DIVISION OF POLYMER AND CHEMICAL ENGINEERING TECHNOLOGY

LABORATORY WORK

Polymer Technology

Practical Work Book

Semester 3
2020

CONTENT

Exp. No Name of the Laboratory Experiment Name Page

INSTITUTE OF TECHNOLOGY, UNIVERSITY OF MORATUWA

Annex A
SRI LANKA
i
List of Practicals

1. Experiment No: 01 Bulk Polymerization (Chain Growth)

2. Experiment No: 03 Emulsion Polymerization of Styrene
3. Experiment No: 04 Solution Polymerization
4. Experiment No: 05 Determination of molecular weight of polymers using viscosity method
5. Experiment No: 06 Syntheses of Polymer Balls to Observe Viscous and Elastic Behavior
of Polymers
6. Experiment No: 07 Determination of Chemical Properties of Polymers

Annex B

Instructions for Preparation of the Cover Page of Coursework

2
Exp. No : S3/PT/01

BULK POLYMERIZATION (CHAIN GROWTH)

INTRODUCTION

Free radical polymerizations are usually performed using one of four different methods: bulk
polymerization, solution polymerization, suspension polymerization and emulsion
polymerization. This experiment illustrates certain aspects of bulk free radical
polymerization. In this experiment, we shall study the free radical polymerization of MMA to
PMMA.
In bulk polymerization, the reaction mixture consists mainly of monomers, and in the case of
free-radical or ionic polymerization, of vinyl monomers and a soluble initiator. Thus, the
polymerization is carried out in undiluted monomers. Bulk polymerization is more often used
for step-growth polymers such as Polyurethanes, Nylon 6, Polycarbonates and Polyester
(PET).
Bulk polymerization has several advantages over other polymerization techniques; since there
is no solvent or diluent present, it provides polymers of high clarity and high(er) molecular
weight. It is also an environmental friendly polymerization method since no purification is
required and the final product is a 100% solid resin.
However, bulk polymerization has many limitations and drawbacks; for example, this
polymerization technique is not practical for very exothermic reactions because the
temperature is hard to control, particularly at a later stage when the viscosity is high.
Exceptions are vinyl monomers with a low reactivity and enthalpy of polymerization. Two
examples are poly(methyl methacrylate) and polystyrene. But even then, the polymerization
has to be conducted in thin and long reactors with large heat exchangers. Another major
drawback of bulk polymerization is the significant viscosity increase with increasing
molecular weight, which can cause problems with removal of volatile byproducts such as
water, which is a common byproduct of condensation reactions.

3
Initiator Decomposition:
AIBN

MMA PMMA

REAGENTS & APPERATUS:

 Azobis-iso-butyro-nitrile (AIBN) or Benyol Peroxide initiator (BP)
 Methyl Metha Acrylate
 Dichloromethane
 Methanol
 Salt
 25 mL Vial with a cap or 25 mL Test tube with a cap
 2 mL pipette
 Magnetic Stirrer
 Magnets
 Oil bath
 Ice/salt bath
 Suction filters with funnel

4
PROCEDURE:
1. Add 3x10-4 mol of AIBN or Benzoyl Peroxide and 5x10-2 mol of distilled methyl-
methacrylate (MMA) into a 25 mL vial or 25 mL test tube. Shake the vial carefully to
dissolve the initiator.

2. Add the magnetic stir bar to the vial.

3. Bubble N2 gas through the solution to remove oxygen.

4. Close the vial with the lid.

5. Place the vial in an oil bath at 70 °C (exact temperature control is important!!!) and
allow reactions to proceed about 40 min.

6. After reaction time place the vial in an ice bath.

7. Dilute the samples with 5 ml of dichloromethane.

8. Drop the solutions into 50 ml of methanol and stirrer to precipitate the polymer.

9. Collect precipitated polymer by suction filtration, washed with methanol at least 3

times.

10. Take the weight of the precipitated polymer.

11. Dry precipitated polymer overnight at 60 °C in a vacuum oven.

12. Take the weight of the polymer on next day.

13. Calculate the percent yield of polymer that you obtained in the laboratory experiment.

5
Exp. No : S3/PT/02

EMULSION POLYMERIZATION OF STYRENE

INTRODUCTION

Emulsion polymerization is used in the production of a wide range of specialty polymers

including adhesives, paints, and binders for nonwoven fabrics, additives for paper, textiles and
construction materials, impact modifiers for plastic matrices. The definition for emulsion is: "A
stable colloidal suspension as milk, consisting of an immiscible liquid dispersed and held in
another liquid by a substance called an emulsifier."
Emulsion polymerization is one of the most important methods for the polymerization of a large
number of monomers, like vinyl acetate, vinyl chloride, chloroprene, acrylamide, acrylates, and
methacrylates. It is also used for the production of various copolymers, like acrylonitrile-
butadiene-styrene (ABS).

Emulsion polymerization has several advantages over other polymerization techniques; for
example, it is more rapid than bulk or solution polymerization at the same temperature, the
conversion is essentially 100 percent, and the average molecular weight is usually (much) higher
than at the same polymerization rate in bulk or solution polymerization. Also, heat dissipation and
viscosity control are much less problematic than in bulk polymerization.

In general, an emulsion polymerization system consists of a dispersing medium, monomer,

emulsifier, initiator and, if necessary, modifiers. Water is normally the continuous phase in
which the various components are dispersed by the emulsifiers. The monomers are only slightly
soluble in water. They form droplets that are suspended and stabilized by the emulsifiers, that
is, the emulsifier molecules associate and form micelles that surround small amounts of
monomer. The remaining monomer is dispersed in small droplets.

Common emulsifiers are anionic and nonionic surfactants whereas cationic surfactants such as
quaternary ammonium salts are rarely used. Typical anionic emulsifiers are sodium, potassium,
or ammonium salts of fatty acids and C12 - C16 alkyl sulfates. Typical nonionic surfactants are
poly(ethylene oxide), poly(vinyl alcohol) and hydroxyethyl cellulose. A combination of both
anionic and nonionic surfactants will often improve the stability of the dispersed droplets.

6
REAGENTS AND MATERIALS:

 Sodium Dodecyl Sulfate (SDS)

 Distilled water  100 mL Round Bottom
Flask
 Ammonium peroxodisulfate
 Coil Condenser
 Styrene
 Magnetic Stirrer
 NaCl  Magnetic bar
 Toluene  Oil bath
 Propanol  Suction filters
 Methanol  Glass rod

PROCEDURE

1. Prepare a solution of sodium dodecyl sulfate (SDS) 1.23 x 10-3 mol in water 24 mL in a
100 mL RB flask equipped with a magnetic stir bar.

2. Dissolve the initiator, ammonium peroxodisulfate 9.24 x10-3 mol in SDS/water solution
in the RB flask.

3. Add 6.82 x 10-2 mol of freshly distilled styrene to the solution in RB flask under vigorous
stirring.

4. Degas the solution bubbling nitrogen.

5. Connect the condenser to the RB flask and heat the reaction to 50 °C for 2 hrs.

6. After 2 hrs cool the mixture to room temperature.

Important: Appearance of the solution must be a milky.

7. If DLS is available, remove 1 mL of the suspension to record the particle size.

8. Add NaCl in to the RB flask under vigorous stirring using a glass rod to
precipitate the polymer.

9. Decant the liquid to collect the solid polymer.

10. Dissolve the polymer in small amount of toluene.

11. Add propanol to precipitate the polymer.

12. Collect the solid polymer using suction filtration and wash with water at least 3 times
followed by using methanol at least 3 times.

7
13. Dry precipitated polymer overnight at 50 °C in a vacuum oven.

14. Take the weight of the polymer on next day.

15. Calculate the percent yield of polymer that you obtained in the laboratory experiment.

8
Exp. No : S3/PT/03
SOLUTION POLYMERIZATION

INTRODUCTION

Free radical polymerizations are usually performed using one of four different methods: bulk
polymerization, solution polymerization, suspension polymerization and emulsion
polymerization. At this level you have already performed both bulk and emulsion
polymerization techniques. In this experiment, we shall study the free radical polymerization
of MMA to PMMA using the solution polymerization technique. Poly(methyl methacrylate)
an important plastics which is transparent, clear tough material, replaces glass. It is generally
prepared by free radical solution polymerization in conventional solvents such as toluene,
xylene etc.

Bulk polymerization reaction mixture consists of only liquid monomer/s and a soluble
initiator. Thus, the polymerization is carried out in undiluted monomers. Hence, bulk
polymerization has several advantages over other polymerization techniques such as high
clarity and high(er) molecular weight etc. However, bulk polymerization has many
limitations and drawbacks; difficulty of controlling the temperature, auto-acceleration etc.

Solution polymerization is a method of industrial polymerization. It is mainly used for

applications where the presence of a solvent is desired anyway, as is the case for varnish and
adhesives. In this procedure, monomers and initiator are dissolved in a non-reactive solvent.
Many limitations of bulk polymerization are overcome by solution polymerization. Heat
released by the reaction is absorbed by the solvent, and so the reaction rate is reduced.
Moreover, the viscosity of the reaction mixture is reduced, not allowing auto acceleration at
high monomer concentrations. Decrease of viscosity of reaction mixture by dilution also
helps for the heat transfer.

Important facts regarding Solution Polymerization Technique: 1. Selection of suitable solvent

which dissolves, monomers, initiators, and produced polymer. 2. Once the maximum or
desired conversion is reached, excess solvent has to be removed in order to obtain the pure
polymer.

9
REAGENTS & MATERIALS:

 Azobis-isobutyronitrile (AIBN) or Benyol Peroxide initiator (BP)
 Methyl methacrylate (MMA)
 Toluene
 Methanol
 Vial (25-50 mL)
 Pipette
 Magnetic Stirrer
 Magnets
 Oil bath or Water Bath
 Ice/salt bath
 Suction filters with funnel

PROCEDURE

1.Add the magnetic stir bar to the clean and dry vial (25-50 mL).
2. Add 5 mL of toluene to the vial.
3. Add 3 x10-4 mol of AIBN initiator and 5x10-2 mol of distilled methyl-methacrylate
(MMA) into a 25 mL vial. Shake the vial carefully to dissolve the initiator.
4. Bubble N2 gas through the solution to remove oxygen.
5. Close the vial with the cap.
6. Place the vial in water bath at 70 °C (exact temperature control is important!!!) and allow
reactions to proceed about 45 min. If no magnetic stir bar available, shake the test tube.

10
7. Must observe the viscosity of the solution at the beginning, in the middle, and at the end of
the reaction. Compare change of viscosity of solution polymerization with bulk
polymerization of PMMA in same time interval.
8. After the reaction time, place the vial in an ice bath.
9. Drop the solutions into 50 ml of methanol and stirrer to precipitate the polymer.
10. Decant the liquid to collect precipitated polymer and wash it with methanol at least 3
times.
11. Dry the precipitated polymer overnight at 60 °C in a vacuum oven.
12. Take the weight of the polymer on next day.
13. Calculate the percent yield of the polymer.
14. Calculate the degree of polymerization of Solution polymerization and compare it with
the bulk polymerization.

11
Exp.No : 04

DETERMINATION OF MOLECULAR WEIGHT OF POLYMERS USING

VISCOSITY METHOD

INTRODUCTION

Molecular weight is very important factor for the characterization of polymers. The different
techniques are used for the determination of molecular weight of polymers such as Gel
Permeation Chromatography (GPC), Light scattering, End-group analysis, Mass
spectrometry, Ebulliometry and Cryometry etc. One of the simplest method for the
determination of molecular weight of polymers is Viscometry. It is not absolute method so it
is relative method.

Mark-Houwink equation gives the relationship between viscosity and average molecular

weight that is shown as:

[η] = K 𝐌 a

Or

log [η] = a log 𝐌 + K

Where [η] = intrinsic viscosity

M = average molecular weight

K and a = constants for specific polymer and solvent

Therefore, M can be calculated by above equation by determining [η] and by known

K and a value.
The above logarithm equation is straight line equation which shows that log [η] and log M
have linear relationship.

TERMS RELATED TO VISCOMETRY:

I. RELATIVE VISCOSITY:
It is a viscosity ratio and represented by 𝜼 𝒓.

It is calculated by the formula given as:

Where 𝜼 and 𝜼𝒐 are the viscosity of polymer solution and solvent respectively.

I. SPECIFIC VISCOSITY:

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It is also a ratio of viscosity and is represented by 𝜼𝒔𝒑.

It is calculated by the formula given as:

II. REDUCED VISCOSITY:

t is viscosity number and its symbol is 𝜼 𝒓𝒆𝒅.

It is calculated by the formula given as:

III. INHERENT VISCOSITY:

It is a natural log of viscosity number and is represented by 𝜼𝒊𝒏𝒉.

It is calculated by the formula given as:

IV. INTRINSIC VISCOSITY:

It is a limiting viscosity number and is represented by [ ] or by LVN.

It is calculated by the formula given as:

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APPARATUS AND REAGENTS

 Beakers
 Paper tissues
 Spatula
 Solvent
 Polymer solutions (20%, 40%, 60%, 80%)
 Pipette fillers

PROCEDURE
1. Firstly, keep the temperature constant
2. Add solvent into the instrument and note solvent flow time
3. Repeat the above process at least 2 -3 times
4. Then wash the viscometer with any solvent and dry it
5. Put the polymer solution in to it and note its flow time
6. Repeat the process
7. Fill the Table 1, draw the graph and find the molecular weight using graph

Table 01.

Concentration Time (t) Relative Specific Reduced viscosity

(g/mL) viscosity (t/t0) viscosity (t/t0-1) 𝒕

Toluene

Polymer
solution (20%)
Polymer
solution (40%)
Polymer
solution (60%)
Polymer
solution (80%)

DISCUSSION
1. Draw the apparatus
2. What are the advantages of using viscometry method to determine the molecular
weight of polymer?
3. Discussed the terms related to the viscometry

14
Exp. No : S3/PT/05

SYNTHESIS OF POLYMER BALLS TO OBSERVE VISCOUS AND

ELASTIC BEHAVIOR OF POLYMERS

INTRODUCTION

Slime is a type of polymer, which is a large molecule formed by many repeating units of
smaller molecules. Slime has properties of both solids and liquids. Like a solid, slime can be
formed into a ball and keep its shape. Poly(vinyl alcohol), or PVA, is a polymer used to make
many plastics. Borax is the common name for sodium tetraborate decahydrate,
Na2B4O7.10H2O. When added to water, borax forms the borate ion. When PVA and borax
are mixed, the borax connects chains of PVA so that a 3-dimensional network of chains is
formed.

Silicone polymers do not have carbon as part of the backbone structure. Silicones are
synthetic polymers with a silicon-oxygen backbone similar to that in silicon dioxide (silica),
but with organic groups attached to the silicon atoms by C-Si bonds. The silicone chain
exposes organic groups to the outside. Silicones have unique properties amongst polymers
because of the simultaneous presence of organic groups attached to a chain of inorganic
atoms. They are used in many industries including those devoted to electronics, paints,
construction and food.

15
The silicones with short chains are fluids, silicone gels are based on the
poly(dimethylsiloxane) chains but with a few cross-links between the chains, and silicone
elastomers (rubbers) are made by introducing even more cross-linking into the linear chain
polymers.

REAGENTS & MATERIALS

 4% poly vinyl alcohol solution

 Food coloring
 4% borax solution
 Sodium Silicate Solution
 95% Ethanol
 Distilled water
 Beakers
 Glass Droppers
 Glass Rod
 Pipette
 Volumetric Flask

PROCEDURE
Slime from PVA:

1. Measure 20 mL of 4 % PVA solution in to a small beaker.

2. Add 2-3 drops of food coloring to the PVA.

3. Add about 2 mL of a 4% borax solution (4g borax to 100 mL water) to the alcohol and stir
vigorously.

4. Remove the “slime” (gel) from the cup and knead it.

5. Pull the slime slowly. Record the observation.

6. Pull the slime abruptly. Record the observation and compare with the observation from #5
above.

7. Roll the slime into a ball and dropt it alone with the polymer ball prepared using silicate
solution from the same height. Record the observation.

Silicone Polymer Ball:

1. Measure 20 mL of sodium silicate solution and pour into a beaker.

2. Measure 5 mL of 95% ethanol in to a clean pipette.

16
3. Add the ethanol to the sodium silicate solution (add some food coloring too). Mix the solution
until a solid substrate forms.

4. While wearing gloves, remove the substance form the beaker and place it in the palm of one
hand.

5. Gently press it until a ball forms that does not crumble. A mixture of ethanol and water will
come out of the ball as you work with it.

6. If it crumbles, pour a little water on it and reshape it with pressure until it forms a solid ball.

7. Drop the polymer ball along with other polymer ball prepared from same height. Record the
observation.

17
Exp. No : S3/PT/06

DETERMINATION OF CHEMICAL PROPERTIES OF POLYMERS

INTRODUCTION:
In this experiment, you are going to follow simple procedures to understand flame resistance
and solvent resistance of selected polymers.

MATERIALS;
Polyethylene (PE) Hexane
Polystyrene (PS) Toluene
Polyvinylchloride (PVC) DCM
Natural Rubber (NR) Acetone
Styrene Butadiene Rubber (SBR) MEK (Methyl Ethyl Ketone)
Nitrile Rubber (NBR) Methanol
Chloroprene Rubber (CR) THF
Vulcanized NR Compound Cooking Oil
Cured NBR Compound Engine Oil
Cured CR Compound Petrol
Bunsen burner

PROCEDURE

Determination of Flame Resistance of Polymers:

Important: You must do this part of the lab inside of the fume hood.
Procedure;
1. Take about 1-inch width and 2-inch long polymer piece (Use samples with same thickness
if possible).
2. Using a tong, hold the piece of polymer into the flame of the burner and start the stopwatch
as soon as you hold the piece into the flame.
3. Record the time it takes to start the flame.
4. Once polymer piece catch fire, record how much time it takes to burn it completely.

Important: Some polymers catch fire but flame won’t propagate. It is an important
observation.

5. Use a table to record your finding and attach it to the post lab question answer sheet.

I
Determination of Solvent Resistance and solubility of Polymers:
Procedure;
1. Using samples with same thickness take about 0.2 cm x 0.2 cm piece of polymer sample.
2. Place the polymer piece in the test tube with about 2 mL of solvent.
3. Shake the test tube to dissolve the polymer for several minutes.
4. Record your observations in a table and attach it to the post lab answer sheet.

Annex A

INSTRUCTION FOR PREPARATION OF THE COURSEWORK

Report writing is one of the primary professional responsibilities of the practicing diplomate.
Hence, acquiring the ability to write a clear and concise report on experimental work is an
important part of your training a diploma student. The objective in writing a report is to pass
information to others, i.e. it is an exercise in communication. A badly written report may fail
to convey vital points, it may be misleading or it may be misunderstood.

II
A well-written report has two characteristics. Firstly, the material should divide into logically
arranged sections, and within each section there should be a well-organized substructure.
Secondly, the report must be written, sentence by sentence, with absolute clarity.

Note: The report should be short as possible while still including all relevant subject matter.
The value of the report depends not on its length but on its accuracy and utility of its readers.

Structure your reports under the headings given below as far as it is appropriate.

The following standard features and format should be maintained or course work should be
legibly written and worked out according to the instruction given in section C and annex B.

A. Cover Page

1. Paper: Size A4, White color

2. Border: Black color
3. Border margins: left 25mm, others 10mm
B. Inner Pages:
1. Paper: Size A4, White color
2. Page margins: left 25mm, others 10mm
3. Font:
4. Colored drawings, photographs, charts, images and tables are allowed in the body of
the report. These should be properly numbered and described, using an appropriate
title. The title should be placed immediately above a table and immediately below a
figure. These figures and tables should be placed immediately after the paragraph
which is relevant to them.
5. Writing Body Text:
a) Use simple words and phrases
b) Coursework must be hand written.

C. Sequence of Content:

Structure your reports under the headings given below as far as it is appropriate. Before
submitting the report always check each section of it against the list.

III
INTRODUCTION : Describe the aim and scope of the experiment.

APPARATS AND List the apparatus and reagents

REAGENTS :

THEORY : Give a clear statement of the assumptions on which the theory is

based. Also give details of any rearrangement of well-
established theory that you make to suit the needs of the
experiment. Resist the temptation to reproduce bookwork or
portions of the practical manuscript; you can make references to
books and the manuscript as required.

PROCEDURE : Describe your experimental techniques concentrating on those

details that have a particular bearing on the results obtained.
Student must write the procedure in Past Passive Tense and in
Paragraph form.

OBSERVATIONS : Attach your observation sheet.

CALCULATIONS : Do calculations for one data set and tabulate the results without
showing all the calculations in the report.

RESULTS : Present your results in a form that is immediately

comprehensible to the reader using SI units. Use tables and
graphs were appropriate.

DISCUSSION : Discuss and interpret your results. Are they consistent with the
theory? How good is the theory? How good are your own
results?

CONCLUSION : State your main results and conclusions briefly. Keep this
section short and to point.

REFERENCE State the references by referring following example

:
Hamill, L. 2001, Understanding Hydraulics, Second edition,
Palgrave, New York.

(Author's name and initials, year of publication, title of

publication in italics and with minimal capitalization, edition,

IV
 publisher, place of publication)

Special Notice

1. Sub topics like INTRODUCTION, THEORY, DISCUSSION must be in capital,

5mm height and Underlined.
2. Graphs: Attached the graphs and corresponding data tables facing to each other (data
table to the left). Graph tittle: Y axis vs X axis, x & y axis should be labeled near the
axis. Graph tittle should be write above the graph and underlined. y & x axis scale
should be mentioned at the top right hand of the graph. If several graphs are plotted in
the same xy plane, legend should be shown.

3. Student is allowed one week for course work submission.

4. One week is given for course work second submission. (If there are any corrections)
and only one week is given for resubmission of corrected report.

V
 10mm

10mm
Experiment No:
Annex B

100mm
25mm

10mm

HYDROSTATIC PRESSURE APPARATUS 7mm

INSTRUCTOR NAME NAME : Letters 3mm, spacing 4mm

Dr/Mr/Mrs: SERIAL NUMBER :

NAME OF PARTNERS FIELD

1. GROUP/SUB GROUP :

2. DATE :

3. 1. PERFORMANCE :

4. 2. 1stSUBMISSION :

5. 3. 2nd SUBMISSION :

10mm
VI

10mm
 OBSERVATION SHEET

EXPERIMENT : Determination of KOH number of latex concentration

NAME :

INDEX NO :

GROUP :

DATE OF PER. :

INSTRUCTED BY :

Volume of KOH pH
solution added
6cm2 10.46
….