification schemes
Classification by Origin
 Synthetic organic polymers

 Biopolymers (proteins, polypeptides, polynucleotide,

polysaccharides, natural rubber)

 Semi-synthetic polymers (chemically modified synthetic polymers)

 Inorganic polymers (siloxanes, silanes, phosphazenes)

 Classification by Monomer Composition

Homopolymer Copolymer

Block Graft Alternating Statistical

Homopolymer
Consist of only one type of constitutional repeating unit (A)
AAAAAAAAAAAAAAA
copolymer
Consists of two or more constitutional repeating units (A.B )
 Several classes of copolymer are
possible
 Statistical copolymer (Random)
ABAABABBBAABAABB
two or more different repeating unit
are distributed randomly
 Alternating copolymer
ABABABABABABABAB
are made of alternating sequences
of the different monomers
 Block copolymer
AAAAAAAAABBBBBBBBB
long sequences of a monomer are followed
by long sequences of another monomer
 Graft copolymer
AAAAAAAAAAAAAAAAAA
B B B
B B B
Consist of a chain made from one type of
monomers with branches of another
type
)d(
Classification by Chain structure (molecular architecture)
 Linear chains :a polymer consisting of a single continuous chain of
repeat units
Branched chains :a polymer that includes side chains of repeat
units connecting onto the main chain of repeat units
Hyper branched polymer consist of a constitutional repeating unit
including a branching groups
Cross linked polymer :a polymer that includes interconnections
between chains
Net work polymer :a cross linked polymer that includes numerous
interconnections between chains

Linear Branched Cross-linked Network

Direction of increasing strength

 Classification by Chain Configuration and Conformation

Configuration or cis-trans isomerism

Configuration : Is defined by polymerization method. A
change in configuration require the rupture of covalent
bonds .
Stereoisomerism or tacticity
Isotactic
Syndiotactic
Atactic

Conformation : is defined by its sequence of bonds and

torsion angles. The change in shape of a given
molecule due to torsion about single (σ ) bonds
Geometric Isomerism

CH2 CH CH CH2
 Microstructure - Tacticity

atactic syndiotactic isotactic

Side groups on random Side groups on alternating Side groups on the same
Sides of the backbone sides of the backbone side of the backbone
Polyolefins with side chains have stereocenters on every other carbon

CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex.

There are three main stereochemical classifications for polymers.
Atactic: random orientation

Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

1. Tacticity affects the physical properties
1. Atactic polymers will generally be amorphous, soft, flexible
materials
2. Isotactic and syndiotactic polymers will be more crystalline, thus
harder and less flexible
2. Polypropylene (PP) is a good example
1. Atactic PP is a low melting, gooey material
2. Isoatactic PP is high melting (176º), crystalline, tough material
that is industrially useful
3. Syndiotactic PP has similar properties, but is very clear. It is
harder to synthesize
 Classification by Thermal Behavior
Thermoplastics - materials become fluid and processible upon
heating, allowing them to be transformed into desired shapes that
are stabilized by cooling.

Thermosets - initial mixture of reactive, low molar mass compounds

reacts upon heating in the mold to form an insoluble, infusible
network

Classification by Application
 Plastics
 Fibers
 Elastomers
 Coatings
 Adhesives

Classification Based on Kinetics or Mechanism

Step-growth
Chain-growth
 Molecular weight averages
To create a solid with useful mechanical properties the chain must be
!! long
One may describe chain length in terms of polymer average molecular
:weight, which can be defined in several ways

1. A number-average molecular weight Mn : divide chains into series of

size ranges and then determine the number fraction Ni of each size
range
Mn = ∑ M i N i / ∑ N i

where Mi represents the mean molecular weight of the size range i, and
Ni is the fraction of total number of chains within the corresponding size
range
A weight average molecular weight Mw is based on the weight .2
:fraction wi within the size ranges
Mw = ∑ M i W i / ∑ W i
 (1)The number-average molecular weight for a
discrete distribution of molecular weights is
given as
   

where N is the total number of molecular-

weight species in the distribution.
(2) The weight-average molecular weight is given as
A measure of the molecular-weight distribution is given by the ratios of molecular
-weight averages.
For this purpose, the most commonly used ratio is Mw/Mn, which is called the
polydispersity index or PDI.

PDI= Mw/Mn

Mw/Mn = 1 monodisperse
Polymer sample consisting of molecules all of which have the same
chain length

Mw/ Mn > 1 polydisperse

Polymer consisting of molecules with the variety of chain length
Description of polymer physical properties
Primary bonds : the covalent bonds that connect the atoms of the main-1
chain
Secondary bonds : non – covalent bonds that hold one polymer chain to -2
another including hydrogen bond and other dipole –dipole attraction
Crystalline polymer : solid polymers with a high degree of structural order-3
and rigidity
Amorphous polymers : polymers with a low degree of structural order -4
Semi – crystalline polymer : most polymers actually consist of both-5
crystalline domains and amorphous domains with properties between that
expected for a purely crystalline or purely amorphous polymer
Glass : the solid form of an amorphous polymer characterized by rigidity-6
and brittleness

Amorphous Crystalline
7 – Crystalline melting temperature (Tm ) : temperature at which crystalline
Polymer converts to a liquid or crystalline domains of a semi crystalline
Polymer melt (increased molecular motion )
8- Glass transition temperature (Tg ) : temperature at which an amorphous
polymer converts to a liquid or amorphous domains of a semi crystalline
polymer melt
9 – Thermoplastics (plastics( :polymers that undergo thermally reversible
Interconversion between the solid state and the liquid state
10- Thermosets : polymers that continue reacted at elevated temperatures
generating increasing number of crosslinks such polymers do not exhibit
melting or glass transition
11- Liquid – crystalline polymers : polymers with a fluid phase that retains
some order
12- Elastomers : rubbery , stretchy polymers the effect is caused by light
crosslinking that pulls the chains back to their original state ‫ا‬
 Glass phase (hard plastic)
9

8 Leathery phase

Log (stiffness)7
Pa 6 Rubber phase (elastomer)

4
Liquid
3

Temperature
 Polymerization mechanisms

Chain Growth Step Growth

The only growth reaction is Reaction can occur
addition of monomer to a independently between any
growing chain with a pair of molecular species
reactive monomer
The reaction mixture consists The reaction mixture consists of
of high polymer and oligomers of many sizes in a
unreacted monomers with statically calculable
very few actively growing distribution
chain
Monomer concentration Monomer disappear early in favor
decreases steadily as of low oligomer
reaction time increases
 Polymerization mechanisms

Chain growth Step Growth

High polymer appears Oligomers steadily
immediately , average increases in size,
molecular weight does polymer average
not change much as molecular weight
reaction proceeds increases as reaction
proceeds
Increased reaction time
increases overall Long reaction time are
product yield , but does essential to produce
not affect polymer polymer with height
average molecular average molecular
weight weight
 Lecture 2
Polymerization mechanisms
 Polymerization mechanisms

- Step-growth polymerization
 Stepwise (Condensation) polymerization Reaction

Requirements for Step-Growth Polymerization

High monomer conversion •
High monomer purity •
High reaction yield •
Stoichiometric equivalence of functional groups •

The characteristic features of this type of polymerization

. process as follow
1-Growth occurs throughout the matrix
2-There is the rapid loss of the monomer species
3-The molecular weight slowly increases throughout the reaction
4- The same mechanism operate throughout the reaction
5-The polymerization rate decreases as the number of functional
group decreases
6-No initiator is required to start the reaction
 Step-Growth Polymerization
Stage 1
n n
Consumption
of monomer

Stage 2

Combination
of small fragments

Stage 3

Reaction of
oligomers to give
high molecular
weight polymer
Example
formation of polyester
nHO-R-OH + nHOOC-Rˉ-COOH H-(O-R-OOC-Rˉ-CO-)nOH+(2n-1)H2O

Kinetics of condensation (step – Growth ) polymerization

Consider the synthesis of polyester from a diol and a diacid. The first
step is the reaction of the diol and the diacid monomers to form
dimer,
HO-R-OH + HOOC-R"-COOH--> HO-R-OCO-R'-COOH + H2O
The dimer then forms trimer by the reaction with diol
monomer,
HO-R-OCO-R'-COOH + HO-R-OH--> HO-R-OCO-R'-COO-R-OH +H2O
and also with diacid monomer,
HO-R-OCO-R'-COOH + HOOC-R'-COOH-->
HOOC-R'-COO-R-OCO-R'-COOH + H2O
 Kinetics of Condensation (Step-Growth) Polymerization
• Step-Growth polymerization occurs by consecutive reactions in which
the degree of polymerization and average molecular weight of the
polymer increase as the reaction proceeds. Usually (although not
always), the reactions involve the elimination of a small molecule (e.g.,
water). Condensation polymerization may be represented by the
following reactions:
Monomer + Monomer Dimer + H2O
Monomer + Dimer Trimer + H2O
Monomer + Trimer Tetramer + H2O
Dimer + Dimer Tetramer + H2O
Dimer + Trimer Pentamer + H2O
Trimer + Trimer Hexamer + H2O
• Generally, the reactions are reversible, thus the eliminated water must be
removed if a high molecular weight polymer is to be formed.
• Based on the assumption that the polymerization kinetics are
independent of molecular size, the condensation reactions may all be
simplified to:
~~~~COOH + HO~~~~  ~~~~COO~~~~ + H2O
Kinetic analysis
~~~~COOH + HO~~~~  ~~~~COO~~~~ + H2O
Most step polymerization involve bimolecular reaction that are often catalyzed
~~~~A + B~~~~ + catalyst  ~~~~AB~~~~ + catalyst
The rate is accelerated according to
-d [A]
= k [A][B] [catalyst]
dt
Or
-d [A]
= k '[A][B] = ‘ Where k k [catalyst]
dt
-d [A]
I f [A] = [B] = k '[A]2
dt
By 1 1 **
integration - = k 't
[M] [M]o

By use the extent of the reaction P (fraction of A or B functional groups

that has reacted at time t )
P = extent of the reaction = the fraction of conversion
The concentration [M] at any time given by

[M] = [M]o - [M]o P = [M]o (1- P )

) **( By substitution in
1 = k '[A]o t + 1
(1-p)
•Note that experimental data are usually linear only beyond ca. 80% conversion.
 Polyesterification Without Acidic Catalyst
The rate equation is given by

- d[A]
= k [A]2[B]
dt
Or
-d [A]
I f [A] = [B] = k [A]3
dt
By
integration 1 1 **
- = 2k t
[M]2 [M]o2
[M] = [M]o - [M]o P = [M]o (1- P )

) **( By substitution in
1 =2 k [A]2ot + 1
(1-p)2
 Uncatalyzed Polyesterification

Note that experimental data for esterification reactions show that plots of 1/
(1-p)2 vs. time are linear only after ca. 80% conversion.
 Polyesterification Without Acidic Catalyst (continued)

• This behavior has been attributed to the reaction medium changing

from one of pure reactants to one in which the ester product is the
solvent.

• Thus, the true rate constants for condensation polymerizations

should only be obtained from the linear portions of the plots (i.e., the
latter stages of polymerization).

• For example, the kinetic plots for the polymerization of adipic acid and
1,10-decamethylene glycol show that at 202oC, the third-order rate
constant for the uncatalyzed polyesterification is k = 1.75 x 10-2
(kg/equiv)2 min-1.
 The Number Average Molecular Weight in
Polycondensation

. The number-average degree of polymerization Xn is given as the total

number of monomer molecules initially present divided by the total number
of molecules present at time t,

Xn = N o / N = [ M ] o / [ M ] [ M ] = [ M ]o ( 1 – P )

Xn = 1 / 1 - P
•This relationship is the Carother's Equation.

Example
If monomer conversion is 99% what is Xn ?
Xn = 1 / 1 – P = 1 / 1 - 0.99 = 100
If P =99.5 % Xn = 1 / 1 - 0.995 = 200
If P =99.6 % Xn = 1 / 1 - 0.996 = 250
 H-(O-R-OOC-Rˉ-CO-)nOH
The number-average molecular weight Mn, defined as

Mn = Mo Xn + Meg = Mo / 1 – P + Meg
where Mo is the mean of the molecular weights of the structural
units, and Meg is the molecular weight of the end groups. The latter
becomes negligible at even moderate molecular weight
Mn = Mo Xn + Meg = Mo / 1 – P
1
= k '[A]ot + 1
(1-p)

Xn= k '[A]ot + 1

X2n=2 k [A]2ot + 1
Mn as a Function of Conversion
 Molecular Weight Control in Linear Polymerization
In the synthesis of polymers one is usually interested in obtaining a
product
of very specific molecular weight since its properties are highly
dependent on its molecular weight.

The desired molecular weight can be obtained by

1-Quenching the reaction (e.g., by cooling) at the appropriate time.
However, the polymer obtained in this case is unstable, since it can
undergo further polymerization if it is heated. This is because the end
groups on the polymer chains are still active and they can react with
each other.

2-By increasing one reactant over the other. In this way the monomer in
excess will block any further increase in the polymer chains.
Excess H2N-R-NH2 + HOOC-R'-COOH ---> H-(-NH-R-NHCO-R'-CO-)n-NH-R-NH2
The use of excess diacid accomplishes the same result; the polyamide
in this case has carboxyl end groups
ExcessHOOC-R'-COOH+H2N-R-NH2 --->HO-(-CO-R'-CONH-R-NH-)n-CO-R'-COOH
Another method of controlling the molecular weight is by adding -3
small amounts of monofunctional monomer. (Acetic acid )
Type (2)
For the polymerization of bifunctional monomers A-A and B-B where B-B
is present in excess, the numbers of A and B F.gs. are given by NA and NB
Notice that NA and NB are equal to twice the number of A-A and B-B .
molecules, respectively.
The stoichiometric imbalance r of the two f.gs. is given by
r = NA /NB. ≤ 1
The total number of monomer molecules is given by
(NA+NB)/2 or NA(1+1/r)/2.
, the total number of polymer molecules is one half the total number
of chain ends or
[NA(1-p)+NB(1-rp]/2.

The number-average DP( Xn )is the total number of A-A and B-B molecules
initially present divided by the total number of polymer molecules:

Xn = NA(1+1/r)/2.
[NA(1-p)+NB(1-rp]/2.
 If r = 1
Xn = 1 / 1-p

Xn = 1+r If p = 1
1 + r – 2rP Xn = 1 + r / 1 - r

Example
What is Xn when P = 1 but use 0. 9800 moles of A-A and 1. 0100
moles of B – B
r = NA / NB = 0.98 x 2 / 1.01 x 2 = 0.97
Xn = 1 + r / 1 – r = 1.97 / 0.03 = 66
Type (3)
the molecular weight can also be controlled by adding small
.amounts of monofunctional monomer
Moles of A-A = NA / 2
Moles of B-B = NB / 2
ˉMoles of mono functional B = NB
ˉr = ½ N A / ½ N B + N B ˉ = N A / NB + 2 N B

Example
Find Xn for 1 mole of A-A ,1mole of B-B and 0.01 mole of RBˉ when P = 1
r = 1/ 1 + 2x 0.01 = 0.99
Xn 1 + r / 1 – r = 1 + 0.99 / 1 – 0.99 = 199

The poly dispersity index

Xw / X n = 1 + P
Xn = 1 /1-P Xw = 1 + p / 1 - P
 1 Summary
= k '[A]o t + 1
(1-p)
1
2 =2 k [A] ot + 1
2
(1-p)
Xn = No / N = [ M ]o / [ M] Xn = 1 / 1 - P

Mn = Mo Xn + Meg = Mo / 1 – P
Xn= k '[A]ot + 1
X2n=2 k [A]2ot + 1

r = NA /NB. ≤ 1 ˉr = ½ N A / ½ N B + NB ˉ = N A / N B + 2 N B
Xn = 1 + r If r = 1 If p = 1
1 + r – 2rP Xn = 1 / 1-p Xn = 1 + r / 1 - r
The poly dispersity index
Xw / Xn = 1 + P
Xn = 1 /1-P Xw = 1 + p / 1 - P
 Lecture 3
Polymerization mechanisms
 Polymerization mechanisms

- Chain-growth polymerization
 Chain polymerization
: The characteristic of chain polymerization are as follow
1- Growth is by the addition of the monomer at the end of the chain
2-Even at long reaction time some monomer are remain in the reaction
mixture
3-The molecular weight of the polymer are increase rapidly
4-Different mechanisms operates at different stages of the reaction
5-The polymerization rate initially increases and then become constant
6-An initiator is required to start the reaction

Chain polymerization reaction consists of three stages

1- Initiation
2- Propagation
3-Termination
Polymerization depend on thermodynamic
Polymerization is possible only if the free energy difference between
monomer and polymer is negative
G = H - TS  0
Always –ve in chain
Must be -ve for
polymerization
Polymerization to
work In chain Always
polymerization ve+
are exothermic
 Chain polymerization

Radical polym. .Ionic polym

The C=C is prefer
the Polym. by R.P.
and also can be Anionic polym. Cationic polym.
used in the steric Electron with drawing Electron donating
hindrance of the substituent decreasing substituent increasing
substituent the electron density on the electron density on
the double bond and the double bond and
facilitate the attack of facilitate the attack of
anionic species cationic species
such as cyano and such as alkoxy, alkyl,
carbonyl alkenyl, and phenyl
δ+ δ- δ- δ+
CH2=CH Y CH2 =CH Y

X X X

radical cationic anionic

 Vinyl monomers for addition
polymerizations
Unsubstituted (ethylene)
.Works fine

Monosubstituted
.Works fine
The only exceptions to the
unreactivity of tri- and tetra-
1,1-Disubstituted
substituted vinyl monomers are
Usually works.
those with fluorine, like
tetrafluoroethylene (CF2=CF2). The
main cause of this reactivity
Disubstituted-1,2 pattern is the steric size of the
.Seldom works substituents.

Trisubstituted
.Almost never works

Tetrasubstituted
.Almost never works
 Free Radical Vinyl Chain Polymerization
Rate of Radical Chain Polymerization
Radical polymerization consists of three steps-initiation, propagation,
and termination.
The initiation step consists of two reactions.
1-The production of the free radical
kd
I ------> 2R˙
2- Addition of this radical to a monomer molecule to produce the
chain initiating species M1
ki
R˙ + M1 -----> M1˙
The propagation consists of the growth of M1
kp
Mn + M1˙ ------> Mn+1˙ (Rapid reaction )
Termination with the annihilation of the radical centers occurs by .
,,bimolecular reaction between radicals either by combination or
by disproportionation
ktc
M n˙ + M m ˙ -----> Mn+m
ktd
Mn˙ + Mm ˙ -----> M n+ Mm
The termination step can be represented by
kt
Mn ˙+ Mm ˙ ----> dead polymer
 Kinetic Rate Expression
The rate of monomer disappearance, = the rate of polymerization,
is given by
d[M ]
  Ri  Rp
dt
Since for the production of high molar mass material Rp »
Ri this equation can be re-written as:
d[M]
  R p  k p [M ][M•] **
dt

From the beginning of the polymerization:

• increasing number of radicals due to decomposition of the
initiator
• increasing termination due to increasing radical
concentration (Rt  [M·]2)
• eventually a steady state in radical concentration:
This is equivalent to stating that the rate of initiation Ri equals the
rate of termination Rt

Ri = 2kt[M.]2

[ M˙ ] = ( Ri /2kt ) ½

and substitution in Eq.* * yields for the rate of polymerization.

Rp =kp [M] ( Ri /2kt) ½

Initiation free radical polymerization

• Thermal initiators
• Photochemical
• Redox initiators
• Ionizing radiation
 Thermal initiators:

•Most common kind of FR initiator.

•Unimolecular decomposition.
(I  2R•)
•First order kinetics.

•Most common examples: peroxides (benzoyl peroxide)or

azo compounds(azo isobuteronitrile).

Peroxides Azo compaunds

(Temperatures are for 10 hour half-lives.)

The thermal, homolytic dissociation of initiators is the most widely
used method for generating radicals to initiate polymerization.
The compounds used as initiators are those with bond dissociation
energies in the range 100-170 kJ/mole.

The rate of producing primary radicals by thermal homolysis of an

initiator Rd is given by
Rd= 2fkd[I]
where [I] is the concentration of the initiator and f is the initiator
efficiency.
and the rate of initiation is given by
Ri=2fkd[I]
By substitute in Rp =kp [M] ( Ri /2kt) ½

Rp =kp [M] (fkd [I] /kt ) ½

 Photochemical initiators:
initiators
•One or two component.
•Used for thin films.

Peroxides Ketones

Azo compaunds Disulfides

h
S S 2 S

Redox initiators: Ionizing radiation:

•Usually 2 component. •X-ray, gamma-ray.
•Rarely used. •Random destruction leads to
radical formation.
Fentons reagent •Used only in very special cases.
cases
 Experimental Determination of Rp
Rp can be experimentally determined by measuring the change in any
property that differs for the monomer(s) and polymer, for example,
solubility, density, refractive index, and spectral absorption

The polymerization can also be followed by separation and isolation of

the reaction products. Chemical analysis of the unreacted monomers
as a function time is also used.

The disappearance of monomers or the appearance of polymer can be

followed spectroscopically, i.r. or uv spectroscopy

Dilatometry
Dilatometry is the volume changes that occurs upon polymerization to
follow the conversion. It is the most accurate method for chain
polymerization because of the large difference in density between
monomer and polymer
 Kinetic chain length 
Kinetic chain length v is defined as the average number of monomer
molecules polymerized per each radical, which initiate a
polymer chain. In other words, v is the ratio between the
propagation
.rate to that of number
initiation,
of or termination
monomer units R p
 
initiating species Ri
By substitute

Ri=2f kd [I] Rp =kp [M] (f kd [I] /ki ) ½

ν =Rp/Ri =Rp/Rt = kp [M] / 2 (f kd kt [I] )1/2

The number average degree of polymerization Xn of chains
formed at a certain moment is dependent on the termination
mechanism:
* combination: Xn = 2
* disproportionation: Xn = 

chemistry: H H H
CH2 C + C CH2 CH2 C C CH2
H

CH3 CH3 CH3 CH2

CH2 C + C CH2 CH2 C H + C CH2
C O C O C O C O
OMe OMe OMe OMe
 Lecture 4
Polymerization mechanisms

Polymerization

Monomer Polymer
 Chain Transfer
Chain transfer is a chain breaking reaction; it is a premature termination
of polymer growing radical by the transfer of hydrogen or other atom
. or species to it from some compound present in the system
.This leads to a decrease in the molecular weight than expected
nM ˙ + XY ktr M -X +Y .
n
where XY may be monomer, solvent, initiator, or other molecule
.and X is the atom or species transferred
The rate of chain transfer reaction is given by

Rtr = Ktr [M .][XY]

where Ktr is the chain transfer rate constant.

Chain transfer results in the production of a new radical Y ˙ which could

induce polymerization. The effect of chain transfer on the polymerization
rate depends on whether the rate of reinitiation is comparable to the
original rate of initiation
 Effect of Chain Transfer on Rp and Xn

Effect on Xn Effect on Type of effect Relative rate constants Case

Rp for Transfer,
Propagation, and
Reinitiation
Decrease None Normal chain Kp>>ktr ka~Kp 1
transfer
Large None Telomerization Kp<<ktr ka~Kp 2
decrease
Decrease Decrease Retardation Kp >>ktr ka<Kp 3
Large Large Degradative Kp<<ktr ka<Kp 4
decrease decrease chain transfer

In case (1) ν ( chain length ) is not changed

Xn (number average degree of polymerization ) is altered
The degree of polymerization now should be redefined as the
polymerization rate divided by the sum of all the chain breaking
reactions:
Xn = Rp
(Rt/2) + KtrM [M˙][M] + Ktrs [M˙][S] + KtrI [M˙][I]

C=chain transfer constant = Ktr / Kp

CM=KtrM /Kp CS=KtrS /Kp CI=KtrI /Kp Rp=Kp [M][M˙]

1/Xn=Rt /2Rp+ KtrM [M˙][M]/Rp+ Ktrs [M˙][S]/Rp+KtrI [M˙][I]/Rp

Substitute by the value of Rp
1/Xn=Rt / 2Rp+KtrM / Kp+ Ktrs [S] / Kp[M] +KtrI [I] / Kp [M]
Substitute by the value of C
Xn=Rt/ 2Rp+CM+CS [S] / [M] +CI [I] / [M] Mayo – walling equation/1

Xn= 1/(Xn)o +CM+CS [S] / [M]+CI [I] / [M]/1

For a given amount of initiator [I] and monomer [M] and
In the presence of chain transfer agent

1/Xn = 1/(Xn)o +CS [S] / [M ]

Cs
1/DP

1/DP0

[S]/[M]

Generic Mayo plot

 Energetic Characteristics
Activation Energy and Frequency Factor
. Increasing the temperaure usually increase the rate and decrease the
molecular weight.
The rate constants of initiation, propagation, and termination can be
expressed by an Arrhenius-type relationship

k = A e – E / RT
or
lnk = lnA – E / RT
where A is the collision frequency factor, and E the Arrhenius
activation energy. A plot of ln k vs 1/T allows the determination
of both values.
 Rate of Polymerization
For a polymerization initiated by the thermal decomposition of an
initiator the polymerization rate depends on three rate constants
Kp ( kd / kt )1/2

  k 1/ 2    A 1/ 2   E  ( E / 2)  ( E / 2)

ln k P  d    ln  AP  d    P d t
(3 - 40)
  kt     At   RT

The composite or overall activation energy for the rate of polymerization

ER is [Ep + (Ed/2)-(Et/2)]. can be written as

 A 
1/ 2

ln RP  ln  AP  d    E
  ln ( f [ I ])1/ 2 [ M ] - R (3 - 41)
  At   RT

Whereً Rp =kp [M] (fkd [I] /kt ) ½

 Thermodynamics of Polymerization
G = H - TS  0
Always –ve in chain
Always –ve in chain
Must be -ve for
polymerization
Polymerization to
work In chain Always
polymerization ve+
are exothermic

Polymerization of 1,2-Disubstituted Ethylenes

R R substituted

Disubstituted ethylenes exhibit very little or no tendency to-1,2

undergo polymerization. Steric inhibition is the cause of this
behavior
 Polymerization-Depolymerization Equilibria
Ceiling Temperature
For most chain polymerization there is some temperature at which the
reaction becomes a reversible one, that is, the propagation step should
be written as an equilibrium reaction
kp
Mn + M M n+1 (3-43)
kdp
where kdp is rate constant for the reverse reaction-termed
depolymerization or depropagation
The reaction isotherm
∆G = ∆Go + RT lnK
. For an equilibrium situation G=0 by
Go = Ho - TSo = - RT ln K
equilibrium constant is defined by Kp/kdp or by
H o
1
[M ]
.
1 Tc   (3 - 47)
K  . n1  S o  R ln[M ]c [ M ] (3 - 46)
[M n ][M ] [M ]
or
H o S o
ln[M]c   (3 - 48)
RTc R
 Ionic chain polymerization
The characteristic of ionic chain polymerization are as follow
1-Ionic polymerization is limited because the ions are usually unstable
and require stabilization by solvation and lower temperature for
polymerization to proceed

2- The ionic polymerization proceeds with very high rates and is very
sensitive to the presence of small amounts of impurities

3-Cationic and anionic polymerizations have very similar characteristics.

both depend on the formation and propagation of ionic species

4-solvents of high polarity cannot be used. The highly polar hydroxylic

solvents (water, alcohol) react and destroy most ionic initiators. Other polar
solvents such as ketones form highly stable complexes with the initiators
preventing thus the polymerization. Ionic polymerization,thus require solvent
of low or moderate polarity such as CH3Cl,CH2Cl2, and pentane.

5-Ionic polymerizations are characterized by a wide variety of modes

of initiation and termination.
 CATIONIC POLYMERIZATION
Initiation
a-Protonic Acids
Protonic acids can be used to some extent but the anion of the acid
should not be highly nucleophilic
HA + RR"C=CH2 + -
RR"C (A) (4 _ 1)
CH3
Halogen acids are not used because of the highly nucleophilic
character of the halide ion
Other strong acids such as perchloric, sulfuric, phosphoric,
chlorosulfonic, methansulfonic,etc, used for cationic
polymerization.
mineral acids (initiators): H2SO4, H3PO4 ( provide H+)
The molecular weight obtained is low (few thousand).
 b-Lewis Acids
Lewis acids used to initiate cationic polymerization at low
temperatures, may yield high molecular weight polymers

Lewis acids (co-initiators): AlCl3, BF3, TiCl4, SnCl4

)often require other proton or cation source(
 Forming (co-initiator / initiator) system
BF3 + H2O HOBF3-H+ (7.2)

AlCl3 + RCl AlCl4-R+ (7.3)

Very active Lewis acids  can undergo auto-
ionization
2AlBr3 AlBr4-AlBr2+ (7.4)
The initiation process can be generalized as
k + -
Y (IZ)
I + ZY
+ - ki +
YM (IZ)
-
(4-5b)
Y (IZ) + M
Propagation:
depending on the association degree between ions

The initiator ion pair (the carbonium ion and its counter ion)
produced in the initiation step proceeds to grow by the
successive addition of monomer molecules

This addition can be occuring by insertion of ( M ) between the

carbonium ion and its counter ion

HMn+(IZ) - + M HMnM+(IZ)-
Termination
1-Chain Transfer to Monomer
. This involves transfer of a proton to a monomer molecule
with the formation of terminal unsaturation in the polymer
molecule

HMnM+(IZ)- + M Mn+1 + HM+(IZ)-

2-Spontaneous Termination
Spontaneous termination involves regeneration of the initiator-
coinitiator complex by expulsion from the propagating ion pair
with the polymer molecule left with terminal unsaturation.

HMnM+(IZ)- Mn+1 + H+(IZ)-

3-Combination with counter ion

Termination by combination of the propagating carbonium ion
with its counter ion occurs

HMnM+(IZ)- HMnMIZ
 Kinetics
Under steady state conditions (Ri=Rt) follows in a manner similar
,to that for radical polymerization. The rates of initiation, propagation
and termination are given by

Ri = Kki [I][ZY][M] Rp = Kp [YM+(IZ)-][M] Rt = kt [YM+(IZ)-]

Where [YM+(IZ)-] is the total concentration of all sized

propagation centers
  Kki [ I ][ ZY ][ M ]
[YM ( IZ ) ]  (4 -13)
kt
Ri k P [ M ] Kki k P [ I ][ZY ][M ]2
RP   (4 - 14)
kt kt
The number-average degree of polymerization is obtained as the
propagation rate over the termination rate
RP k P [ M ]
Xn   (4 - 15)
Rt kt
When chain breaking involves chain transfer to monomer and/or
termination in addition to combination with gegenion, the degree of
polymerization is
RP
Xn  (4 - 15)
Rt  Rtr ,M

The rate of chain transfer to monomer is given by

Rtr,M = ktr,M[YM+(IZ-)][M]

Then kP [M ]
Xn  (4 - 17a)
kt  ktr,M [ M ]
Or
1 k
 t  CM (4 -17b)
X n k P [M ]

.where CM is the chain transfer constant for monomer

 Effect of Reaction Medium
Solvent Effects
Large increase in the rate and degree of polymerization are observed
.if one increases the solvating power of the solvent
. The free ion concentration increases with increased solvating power,
this leads to an increase in Rp as the free ions propagate faster than
the ion pair.
Effect of Gegenion
The larger and less tightly bound the gegenion, the greater should
be the reactivity of the ion pair toward propagation
 Energetics
Cationic polymerization is also exothermic, since the reaction involves
the conversion of π-bond into σ-bond.

the activation energies for the rate and degree of polymerization are
obtained as

ER = Ei+Ep-Et
Trommsdorff effect

In radical polymerization we speak about:

1) low conversion, i.e. polymer chains are in dilute solution (no
contact among chains)
2) “intermediate” conversion, i.e. the area in between low and
high conversion
3) high conversion, i.e. chains are getting highly entangled; k p
decreases.

Somewhere in the “intermediate” conversion regime:

* polymer chains loose mobility.
* Termination rate decreases
* Radical concentration increases
* Rate of polymerization increases
* Molar mass increases

This effect is called: gel effect, Trommsdorff effect,or auto-

acceleration

In the polymerization of MMA this occurs at relatively low

conversion.
 Molar mass
in the ideal case:

Pn  2 If termination takes place by combination)

Pn   If termination by takes place disproportionation)

However, a growing chain may transfer its activity to a new chain:

ktr
Mi + T Mi + T

This reaction is then followed by re-

initiation, the start of a new chain:

ki'
T + M M1
Kinetics of free-radical chain polymerization
considering chain transfer reactions

RMn• + S-H  RMn-H + S•

Rtr = ktr[M•][Transfer agent]

 Chain transfer

chain transfer to:

• monomer
• initiator
• solvent or chain transfer agent
• polymer
• allylic transfer

monomer, initiator and chain transfer agent

are mathematically treated identically:
d[polymer]
 k tc [M•]2  2k td [M•]2  k tr , X [M•][X]
dt
As derived before 1 k tc [M•] 2k td [M•] k tr ,X [X ]
   
this leads to: Pn k p [M] k p [M] k p [M]
k tc [M•] 2k td [M•] k tr ,M k tr ,S [S] k tr ,I [ I]
    
k p [M] k p [M] kp k p [M ] k p [M]
 The rate of “polymer formation” is now defined as:

d[polymer]
 k tc [M•]2  2k td [M•]2  k tr [M•][T ]
dt
The rate of polymerization as derived before:

d[ M ]
  k p [M ][M•]
dt
From the definition of number average degree of polymerization it follows:
d[M ] d[ polymer]
Pn  
dt dt
thus:
1 k tc [ M•]2  2k td [ M•]2  k tr [M•][T ]
 
Pn k p [M ][ M•] 1
Pn 
k tc [ M•] 2k td [M•] k tr [T ] 1 [T ]
    CT
k p [M] k p [M] k p [M] Pn , 0 [M]
Chain transfer to polymer
• Intermolecular chain transfer
• Intramolecular chain transfer

Traditional approach: intermolecular, strong increase in

branching density towards high conversion.
Recent results:
8
• Hardly conversion dependent conversion ca. 25%
7 conversion > 80%
• Dilution results in higher
6
degree of grafting
mol% branches
5

1
0 10 20 30 40 50
[BA]0 / %(w/w)
 Summary

Chain-length L  k p [ M ]t
1
Time of chain-growth t~
[ M ]
Rate of polymerization R p  k p [ M ][ M ]
Initiator decomposition is the reaction step most strongly
influenced by temperature.
 Thermodynamics of radical
polymerisation
Overall activation energy of polymerization: Ea = 1/2Ed+(Ep-1/2Et)

Ed  125 – 170 kJ mol-1 (Ep-1/2Et)  20 – 30 kJ mol-1 Thus, initiation is the rate determining step

Polymeriszation rate  exp(-Ea/RT) Thus, it will increase as the temperature is raised

 Thermodynamics of radical
polymerisation
G = H - TS  0 G will increase if T is raised

Increasing the temperature G eventually becomes 0 and the polymerization stops.

This occurs because the loss in entropy arising from joining many molecules into
one starts to outweigh the energetic benefit of converting double bonds to single
bonds. The temperature above which a monomer cannot be converted to long chain
polymer is known as the ceiling temperatute Tc.
kp
RMn• + M 
 RMn+1•
kdp
Rp = kp[M•][M] - kdp[M•] = 0
[M•](kp[M] – kdp) = 0 or kp[M] = kdp if [M•] 
const
K = (kp / kdp) = 1/ [Me]
G = -RTclnK = RTcln [Me] = H - TcS
RTcln[Me] + TcS = H

Tc = H/(S + Rln[Me])
Copolymerization
k11
—M1• + M1  —M1•
k11
k12
} r1 
k12
—M1• + M2  —M2•
k21
—M2• + M1  —M1• k 22
} r2 
k 21
k22
—M2• + M2  —M2•
 Copolymerization
fi : fraction of monomer i in reaction mixture
f1 = [M1] / ([M1] + [M2])

Fi: fraction of monomer i built into polymer

F1 = d[M1] / (d[M1] + d[M2])
r1f12  f1f2
F1  2
r1f1  2f1f2  r2f22
r1f12  2f1f2  r2f22
Average copolymerisation rate:  kp  
r1f1 k11  r2f2 k 22

Long chain assumption (ki, kd ignored; kp, kt not ~ chain

length)
Reactivity ratios independent of environmental factors
 Ideal copolymerisation
1
MMA / BA
Ethene / VAc Composition drift
0.8 VDC / VC

If f1 ≠ F1
0.6
F1 → f1 changes
0.4
→ F1 changes
0.2 What does composition
drift mean for the polymer
0 that is formed?
0 0.2 0.4 0.6 0.8 1
f1
Polymerization techniques
Sometimes for one monomer several techniques of
polymerizing are available. Choice of a specific
technique depends on a number of factors:

• Kinetic / mechanistic factors related to chain

length, chain composition
• Technological factors e.g. heat removal,
reaction rate, viscosity of the reaction mixture,
morphology of the product
• Economic factors; production costs,
enviromental aspects, purification steps etc.
 Polymerization techniques
Homogeneous systems
• Bulk polymerization
• Solution polymerization

Heterogeneous systems
• Suspension polymerization
• Emulsion polymerization
• Precipitation polymerization
• Polymerization in solid state
• Polymerization in the gas phase
 Bulk polymerization

Advantages: Disadvantages:
• Simple, only the monomer and initiator Exotherm of the reaction might be hard to
are present in the reaction mixture control- molecular weights very
• High molecular weight disperse

Rp
The polymer is soluble
in the monomer:
Viscosity of the reaction
increases markedly (gel
effect)

The polymer is not soluble

in the monomer:
Polymer precipitates out
without increase in solution
viscosity
 Solution polymerization
Monomer dissolved in solvent, formed polymer stays
dissolved. Depending on concentration of monomer the
solution does not increase in viscosity.

Disadvantages Advantages
* Product sometimes * Contamination with
directly usable solvent
* Controlled heat * Chain transfer to
release solvent
* Recycling solvent
Applications
Acrylic coating, fibrespinning, film casting
 Suspension polymerization
• Water insoluble monomers are dispersed in water.
• Initiator dissolved in monomer.
• Stabilization of droplets/polymer particles with non-micelle forming
emulsifiers like polyvinylalcohol or Na-carboxymethylcellulose.
• Equivalent to bulk polymerization,
small droplets dispersed in water.
• Product can easily be separated,
particles 0.01-1mm.
• Pore sizes can be controlled by adding a combination of solvent
(swelling agent) and non-solvent.
• Viscosity does not change much.
 Suspension Polymerization

Advantages Disadvantages
* Heat control simple * Contamination with
* Product directly stabilizing agent
usable * Coagulation possible
* Easy handling

Applications
Ion-exchange resins, polystyrene foam, PVC
Emulsion Polymerization
• A micelle forming emulsifier is used.
• Initiator is water soluble.
• The formed latex particles are much smaller
than suspension particles (0.05-2 µm).
• Kinetics differ considerable from other techniques.
• Polymer is formed within the micelles
and not in the monomer droplets.
Emulsion Polymerization

Advantages Disadvantages
* Low viscosity even * Contamination of
at high solid contents products with additives
* Independent control * More complicated
of rate and in case of water
molecular-weight soluble monomers

* Direct application of
complete reactor contents
 :Overview of Ionic Polymerization
Selectivity
• Ionic polymerizations are more selective than radical processes due to strict
requirements for stabilization of ionic propagating species.
Cationic: limited to monomers with electrondonating groups

Anionic: limited to monomers with electron withdrawing groups

 :Overview of Ionic Chain Polymerization
Counterions

• A counterion is present in both anionic and cationic polymerizations,

yielding ion pairs, not free ions.
Cationic: ~~~C+(X-) Anionic: ~~~C-(M+)

• There will be similar effects of counterion and solvent on the rate,

stereochemistry, and copolymerization for both cationic and anionic
polymerization.

• Formation of relatively stable ions is necessary in order to have

reasonable lifetimes for propagation. This is accomplished by using low
temperatures (-100 to 50 °C) to suppress termination and transfer and
mildly polar solvents (pentane, methyl chloride, ethylene dichloride).
 Overview of Ionic Polymerization
Ion-pair Binding

There are four states of ion-pair binding:

BA ~~~B+A - (II)~~~ ) I(
covalent bond tight or contact ion pair,
intimate ion pair

(III) ~~~B+||A- ~~~B+ + A- (IV)

solvent-separated, Free ion, very reactive
loose ion pair but low concentration

Most ionic polymerizations have equilibrium between ion pairs (II or III,
depending upon solvent) and free ion (IV).
:Overview of Ionic Chain Polymerization
Mechanistic Analysis

Reactions are fast but are extremely sensitive to small amounts of •

impurities. Highly polar solvents (water, alcohols, ketones) will react
with and destroy or inactivate the initiator. Moreover, heterogeneous
initiators are used making the nature of the reaction medium unclear
.and determination of the mechanism difficult

• Termination by neutralization of the carbo-cation (carbonium ion,

carbenium ion) occurs by several processes for cationic
polymerization, but termination is absent for anionic polymerization.
 Initiation of Cationic Chain Polymerization:

Protonic Acids HBr, HI

HA + (CH3)2C=CH2 → (CH3)3C+(A-)

Lewis Acids AlCl3, BF3, SnCl4

A co-initiator (water, protonic acids, alkyl halides) is needed to activate

the Lewis acid.

BF3 + H2O → BF3-OH2

BF3-OH2 + (CH3)2=CH2 → (CH3)2C+(BF3OH)-

 m
o
:Cationic Chain Propagationn
Monomer Structure o
m
Substituents must be able to stabilize
e a formal positive charge. For
olefins, tertiary > secondary > primary
r due to inductive effect.
For styrenic monomers: s
:
C
H Monomer kp, liter/mole sec
2 R = Cl 0.0012
= R=H 0.0037
C
R = CH3 0.095
H
R R = OCH3 6
Steric effects dominate for ortho substitution
M in styrene,
and all substituents reduce kp irrespective
o of inductive effects.
n
o
m
e
r
 :Cationic initiators
Proton acids with unreactive counterions
R R R

H NOT H O
H O
O O S O
O S O
O S O OH
OH
OH

Lewis acid + other reactive compound

With Lewis acid initiator one must need a co-initiator,
a protogen:
or
a cationogen:
 Common steps of cationic polymerization:
(i, ii) initiation, propagation
The mechanism of cationic polymerization is a kind of repetitive alkylation reaction.

Electron donating groups are needed as the R groups because these can stabilize the
propagating species by resonance. Examples:
Propagation is usually very
fast. Therefore, cationic
vinyl polymerizations must
often be run at low
temperatures. Unfortunately,
cooling large reactors is
difficult and expensive.
Also, the reaction can be
inhibited by water if present
in more than trace amounts,
so careful drying of
ingredients is necessary
(another expense).
Lewis acids form active catalyst-co-catalyst
complexes with proton donors
 Regiochemistry of propagation

Markownikov addition – form the most stable carbocation:

E

H R H R H R
E NOT E
H H H H H H

Electron-donating groups R stabilize a cation and affect regiochemistry by

directing the incoming group E to an opposite side to the donating group.

R = Alkyl,
Aryl,
Halide,
OR
 Common steps of cationic polymerization: (iii)
termination by unimolecular rearrangment of the ion pair

B
 Common steps of cationic polymerization:
(iv) chain transfer to monomer

Cationic vinyl polymerization can

be stopped also by numerous
side reactions, most of which
lead to chain transfer. It is
difficult to achieve high MW
because each initiator can give
rise to many separate chains
because of chain transfer. These
side reactions can be minimized
but not eliminated by running the
reaction at low temperature.
 Common steps of cationic polymerization:
(iv) chain transfer to polymer

backbiting:

hydraide transfer:

H
H

+ +
 General kinetic scheme for cationic polymerisation
•Initiation X
X
I+ A─ + M  IM+ A─ I+ A + I A
i = kic[M] M
IM+A
•Propagation X X X X
IM1+ A─ + M  IM2+ A─ I + I
M
IM1+A
… IM2+A
X X X X X
IMn A + M  IM
+ ─
n+1
+
A
─
R + R
p = kp[M+][M] n-1
M
n

IMn+A IMn+1+A

•Termination X X X X
I A R + H+ A
IMn+ A─  IMn + H + A─ n-1 n

t = kt[M+] IMn+A IMn

 General kinetic scheme for cationic polymerisation
(continuation)

Steady-state approximation:
i = t
kic[M] = kt[M+]
[M+] = kic[M]/kt
p = kp[M+][M] = (kp ki /kt)c[M]2

Xn = vp/vt = (kp /kt) [M]

 Common steps of anionic polymerization:
(i, ii) initiation, propagation
The mechanism of anionic polymerization is a kind of repetitive conjugate addition
reaction (the "Michael reaction" in organic chemistry).

Electron withdrawing groups (ester, cyano) or groups with double bonds (phenyl, vinyl)
are needed as the R groups because these can stabilize the propagating species by
resonance. Examples:
 :Anionic initiators
For initiation to be successful, the free energy of the initiation step must be favorable.
Therefore, it is necessary to match the monomer with the appropriate strength of
initiator so that the first addition is "downhill." If the propagating anion is not very
strongly stabilized, a powerful nucleophile is required as initiator. On the other hand,
if the propagating anion is strongly stabilized, a rather weak nucleophile will be
successful as initiator. (Of course, more powerful ones would work, too, in the latter
case.)

But two EWGs are so effective in stabilizing anions that even water can initiate
cyanoacrylate ("Super Glue"). Weak bases (such as those on the proteins in skin)
work even better.
 :Anionic initiators (continuation)
There is one other category of initiator, known as electron transfer, that works best
with styrene and related monomers. The actual initiating species is derived from an
alkalai metal like sodium. An aromatic compound is required to catalyze the
process by accepting an electron from sodium to form a radical anion salt with Na+
counterion. A polar solvent is required to stabilize this complex salt. The electron is
subsequently transferred to the monomer to create a new radical anion which
quickly dimerizes by free radical combination (similar to the termination reaction in
free radical polymerization). The eventual result is a dianion, with reactive groups at
either end. Propagation then occurs from the middle outwards. This system is
especially useful for producing ABA block copolymers, which have important
technological uses as thermoplastic elastomers.
 Common steps of anionic polymerization:
(iii) chain transfer
Acrylates have problems in anionic propagation because of chain transfer to
polymer. The hydrogen atoms adjacent to the ester groups are slightly acidic, and
can be pulled off by the propagating anion. The new anion thus created can
reinitiate, leading to branched polymers. This side reaction is difficult to suppress.
 Common steps of anionic polymerization:
(iv) termination (continuation)

When carried out under the appropriate conditions, termination reactions do not
occur in anionic polymerization. One usually adds purposefully a compound such
as water or alcohol to terminate the process. The new anionic species is too weak
to reinitiate.

The "Dark Side:" Compounds such as water, alcohols, molecular oxygen, carbon dioxide,
etc. react very quickly with the carbanions at the chain ends, terminating the propagation.
Therefore, one must scrupulously dry and deaerate the polymerization ingredients to be able
to get a truly living system. This is not easy to do, and adds to the potential costs of the
process.
Functionalization of the chain ends in anionic polymerization

The beauty of anionic polymerization lies in the lack of termination reactions when
carried out under the appropriate conditions (living polymerization). This means that
the propagating species remains unchanged at the chain end when the monomer is
consumed, so subsequent chemical reactions can be carried out. (The chain end is a
carbanion, and the organic chemistry of carbanions is diverse.) Here are a few
examples among many possible:

Carboxylation of end groups:

Alcohol end groups via

ethylene oxide:

Coupling agents:
 Living anionic polymerization

The usual circumstances:

• Chains are initiated all at once (fast
initiation)
• Little or no termination (except
purposeful).
• Little or no depolymerization.
• All chains grow under identical conditions.
The result is that the monomers get divided evenly among chains.
• Narrow MW distribution (PD approaches 1.0, typically 1.05 - 1.2).
• The MW is predictable (unlike other polymerizations).

For monofunctional initiators, the chain length is simply x = [monomer] /

[initiator]. For difunctional initiators (electron transfer), the chain length
is twice as large.
Anionic Initiation: Direct Attack by Base

B: + CH2=CHR → BCH2C:-HR carbanion

.The strength of the base depends upon monomer reactivity •

• Monomers with strongly electron-withdrawing substituents require

relatively weak bases (low pKa).

• Ability of substituents to stabilize carbanions decreases as:

-NO2 > -C=O > -SO2 > -CO2 ~ -CN > -SO >
Ph ~ -CH=CH2 >>> -CH3
:Types of Base Initiators

Base Initiators are often organometallic compounds or salt of a •

.strong base, such as an alkali metal alkoxide
:Examples
.Potassium with liquid ammonia •
Stable alkali metal complexes may be formed with aromatic •
.compounds (e.g. Na/naphthalene) in ether

.Sodium metal in tetrahydrofuran •

 Anionic Initiation:
Direct Electron Transfer from Alkali Metal

M• + CH2=CHR → [CH2=/•CHR]-M+
monomer radical anion

2[CH2=/•CHR]-M+ → M+-RHCCH2CH2CHR-+M
dianion

The dianion allows propagation from both ends of the initiator.

Highly reactive radical anions usually dimerize.
 Anionic Initiation:
Transfer of an Electron to an Intermediate

M• + A: → A:• -M+
A:•-M+ + CH2=CHR → [CH2=/•CHR]-M+ + A:
Monomer radical anion

• Stable alkali metal complexes may be formed with aromatic compounds

(e.g. Na/naphthalene) in ether.

• Rapid dimerization often occurs due to high free radical concentration:

2[CH2=/•CHR]-Na+ → Na+-RHCCH2CH2CHR-+Na
Propagation from both ends! dianion
 :Anionic Initiation
Transfer of an Electron to an Intermediate
• For Ri >> Rp, all chains start at almost the same time.
If there is no chain transfer and no termination, chains will have equal
lifetimes and grow to about the same size.

[M] = monomer concentration

[C] = aromatic complex concentration

To obtain instantaneous initiation, the electron affinity of the•

.monomer must be much greater than that of the aromatic compound
 :Mechanism of Base Initiation
Relative Initiator Activity
Initiation could be instantaneous, of comparable rate, or much slower
than propagation. If termination is absent,

Termination

By impurities and transfer agents:

• Oxygen and carbon dioxide can react with propagating anions, and
water will terminate the chain by proton transfer. Thus, the reactions
must be carried out under high vacuum or in an inert atmosphere.

By nucleophilic attack of initiator on polar monomer

• Polar monomers such as methyl methacrylate, methyl vinyl ketone,
and acrylonitrile have substituents that will react with nucleophiles.
These side reactions broaden the molecular weight distribution. To
minimize the effect, use a less nucleophilic initiator, lower reaction
temperatures, and more polar solvents.
 Effect of Reaction Medium: Solvent

Solvent Dielectric Constant kp (liter/mole sec)

Benzene 2.2 2
Dioxane 2.2 5
Tetrahydrofuran 7.6 550
Dimethoxyethane 5.5 3,800-1,2

As the dielectric constant increases, the solvating power of the reaction •

medium increases and there is an increased fraction of free ions (which
.are highly reactive)
 Effect of Reaction Medium: Counterion

The separation between the counterion and the carbanion end group on
the polymer is the major factor determining the rate, equilibrium, and
stereochemistry.
Counterion kp, liter/mole sec
in tetrahydrofuran in dioxane
Cation
size
Li+ 160 0.94
Na+ 80 3.4
K+ 60-80 19.8
Rb+ 50-80 21.5
Cs+ 22 24.5
Free anion 65,000!

Tetrahydrofuran is a good solvating solvent (ε = 7.4)

Dioxane is a poor solvating solvent (ε = 2.2)
 Kinetics of Anionic Polymerization:

Reaction Set
Initiation:
GA → G+ + A-
G+ + A- + M → G+ + AM-
Note that the nature of the solvent will determine whether the propagating
anion behaves as a free ion, AM-, as a loose or tight ion pair, AM-G+, or
both. We will assume free ions for this treatment.

Propagation:
AM- + M → AMM-
AMM-+ M → AM2M-
AMn-1M- + M → AMnM-
Termination:
There is no termination step in the absence of impurities.
 Rate of Polymerization

[A-] = total concentration of anions of all lengths

=[GA]o = concentration of initiator before dissociation

Integrate to obtain:
Solid-State Properties
 POLYMERS IN THE SOLID STATE

Amorphous
Semi-crystalline

Glassy Rubbery

Questions: Relationship to microstructure

Relationship of structure to properties
 Glass Transition Temperature

• The glass transition, Tg, is temp. below which a

polymer OR glass is brittle or glass-like; above that
temperature the material is more plastic.

•The Tg to a first approximation is a measure of the

strength of the secondary bonds between chains in a
polymer; the stronger the secondary bonds; the
higher the glass transition temperature.

Polyethylene Tg = 0°C; Polystyrene = 97 °C

PMMA (plexiglass) = 105 °C.
Since room temp. is < Tg for PMMA, it is brittle at
room temp.
For rubber bands; Tg = - 73°C…. So to make rubber
brittle
you need to cool it. Had the Challenger taken off on a
warm day the disaster may never have happened!
 Determination of the glass transition temperature:

 Dynamic Mechanical tests: E', E", Tan 

 Torsion pendulum
 Tensile or flexural vibration vs T,
 Torsional braid
Dilatometry,
 DSC,
 Dielectric loss,
 Bouncing ball
 
 Glass Transition Temp.
1. Breakdown of Van Der Waals Forces
2. Onset of large scale molecular motions
3. Polymer goes from Glassy/Rigid to rubbery behavior
4. Upper service temperature in amorphous polymers

Molecular Factors and Tg

 Free Volume
 Backbone Stiffness
 Steric effects (side groups)
 Network structure (thermosets)
 Anything which makes movement more difficult will increase Tg
 Crystallinity
Crystallization in linear polymers involves the folding back and forth
of the long chains upon themselves to achieve a very regular arrangement
of the mers
Crystalline polymers 
stereoregular/ linear/ strong dipole-dipole interaction
Crystallites 
Crystalline and ordered microdomains; fringed micelle
Induction of crystallinity
● cooling of molten polymer
● evaporation of polymer solution
● annealing  heating of polymer at a specific temperature
● drawing  stretching at a temperature above Tg
Crystalline regions
● a plateletlike
structure (~ 100 Å thick)
● folded-chain
lamella model

Extended-chain crystals
● less common; and often take a needle form
● usually formed with low MW polymer by slow crystallization or
under pressure
Nucleation  onset of crystallinity
• homogeneous nucleation  occur randomly throughout the
matrix
• heterogeneous nucleation  occur at the interface of a foreign
impurity (e.g. a finely divided silica)
Crystalline morphologies
Spherulite  aggregates of small fibrils in a radial pattern
(crystallization under no stress)
Drawn fibrillar  obtained by drawing the spherulitic fibrils
Epitaxial  one crystallite grown on another; lamella growth on
long fibrils; the so-called shish-kebab morphology
(crystallization under stirring)
Crystalline polymers (vs amorphous polymers)
● tougher, stiffer (due to stronger interactions)
● higher density, higher solvent resistance (due to closely packing
morphology)
● more opaque (due to light scattering by crystallites)

Detection of crystallinity degree 

insoluble fraction / density / XRD / thermal analysis / (IR)
 Factors Influencing Crystallinity
• Backbone stiffness
• Backbone symmetry
• Absence or presence of branches
• Pendant group size
• Pendant group polarity
• Pendant group regularity

 A number of factors determine the capacity and/or tendency of a polymer

to form crystalline regions within the material.
 As a general rule, only linear polymers can form crystals
 Stereoregularity of the molecule is critical
 Copolymers, due to their molecular irregularity, rarely form crystals
 Slower cooling promotes crystal formation and growth
 Effect of Crystallization
• Increased Density
• Increases Stiffness (modulus)
• Reduces permeability
• Increases chemical resistance
• Reduces toughness
Thermal & Mechanical Properties
Thermodynamics of Tm and Tg
dG = - SdT + Vdp

V
First-order Transition

Cp

Second order Transition

T
Crystalline vs. Amorphous

Phase transitions for long-chain polymers.

=>
Detect the occurrence of glass transition
dilatometry  measure volume increase
calorimetry  measure the enthalpy change
mechanical measurements  modulus and stiffness
 Semi-crystalline Amorphous

V or V
H

Tm Tg
Modulus & Temperature
Rheology
Rheology  the science of deformation and flow
To cause a polymer to deform or flow 
● need a force
(a) if the force is withdrawn quickly)
 polymer will rebound (a relaxation process)
(b) if the force is applied consistently
 polymer will flow irreversibly
● the flowing polymer liquid will be very viscous
due to chain entanglement and frictional effects
● amorphous polymers are viscoelastic materials
 combination of elasticity and viscous flow
Shear (tangential stress)  the most concerned force type
Shear stress
F (dyne/cm 2
; newton/m 2
)
 F: force (dynes; newtons) A: surface area (cm2;
A m2 )
Shear strain (amount of deformation of one plane with respect to
X another)
 
Y
Shear modulus
(Resistance to shear)

G

(: shear strain) ( = G )

Shear rate (velocity gradient)

 d
  (s-1)
dt
An ideal (or Newtonian) liquid follows Newton’s law of viscosity
(i.e. shear stress increases linearly with shear rate)
   
    
 
: viscosity (a measure of resistance to flow)
poises (dyne s/cm2)
SI system: Pascal-seconds (Pa s = newton s/m2)

Viscosity: air (10-5 Pa s), H2O (10-3 Pa s), glycerin (1 Pa s),

molten polymer (102 － 106 Pa s)

Viscosity can be related to temperature by an Arrhenius-type equation

  Ae  Ea / RT
A: related to molecular motion
Ea: activation energy for forming viscous flow
Ea
● determined mainly by local chain segmental motion
● relatively insensitive to MW
● highly depending on chain structure and branching
● bulkier chain branch or substituent  higher Ea
● bulkier group  makes viscosity more sensitive to
temperature

Bingham Newtonian
 fluid (Eugene Cook Bingham)
τ  τ c η γ c : critical shear stress; threshold stress

• Probably caused by some special type of structural arrangement,

arising from conformational and secondary bonding forces
Non-Newtonian  shear stress is not linearly proportional
to shear rate
shear thinning (pseudoplastic)  more common
shear thickening (dilatant)  less common
τ
shear viscosity at a specified shear rate  η   
(i.e., the slope of a secant drawn from the origin) γ
 Increasing shear rate make disentangling faster than reentangling

thixotropic liquid 
● has gel-like properties or a high viscosity under low stress, but
thin out on stirring
● depending on shear time, but not shear rate (different from shear
thinning)
● commercial paints are typical examples
 B 
General expression    A  log   log A  B log 

• for a Newtonian fluid  B = 1 and A =  ( =   )

• plot log  vs logγ  slope = B; intercept = log A
  B 
General expression    A  log   log A  B log 

• for a Newtonian fluid  B = 1 and A =  ( =   )

• plot log  vs logγ  slope = B; intercept = log A
MW effect
M c  critical molecular weight for entanglement to begin
● typical range  4,000 to 15,000
● typical chain length DP  about 600
 MW distribution effect

Chain branching effect

● lower hydrodynamic volume and lower entanglement
 lower viscosity at a given shear rate and MW
● weaker secondary bonding forces  poorer mechanical properties

Polymer conformation (or shape) effect

   KM v a
● a  0.5 for a random coil; a  1 for a more rodlike extended shape
● more rigid polymers are significantly more viscous
Determine viscosity of a polymer melt

● using a cone-plate rotational viscometer

M  FR
● shear stress  3M F M /R
   ( )
2R 3 A R 2

M
M: torque; dynes/cm (CGS) or newtons/m (SI)   3
R
R: cone radius; cm or m

shear rate 
: angular velocity; degrees/s (CGS) or radians/s (SI)
 
  : cone angle; degrees or radians

viscosity   3M kM 3
    k 
 2 R 3
  2R 3

(k is a constant defined by viscometer design)

Other types of viscometers
● rotating cylinders immersed in the viscous fluid
● steel capillaries through which the molten polymer is forced at
constant pressure or constant flow