Polymer synthesis and characterization

Preliminary Discussion & Report:

In order to understand what you are doing during the laboratory course and not only
follow the recipes from the script, you need to prepare every experiment. This
includes:
 Safety aspects (toxicity of reagents/solvents, etc.)
 Apparatus setup
 Reaction mechanism
 Be able to answer the questions to the reaction
 Think about difficulties and possible questions/problems regarding the
experiment

The tutors will check your preparation by an oral exam before you are allowed
to start the experiment. If you are not prepared, you are NOT ALLOWED to conduct
the experiment and you will have to repeat it during the catch up week.

Every student has to write a report for each experiment which has to be handed
in before starting the next experiment at the latest. Each day the report is delayed
your mark will automatically downgrade by 0.3. If you hand in the experimental
report IN TIME, you will have the chance to correct it and improve your mark.

If you quote literature or any work which is not your one: REFERENCE
IT!!! Be aware of that it is easy to check whether you copied something from the
internet or your colleagues. There is help for literature search provided in this
script.

WIKIPEDIA IS NOT A SCIENTIFIC DATABASE!

The preliminary discussion will make up 1/3 of the mark for the experiment. So it is
worth preparing it!

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 Polymer synthesis and characterization

Contents

Page
Experiments
No.
1 Part (1):Thermal degradation of polymer (polystyrene) 2

Part(2):Preparation of polystyrene by addition

1 5
polymerization (free radical)
The sequential precipitation of polymers and molecular
2 8
weight appointment

3 Viscosity-Average Molecular Weight 10

4 Preparation of polyester by condensation polymerization 14

5 Vinyl Monomer Polymerization 19

6 Preparation of Urea-Formaldehyde resin 22

7 Emulsion polymerization of Acrylonitrile 25

8 Identification of polymers 29

9 Preparation of synthetic rubber (Thiokol) 36

10 Preparation of Rayon 40

References 45

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 Polymer synthesis and characterization

Experiment No. (1) Part one

Thermal degradation of polymer

Introduction

Solid polymeric materials undergo both physical and chemical changes when
heat is applied; this will usually result in undesirable changes to the properties of the
material. A clear distinction needs to be made between thermal decomposition and
thermal degradation. The American Society for Testing and Materials’ (ASTM)
definitions should provide helpful guidelines. Thermal de- composition is “a process
of extensive chemical species change caused by heat. "Thermal degradation is "a
process whereby the action of heat or elevated temperature on a material, product,
or assembly causes a loss of physical, mechanical, or electrical properties. The most
important aromatic hydrocarbon polymers are based on polystyrene {repeating unit: -
[CH (phenyl) - CH2]-}.

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 Polymer synthesis and characterization

Glass transition Crystalline melting

polymers %crystalline
temperature(°C) temperature(°C)
High density polyethylene 95 -125 130-135
Low density polyethylene 60 -25 109-125
Poly propylene 65 -20 170
Poly styrene low <80 230

 Crystalline polymers - solid polymers with a high degree of structural order and rigidity
 Amorphous polymers - polymers with a low degree of structural order
 Semi-crystalline polymers - most polymers actually consist of both 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 and brittleness
even though there is little order on the molecular level

Crystalline Melting Temperature (Tm) - temperature at which a crystalline

polymer converts to a liquid, or crystalline domains of a semi-crystalline polymer melt
(increased molecular motion)

Glass Transition Temperature (Tg) - temperature at which an amorphous

polymer converts to a liquid, or amorphous domains of a semi-crystalline polymer
melt

 A molecular interpretation of polymer melting/freezing behavior:

 above Tm - polymer is liquid, although usually very viscous, with free
random motion of polymer chains

 At Tm - if polymer can crystallize (orderly structure, slow cooling), solid

crystalline domains appear

 At Tg - the remainder of the polymer chains solidify, without much order,

into a glassy state

 Below Tg - the polymer is a rigid solid, containing some crystalline and

some amorphous domains

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 Polymer synthesis and characterization

polyethylene: Tg = -125°C , Tm = 137°C

(polyethylene is a flexible solid at room temp, consisting of some solid crystalline
domains and melted amorphous domains)

polystyrene: Tg = <80 °C , Tm = 230°C

(polystyrene is a rigid, glassy solid at room temp) Thermal degradation of polymers
has been at the center of thermal analysis studies for many years.
Thermal degradation depend on shape of polymer and properties of method:

 Chain degradation (regular), polymer decomposition to monomer

 Random degradation (irregular), polymer decomposition to short chain
EX:
 Poly methyl methacrylate complete degradation to methyl methacrylate
monomer
 Polystyrene degradation 65%
 Polyethylene degradation 1%

The Results of Thermal Degradation

The chemical reactions involved in thermal degradation lead to physical and
optical property changes relative to the initially specified properties. Thermal
degradation generally involves changes to the molecular weight (and molecular
weight distribution) of the polymer and typical property changes include:
 Reduced ductility and embrittlement.
 Chalking
 Color changes
 Cracking
 General reduction in most other desirable physical properties
Apparatus:

1. Distilling flask (250ml)

2. Condenser
3. Stand
4. Conical flask, cylinder
5. Mantel ,Cork (stopper)

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 Polymer synthesis and characterization

Reagent & material:

1. Polystyrene

Procedure:

1. Small pieces of polystyrene polymer is heated inside round bottom flask. Then,
the round will be connected with the condenser to make distillation process.
2. The polymer fumes where condensed and drops of styrene monomer are
collected in the receiver.
3. Collecting of the styrene monomer continues until polystyrene polymer
become viscous and brown color.
4. (30 ml) of styrene monomer has to be collected and kept in a cool place for
next analysis.

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 Polymer synthesis and characterization

Experiment No. (1) Part two

Preparation of polystyrene by addition polymerization (free radical)

Introduction:

The most common type of addition polymerization is free radical

polymerization. A free radical is simply a molecule with an unpaired electron. The
tendency for this free radical to gain an additional electron in order to form a pair
makes it highly reactive so that it breaks the bond on another molecule by stealing an
electron, learning that molecule with an unpaired election (which is another free
radical). Free radicals are often created by the division of a molecule (known as an
initiator) into two fragments along a single bond.
Addition polymerization processes are carried out in bulk, solution, emulsion or by
precipitation techniques. There are three significant reactions that take place in
addition polymerization: initiation (birth), propagation (growth), and termination
(death).
Activation method:

Activating monomer to convert it into free radicals requires an amount of

energy. This process can be done either by physical ways (light, heat), or by chemicals
ways (adding chemical compounds helps to form free radicals when they are
decomposed (which they are called Initiators) or by using the reduced and oxidized
compounds….etc.).

Benzoyl peroxide is considered one of the most important initiators. It

decomposes at (80 °c) to form free radicals.

The characteristics of chain-growth polymerization are:

1) The repeating units are added once at a time to the chain.

2) Monomer concentration decreases steadily throughout the reaction.
3) High molecular weight polymer are formed, the Mw of the polymer changes
throughout the reaction.
4) Long reaction time produces high yield, but affects the Mw.

The following diagram shows the formation of a radical from its initiator, in this
case benzoyl peroxide.

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Polymer synthesis and characterization

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 Polymer synthesis and characterization

Apparatus:

1. Balance
2. Round bottom flask (50ml) {2}
3. Beaker
4. Watch glass
5. Condenser
6. Magnetic stirrer
7. Water bath, thermometer

Reagent & material:

1. Styrene (monomer)
2. Benzoyl peroxide
3. Ethanol

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 Polymer synthesis and characterization

Procedure:

1. Place the collected styrene monomer (from experiment No. (1) part one) in
two round bottom flask (50ml) and record their accurate weight.
2. (0.2g) benzoyl peroxide as an initiator is added. Place the two round bottom
flask within water bath, which is placed on electro mantle with mechanical
stirrer. Connect the round with a condenser and heated at 80-90°C (where the
benzoyl peroxide dissociated to free radical formation) for 30 min.
3. When the styrene monomer become viscous because of the polymerization
process, one of round bottom flask will be moved to the rack.
4. (10ml) ethanol is added gradually with shaking as a precipitator, the
precipitated polystyrene is collected and transferred to watch glass and then
dried a weighted.
5. The second round bottom flask of styrene monomer is heated for another (30
min), the same procedure of polymer precipitation is applied and the second
polystyrene precipitate is collected and then dried and weighted.
6. Calculate the percentage of the two types of the polymer formed.

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 Polymer synthesis and characterization

Experiment No. (2)

The sequential precipitation of polymers and molecular weight

appointment

Introduction:

It is familiar that most classified polymers consist of a mixture of different length

polymers chains. That difference is resulted from the diversity of molecular weights
of these chains. In this case, the polymer is called polydispersed polymer. While, the
similar molecular weights polymer is called monopolymer.

Separating the mixture of different molecular weights similar structure molecular

polymers cannot be done by the normal separating methods (distillation,
crystallization, sublimation), but by the methods which depend on the difference in
the polymeric chains solubility depending on their molecular weights ( solubility
decreases when molecular weight increases) and producing parts that contain
approximate percentage of molecular weight, then, determining the molecular
weight of each part individually.

Polymer separation and fragmentation methods:

a. Precipitation fragmentation
b. Fragmentation by using different solvents.
c. Fragmentation by thermal gradation
d. Fragmentation by osmotic separating columns

The method that we will follow in our experiment is the precipitation

fragmentation, which is based on using precipitation agent added to the polymer
solution. As for the heterogeneity of polymer molecules in terms of weight, they
will be arranged consequently depending on their molecular weights (i.e. the large
molecules will be precipitated first and then the smaller, etc.).

Apparatus:

1. Balance
2. Beaker
3. Burette
4. crucible

1
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 Polymer synthesis and characterization

Reagent & material:

1. Polystyrene
2. N-butyl acetate or Benzene or Toluene
3. Ethanol

Procedure:

This process depends on adding certain precipitator to the polymer solution where it
will separate the polymer chains from their solvents and precipitate them.

1. (2 g) polystyrene is dissolved in (25 ml) n - butyl acetate in a dry Beaker.

2. Use ethanol as precipitate reagent in a graduated burette.
3. Drops of precipitate reagent are added to the polystyrene solution slowly until
the solution become turbid and white precipitate is formed.
4. Close the burette and separate the polymer precipitate completely by
decantation.
5. Add precipitate drops to the precipitator to increase lumpiness.
6. Repeat the process on the remaining part by adding precipitate agent again
until we get four polymeric parts with different molecular weight, then place
each part in a crucible, and leave them for a week to dry, the separated
polymers and measure their molecular weight.

1
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 Polymer synthesis and characterization

Experiment No. (3)

Viscosity-Average Molecular Weight

Introduction to Viscometry:

Measurements of the viscosity of dilute polymer solution provide the simplest

and most widely used technique for routinely determining molecular weights of
polymer samples.
However, it is not an absolute method because each polymer system must first
be calibrated with absolute molecular weight determinations (usually by light
scattering) run on fractionated polymer samples. Viscosities are measured
atconcentrationsofabout0.5 g/100mL of solvent by determining the flow time of a
certain volume of solution through a capillary of fixed length. Flow time in seconds
is recorded as the time for the meniscus to pass between two designated marks on
the viscometer. Viscosities of the polymer solutions are measured at constant
temperature; usually at 30.0±0.1 C.

The Ubbelohde type of viscometer is the most convenient

to use in that it is not necessary to have exact volumes of
solution to obtain reproducible results. Furthermore,
additional solvent can be added (as long as the total
volume can be accommodated by the reservoir); thus,
concentration can be reduced without having to empty
and refill the viscometer.

CAUTION: It is necessary to ensure that the polymer

solution is free from and solid particle, due to either dust
or incompletely dissolved polymer, as any particle that was
stuck at the capillary tube would affect the flow time.

Viscosity can be expressed in several ways as described below.

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 Polymer synthesis and characterization

Relative viscosity (ηr)

Relative viscosity is the ratio of solution viscosity to solvent viscosity, which is

proportional to a first approximation for dilute solutions to the ratio of the solution
flow time to solvent flow time.

Where η and η0 are the viscosities of the solution and solvent respectively; t and t0
are the respective flow time of the solution and the solvent respectively.

Specific viscosity ( ηsp)

Specific viscosity is the fractional increase in viscosity, defined as…..

Both ηr and ηspare dimensionless (i.e. without a unit). As concentration increases, so

does viscosity. Hence, to account for the concentration effects, the specific viscosity
is divided by concentration to give the reduced viscosity ( ηred)

Not uncommonly, viscosities are determined at a single concentration and the

inherent viscosity (ηinh) as defined below is used as an approximate indication of
molecular weight.

red

Where concentration c is commonly expressed as g per 100 ml.

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 Polymer synthesis and characterization

Apparatus:

1. Ubbelohde viscometer
2. Water bath
3. Thermometer
4. Beaker
5. Volumetric flask (25ml)
6. Pipet(10ml)
7. Timer clock

Reagent & material:

1. Polystyrene {from EXP No. (2)}

2. Toluene

Procedure:

(a) Determination of t0
1. Set the water bath at 30.0 ± 0.1 °C. Place 10 ml of toluene (which has been
filtered through a filter stick) into an Ubbelohde viscometer. Leave the
viscometer in a water bath for at least 2 minutes to get thermal equilibrium.
2. Allow the solution to flow under gravity. Start timing with a stopwatch when
the upper meniscus reaches X, stop the stopwatch when the meniscus reaches
Y. Repeat 2 to 3 times, and take the average of the three most consistent
readings to be the solvent flow time t0.
3. Pour out all the toluene, and hang the viscometer upside down in the fume
cupboard to drip dry while you prepare the polystyrene solution as follow.

(b) Preparation of 1% w/v polystyrene solution

4. Prepare a solution of the polystyrene sample by weighing accurately about
(0.25) g of the polystyrene into a (25 ml) volumetric flask. Add toluene into the
flask and allow the polystyrene to dissolve completely (need to wait at least 15
minutes, with occasional shaking), adjust to the mark of the volumetric flask.

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 Polymer synthesis and characterization

(c) Determination of solution flow time t

5. Pipette 10 ml of polystyrene solution into the viscometer. Follow the same
procedure as in (a) to measure the solution flow time.
6. Reduce the concentration of the solution in the viscometer by adding (2 ml) of
solvent directly into the viscometer. Make sure you shake the viscometer for a
few minutes to ensure homogeneous mixing, before you start to determine
the solvent flow time.
7. Repeat the dilution 2 to 3 times, each time by adding (2ml) solvent into the
viscometer. For each concentration, repeat the measurement of flow time at
least 4 times and the average value is computed.

Note: At the end of the experiment, pour the content of the viscometer into a waste bottle.
Fill the viscometer with clean toluene, before you return it back to the laboratory assistant.

Analysis of data
Tabulate your results as follow:
Measurement of solvent flow time t0

Average of three most consistent measurement =

Plot (ηsp/c) versus (c) in graph paper, and determine the intrinsic viscosity [η].
Determine the viscosity average molecular weight of your polystyrene sample.

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 Polymer synthesis and characterization

The intrinsic viscosity of a polymer is related to the viscosity average molecular

weight by the Mark-Houwink Equation.

Where K and an are constants for a specific polymer and are dependent on the
-3
temperature and solvent. In the case of polystyrene in toluene at 30°C, K = 9.2 x 10
-1
ml g and a = 0.72.

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 Polymer synthesis and characterization

Experiment No. (4)

Preparation of polyester by condensation polymerization

Introduction:

Condensation polymers are formed by linking monomers together with

releasing of a smaller molecule, such as water or hydrogen chloride. An example of
this type of polymerization is the formation of a resin called Glyptal from the reaction
of glycerol and phthalic acid.

Polyester:
In principle a polyester can be produced from a monomer that has both –OH and
–COOH functional groups, such as the lactic acid. The general reaction is represented
by:

Such types of monomers are difficult to obtain in pure state, since reaction can
begin even when the monomer is being stored. In addition, the control of molecular
weight of the polyester becomes very difficult to achieve.
More frequently, polyesters are being commercially produced from the combination
of two different monomers, one with two (or more) hydroxyl groups and the other
with two (or more) carboxylic groups. Examples of some well-known commercially
important polyester are PET, PBT, PC
and alkyds.

The reaction between glycerol and phathalic anhydride is esterification. Water

is produced during esterification and is removed by boiling the mixture. This plastic,
glycerol- phathalic anhydride resin is a thermoset plastic. Anhydride acts as across
linker to hold strand of glycerol molecules to gather in a polymer. Using glycerol we
introduces three polymerization points per monomer, this allows for a degree of
cross-linking in final resin:

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 Polymer synthesis and characterization

Esterification is carried only to the point where the polymer is not so cross-
linked; the product is hard, infusible and insoluble.

A linear polymer is obtained with a bi functional anhydride and a bi

functional alcohol (ethylene glycol), but if reactant has three or more reactive sites
then formation of a three- dimensional polymer is possible.

Glyptal has an additional feature to it in that its properties can be modified by a

Process known as cross-linking. A cross-linked polymer is one in which the long
chains of molecules are joined to each other by covalent bonds. The link that is
formed in

16
Polymer synthesis and characterization

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 Polymer synthesis and characterization

Apparatus:

1. Round bottom flask.

2. Thermometer
3. Pipit
4. Crucible (4)

Reagent & material:

1. Phathalic anhydride
2. Glycerol
3. Ethylene glycol
4. NaOH (5N)
5. H2SO4(Conc.)
6. Chloroform, Acetone, Ethanol

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 Polymer synthesis and characterization

Procedure:

1. (4g) of phathalic anhydride and A: (2g) of ethylene glycol B: (2g) of glycerol

are mixed in round bottom flask and connected to condenser.
2. Slow heating of the mixture with stirring is applied by using electro mantle
with mechanical stirrer.
3. The temperature of the electro mantle increases and keeps the reaction
temperature at 160-170C for 15min until all the remaining solids is dissolved.
4. Some drops of produce polymer are pull for next analysis
5. The collected drops of polymer samples are tested, by adding (3 ml) of different
solvents in each crucible.
6. See the changes (soluble or insoluble).

CCl4 or
NaOH H2SO4 Melting
1- ETOH

A: (ethylene glycol)

CCl4 or
NaOH H2SO4 Melting
ETOH
2-

B: (glycerol)

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 Polymer synthesis and characterization

Experiment No. (5)

Vinyl Monomer Polymerization

Introduction:

Vinyl monomers are the monomers which contain the vinyl group in their
structure (CH2=CH2) like methyl methacrylate monomer, styrene monomer and
vinyl acetate monomer.

In this experiment, methyl methacrylate monomer is polymerized by three

process and conditions:

A. Bulk polymerization

This is one of procedure used to

induce radical polymerization with a vinyl
group monomer. It is carried out by adding
only vinyl monomer without solvent usage
or a small amount of initiator. It is a type of
polymerize by heating. Benzoyl peroxide
and azobisisobutyronitrile soluble in
monomers is used for initiator.

The feature of bulk polymerization is

that the polymerization rate is high and
relatively-pure polymer is obtained with
Bulk polymerization. As the removal of
heat of polymerization is difficult, it is hard
to adjust temperature with selective
heating. In addition, post-processing is
complicated for example generated
polymer become solidified and it is attached to the container.

B. Solution polymerization

This is one of procedure used to induce radical polymerization with a vinyl

group monomer. It is a type of polymerize by heating and using monomer and
initiator. Benzoyl peroxide and azobisisobutyronitrile soluble in monomers or
solvents is used for initiator.

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 Polymer synthesis and characterization

The feature of solution

polymerization is that the polymerization
degree and rate is reduced compared with
Bulk polymerization. As the heat released
by the reaction is absorbed by the solvent,
so it is easy to adjust temperature.

Solution polymerization is quite

useful for the use as polymer fluid as it is
after polymerization but need to remove
solvent and collect polymer to take
polymer as solid form.

C. Suspension polymerization

This is one of procedure used to induce

radical polymerization with a vinyl group
monomer. A polymerization process in
which a insoluble monomer is dispersed and
suspended by continuous strong agitation in
a liquid phase, usually water. In addition, the
polymerization in which soluble initiator (for
example: benzoyl peroxide or
azobisisobutyronitrile) is added in the
monomer.

Polyaddition reaction such as polyurethane may also performed in a

suspended form. Polymerization advances in the droplet of a monomer and
particle polymer is obtained. Spherical particles are obtained by performing
suspension polymerization with the use of vinyl acetate, styrene and methyl
methacrylate etc. as a moner, in this case, it is called pearl polymerization.

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 Polymer synthesis and characterization

Polymerization within droplet is essentially the same as bulk polymerization,

and polymerization rate and degree are high. In suspension polymerization, if
polymerization advances, monomer droplet will serve as thick solution of the
polymer which uses a monomer as a solvent, and droplets will stick easily.
Therefore, it needs to perform by constant strong agitation and add water soluble
polymer such as gelatin, starch, polyvinyl alcohol and carboxymethylcellulose, and
insoluble powder such as calcium carbonate and magnesium carbonate to stabilize
droplets.

Generated polymer particle size also changes with agitating speed. As the
heat released during the polymerization is absorbed by the surrounding solvent,
selective heating does not happen and it is easy to adjust temperature.

Suspension polymerization most commonly used as industrial manufacturing

method in order to get polymer for forming material such as polystyrene,
polymethylmethacrylate, polyvinyl acetate, polyvinyl chloride, because a polymer
with a high degree polymerization is obtained with the polymerization and
generated polymer isolation is easy.

Apparatus:

1. Test tube
2. Water bath
3. Filter paper
4. Oven

Reagent & material:

1. Methyl methacrylate (monomer)

2. Benzoyl peroxide
3. Ethanol
4. Benzene
5. Distilling water (D.W.)

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 Polymer synthesis and characterization

Procedure:

A. Polymerization of methyl methacrylate monomer by bulk polymerization.

1. Place (2.5 ml) methyl methacrylate monomer in dry test tube then add (0.1g)
of benzoyl peroxide (initiator).
2. Place the test tube in water bath at (80°C) for (15min) with shaking, and then
put it on the rack for (5min) at room temperature.
3. Add (15ml) ethanol with shaking to precipitate the polymer.
4. That polymer will be separated and placed on weighted filter paper.
5. Place the polymer in an oven at (°C) to be dried.
6. Calculate the percentage of polymer:

% polymer= (weight of polymer/volume of monomer)*100

B. Polymerization of methyl methacrylate monomer by solution polymerization.

1. Place (2.5 ml) methyl methacrylate monomer in dry test tube then add (0.1g)
of benzoyl peroxide (initiator) then add (2.5ml) of benzene.
2. Place the test tube in water bath at (80°C) for (15min) with shaking, and then
put it on the rack for (5min) at room temperature.
3. Add (15ml) ethanol with shaking to precipitate the polymer.
4. That polymer will be separated and placed on weighted filter paper.
5. Place the polymer in an oven at (°C) to be dried.
6. Calculate the percentage of polymer:

% polymer= (weight of polymer/volume of monomer)*100

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 Polymer synthesis and characterization

C. Polymerization of methyl methacrylate monomer by suspension

polymerization.

1. Place (2.5 ml) methyl methacrylate monomer in dry test type then add (0.1g)
of benzoyl peroxide (initiator) then add (2.5ml) of D.W.
2. Place the test tube in water bath at (80°C) for (15min) with shaking, and then
put it on the rack for (5min) at room temperature.
3. Add (15ml) ethanol with shaking to precipitate the polymer.
4. That polymer will be separated and placed on weighted filter paper.
5. Place the polymer in an oven at (°C) to be dried.
6. Calculate the percentage of polymer:

% polymer= (weight of polymer/volume of monomer)*100

Note: After producing the polymeric samples by the three process, all results and
student notes should be recorded on each sample.

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 Polymer synthesis and characterization

Experiment No. (6)

Preparation of Urea-Formaldehyde resin

Introduction:

Any class of synthetic resins is obtained by chemical combination of urea (a

solid crystal obtained from ammonia) and formaldehyde (a highly reactive gas
obtained from methane).

Urea-formaldehyde resins are one type of condensation polymerization; urea-

formaldehyde resin is made up largely from low molecular weight pre polymers. It
consists of three-Dimensional network of interlinked polymers.

Urea-formaldehyde resins are used as adhesives for the bonding of plywood

and other structure wood products. Because urea-formaldehyde resins are lighter in
color than phenol-formaldehyde resins, they are used for interior plywood and
decorative paneling.

Urea-formaldehyde resins are used as major adhesives in the forest

products industry, since they have a number of advantage including low cost, water
solubility, abrasion hardness excellent thermal properties, lack of color and low cure
temperatures.

The major disadvantage associated with urea-formaldehyde resins as

compared with others is their moist ting wood adhesives such as phenol-
formaldehyde, which lacks moist conditions resistance it, especially in combination
with heat. These conditions lead to the reversal of the bond forming reactions and
release formaldehyde.

The urea-formaldehyde resins were formed from the reaction between urea
and formaldehyde, as the following reaction:

25
Polymer synthesis and characterization

26
 Polymer synthesis and characterization

Apparatus:

1. Beaker
2. Round bottom flask
3. Condenser
4. Buckner funnel
5. Balance
6. Water bath

Reagent & material:

1. Urea
2. Formaldehyde
3. NaOH (5%)
4. HCl (5%)
5. Filter paper
6. Litmus paper

Procedure:

1. (3.5g) Urea is weighted and crushed in a dry beaker, then, (10ml) of

formaldehyde is added with stirring for solution dissolve.
2. (4-5) drops of sodium hydroxide solution are added to the solution to become
the media basic (use litmus paper).
3. Pour the mixture in a dry and weight round bottom flask with condenser and
heat the mixture at 70-80C, and use regulated water bath for (1hr).
4. Cool the mixture and add some drops of dilute hydrochloric acid and use
litmus paper to equalize the mixture (pH=6.5-7).
5. Keep the resin dry then weight for percentage yield calculation.

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 Polymer synthesis and characterization

Experiment No. (7)

Emulsion polymerization of Acrylonitrile

Introduction:

Polymers are synthesized in industry and laboratory in different methods and

they can be divided in to:

Polymerization Methods

Heterogeneous
Homogenous polymerization
polymerization
Polymerization in Polymerization
the gas phase between two
Solution Bulk solution surfaces
polymerization polymerization

Emulsion Precipitating Suspension

polymerization polymerization polymerization

Homogenous polymerization: It means that there is one homogenous

medium. All polymerization components are in the same phase (either) liquid, solid,
gas.
Heterogeneous polymerization: It is mean that there is more than one phase
in the polymerization medium, either liquid and solid or liquid and gas…etc.

Emulsion polymerization: It is one type of Heterogeneous polymerization. The

word emulsion it means the distribution and spreading one of liquid phase in another
liquid phase (not solubility).

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 Polymer synthesis and characterization

Emulsion polymerizations involve the formation of colloidal polymer particles

that are essentially permanently suspended in the reaction medium. The reaction
mechanism involves the migration of monomer molecules from liquid monomer
droplets to sites of polymerization that originate in micelles consisting of surface-
active agent molecules surrounding monomer molecules.
Emulsion polymerizations are usually characterized by the requirement of surfactants
during the initiation of the process and by the use of water-soluble initiators. This
process also permits good control of the exothermic nature of the polymerization.
Generally, the molecular weight of the polymers produced by an emulsion process
are substantially greater than those produced by bulk or suspension polymerizations.
The rate of polymer production is also higher. As a large quantity of water is usually
present, temperature control is often simple. Typical emulsion polymerization
recipes involve a large variety of ingredients. Therefore, the possibilities of variations
are many. Among the variables to be considered are the nature of the monomer or
monomers, the nature and concentration of surfactants, the nature of the initiating
system, protective colloids and other stabilizing systems, co solvents, chain-transfer
agents, buffer systems, "short stops," and other additives for the modification of
latex properties to achieve the desired end properties of the product.
From the preparative standpoint, there are two classes of initiating systems.

Mechanism for emulsion

polymerization of a monomer (M),
initiated by radical (I•). At all
times, the monomer that is
incorporated travels from
emulsified monomer droplets;
monomer can be added initially in
the aqueous phase, but later is
incorporated inside separate
micelles.

1. The thermal initiator

system. This system is made up of water-soluble materials that produce free radicals
at a certain temperature to initiate polymerization.
The most commonly used materials for such thermal emulsion polymerizations
are potassium persulfate, sodium persulfate, or ammonium persulfate.

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 Polymer synthesis and characterization

2. Activated or redox initiation systems. Because these systems depend on the

generation of free radicals by the oxidation-reduction reactions of water soluble
Compounds, initiation near room temperature is possible. In fact, redox systems
operating below room temperature are available (some consist of organic Hydro
peroxides dispersed in the monomer and a water-soluble reducing agent).

Properties of poly acrylonitrile:

1. High strength
2. Stiffness
3. Toughness
4. Abrasion resistance
5. Resilience

Apparatus:

1. Round bottom flask (100ml)

2. Cylinder
3. Balance
4. Water bath
5. Buchner funnel
6. Filter paper
7. Magnetic stirrer

Reagent & material:

1. Acrylonitrile (monomer)
2. Potassium thiosulfate & potassium persulfate(oxidation-reduction initiators )or
Azo bis-isoButyronitrile {AIBN}
3. emulsion material
4. Distilling water
5. Aluminum sulfate
6. Ethyl alcohol (ethanol)

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 Polymer synthesis and characterization

Procedure:

1. Mix the following amounts of chemicals in around bottom flask:

 (10ml) of acrylonitrile (monomer)
 (0.5g) of emulsion material
 (0.03g) of Potassium thiosulfate
 (0.03g) of potassium persulfate
 (30ml) distilling water
2. Heat the formed mixture by using water bath at (70°C) for (1hr) with
shaking for precipitation of the polymer.
3. Add 10ml (2.5%) of aluminum sulfate.
4. The produced polymer is filtered using Buchner funnel and wash for two
times by ethanol.
5. Dry the product and calculate the percentage yield.

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 Polymer synthesis and characterization

Experiment (8):

Identification of polymers

Note: these methods of identification do not give the true identification

accurately, but they give the possibilities of the type of polymer. Sometimes, we
add some chemical compounds to the polymers in order to improve their
properties, such as: plasticizers, anti-oxidizers and etc. these materials share in
the tests:

The first test (thermoset or thermoplastic tests):

This test classifies polymer into two types: thermoset and thermoplastic. This test
can be done by two methods:

Polymer exposure to the heat

Melting and formation by Charring (dissociating) and deformation

heat (thermoplastic) by heat (thermoset)

Or by razing

Solid compound (cannot be razed) Can be razed except polystyrene (PS) &poly
((thermoset)) methyl methacrylate (PMMA)

Light color (urea &melamine Brown or black (phenols Floating test

resins) resins) 29
 Polymer synthesis and characterization

 Cellulose acetate, Polyethylene (PE) &polypropylene (PP)

 poly vinyl chloride(PVC)
Scratching and observing the surface of
 poly carbonate
polymer:
 polystyrene(PS)
 poly methyl methacrylate(PMMA)
 poly ethylene terephthalate(PET)
 Nylon
High glitter
 Acrylonitrile butadiene styrene(ABS)
High glitter (Scratched) HDPE High glitter

(Non scratched) (Easily scratched)

By using sodium PP LDPE
thiosulphate
solution (NaS2O3)

Float Sink
 Polystyrene(PS)  Poly methyl methacrylate(PMMA)
 Nylon  Cellulose acetate
 Acrylonitrile butadiene  Poly vinyl chloride (PVC)
styrene(ABS)  Poly ethylene terephthalate(PET)

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 Polymer synthesis and characterization

The second test (measuring polymer density):

Take a small piece of polymer and put it in a test tube contain an amount of water
and observe if it will float or sink:

Float Sink
Polymer density less than Polymer density more than
water density water density

Add alcohol (ethanol or Add sodium chloride or

methanol) drop by drop with sodium thiosulphate solution
shaking drop by drop with shaking

When the polymer piece starts going When the polymer piece starts going up
down the solution (water+alcohol) the solution (water+ (NaCl or NaS2O3
and settle in the middle. solution)) and settle in the middle.
Solution density = polymer density Solution density = polymer density

Place the solution in a dry weighted Place the solution in a dry weighted
conical flask (10ml) w1 conical flask (10ml) w1

Then, weight the conical flask with Then, weight the conical flask with
the solution w2 the solution w2

W2-w1
Density =
vol.

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 Polymer synthesis and characterization

After finding the density of the polymer. Well compare the results with the next table
to find out the unknown polymer.

Density of some polymers

polymers Density
PP 0.850
LDPE 0.90
HDPE 0.96
PS 1.04
PMMA 1.2
PAN 1.18
ABS 1.1
Nylon 1.1
PVC 1.4
Urea 1.5
PET 2.0

Third test (ignition test):

According to this test, polymers are divided into three types:

Polymers burn & extinguish

after taking the source of
Polymers do not burn (PET) flame away (PVC & rubber) Polymers burn & don't
extinguish after taking the
source of flame away (PS & PE)

Tack a piece of polymer by using clamp; expose it to the flame directly. When it
burns, take it far from flam and notice the following:

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 Polymer synthesis and characterization

Ignition degree Burn, not burn, extinguish itself or not

Flame color Yellow, orange, blue and the color of the top and the base
of the flame
Smoke Non, black, light black, white
Vapors Acidic or basic (tested by litmus paper

Compare the results with the next table:

Material ♣ Flame color Smoke Vapors Note

Blue with yellow
Polyethylene(PE) Non Neutral Burn
top flame
Yellow with blue
Poly propene (PP) Non Neutral Burn
base flame
PTFE Not burn ---- ---- ----
Orange yellow or
thick black
Poly styrene (PS) yellow with blue Neutral Burn
smoke
base
Hardly
Yellow with blue Black
ABS Neutral burn and
base smoke
extinguish
Yellow with green White Burn and
PVC Acidic
base smoke extinguish
Little
Cellulose acetate Yellow acidic Burn
smoke
Yellow with blue
PMMA Non Neutral Burn
base
Blue with yellow Burn and
Nylon Non Neutral
top extinguish
Poly formaldehyde
Light blue Non Neutral Burn
acetyl
Black Hardly
Poly carbohydrate yellow Neutral
smoke Burn
Hardly
Phenol resins Yellow with spark Non Neutral burn and
extinguish

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 Polymer synthesis and characterization

Hardly
Light yellow with
Urea resins Non Basic burn and
light blue flame tip
extinguish
Light yellow with Hardly
Melamine resins light green blue Non Basic burn and
flame tip extinguish
Yellow with blue Thick
Poly ester Neutral Burn
base smoke
Yellow with blue
poly urethane Non Neutral Burn
base

♣ Vapors must be tested when the polymer flame extinguishes.

Four test (Melt and smell test):

Put a small piece of polymer on a metal piece placed on Bunsen burner. Observe the
melting attitude (melts (not to be liquid), be solid, be liquid, swells, melts, chars or
melts and chars) as well as the smell (charring rubber, fruit, fish, wool or hair
smell….).

Compare the results with the table below

Polymer Melting attitude Smell

Melts and makes bubbles at
Polyethylene(PE) Charred wax
the tips
Melts (not to be liquid) and
Poly propylene(PP) Wax smell
tends to make a ball
Poly ethylene
Not melt -
terephthalate(PTE)
Melts and makes bubbles at
Polystyrene(PS) Styrene smell
the tips
Acrylonitrile-butadiene-
Melts but not to be liquid Charred rubber
styrene(ABS)
melts (not to be liquid) and
Poly vinyl chloride(PVC) Unacceptable smell
curls and chars at base
Melts, release white smoke,
Cellulose acetates Vinegar smell
then boils and chars

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 Polymer synthesis and characterization

Poly methyl
Boils and makes bubbles fruits
methacrylate(PMMA)
Polycarbonate Makes bubbles -
Nylon Melting and carbonating tips Charred hair or wool
Phenol resins Not melt Phenol smell
Fish or formaldehyde
Urea resins Not melt
smell
Fish or formaldehyde
Melamine Not melt
smell

Five test (Solubility test):

Polymeric compounds solubility differs from organic compounds solubility.
Initially polymer swells in the solvent and then it dissolves. Sometimes it swells only
without solubility because solvent molecules interfere the long chain polymer. Such a
case is not considered solubility method. To ensure polymer dissolving, it is required
to give long time with shake.

Firstly, we can use two solvents: Acetone and N-Propanol and compare them
with the below table:

Polymer Solubility with Acetone Solubility with N-Propanol

PE X X
PP X X
PTE X X
PS O X
ABS O X
PVC + X
Cellulose acetates O +
PMMA O X
Polycarbonate X X
Nylon X X
Phenol resins X X

Where:

X = not dissolve, O = dissolve, + = partially dissolve

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 Polymer synthesis and characterization

Experiment (9):

Preparation of synthetic rubber (Thiokol)

Introduction:

Polysulfide rubbers were among the first commercial synthetic rubbers

produced. Two chemists, Joseph C. Patrick and Nathan Mnookin, were trying to
invent an inexpensive antifreeze in 1926.In an experiment involving ethylene
dichloride and sodium polysulfide; they created a gum whose outstanding
characteristic was a terrible odor. Trying to dispose of it, the substance clogged a sink
in the laboratory, and none of the solvents used to remove it were successful. The
chemists realized that the resistance of the material to any kind of solvent was a
useful property. They had invented synthetic rubber, which they christened
"Thiokol," from the Greek words for sulfur (the ion) and glue (kolla). The Thiokol
Chemical Corporation was subsequently founded on December 5, 1929.
Thiokol rubber is resistant to natural oxidants such as oxygen and ozone and to
organic solvents such as oils and gasoline. This makes it useful for engine O-rings,
gaskets, and hoses which may come in contact with oils.
Thiokol can b e prepared by the reaction of 1,2-dichloroethane and sodium
polysulfide.
Cl-CH2-CH2-Cl + Na2Sx →Cl-[-CH2-CH2-S-S-]n-CH2-CH2-Cl + 2n NaCl
In this experiment, you will prepare a sample of a polysulfide rubber. After the
preparations, you can compare the properties of the rubber.

The Small-Scale Preparation of Thiokol Rubber

This preparation of Thiokol rubber is a two-step process. The first step is the
preparation of sodium polysulfide by the reaction of sulfur, S8, with a strong base,
sodium hydroxide, NaOH.
S8 + 2 NaOH → Na2S8
At room conditions, sulfur is normally in the form of S8 rings and chains. The reaction
with sodium hydroxide produces a mixture of mostly Na2S8 with other chain lengths
of sulfur present. That mixture is called sodium polysulfide.

The second step of this preparation is the reaction of sodium polysulfide with
ethylene dichloride.
Cl-CH2-CH2-Cl + Na2Sx → [-CH2-CH2-S8-]n + 2n NaCl

36
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 Polymer synthesis and characterization

The physical properties of the material depend on:

 The length of the aliphatic group
 The number of sulfur atoms present
The polysulfide elastomers are outstanding in oil and solvent resistance. They have
good resistance to aging and ozone. On the other hand, they have disagreeable
odors, poor heat resistance, poor abrasion resistance and low tensile strength.
Practical applications are in printers, rollers, seals, gasket and heavies for metal,
glass, and plastic …. etc.

Apparatus:

1. Round bottom flask (150ml)

2. Graduated cylinder
3. Beaker
4. Funnel
5. Water bath

Reagent & material:

1. Sodium hydroxide solution (1M).

2. Sulfur
3. 1,2-dichloroethane
4. Distilled or deionized water

Safety
Wear safety goggles at all times in the laboratory. Sodium hydroxide solution is
corrosive. Although the solution used in this experiment is dilute, if any splashes on
the skin, immediately rinse well with room temperature water. If some redness of
the skin occurs, seek medical attention.
1,2-dichloroethane is flammable, avoid any fires or sparks. It is also an irritant to the
skin and eyes and is toxic by ingestion. Work with this only under a fume hood.

Disposal
Dispose of all liquid wastes in the proper waste bottle provided.

37
37
 Polymer synthesis and characterization

Procedure:

1. Place (3g) of sulfur (yellow powder) in clean and dry round bottom flask.
2. Add 12 ml (20%) NaOH solution to the sulfur powder.
3. Add (40 ml) distilled water to the mixture.
4. Reflex the mixture for (1hr).
5. Keep the reflex mixture cool. Filter the remaining mixture to remove the
unreacted sulfur.
6. Add (15 ml) of the filtrate to another round bottom flask contain (5 ml) of
dichloro ethylene.
7. Heat the mixture at (70°C) use water bath with stirring for (45 min). Thiokol the
synthetic rubber will form.

Rubber Industrial process:

i) Vulcanization: it transforms elastomers from a weak thermoplastic mass
without useful mechanical properties into a strong, plastic and tough
rubber. This process takes place in the present of sulfur, peroxide and some
element oxides.
Vulcanization with sulfur:

ii)

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 Polymer synthesis and characterization

Fillers:

We can summary the effect of fillers on the rubber properties to:

1. Tensile strength
2. Modulus
3. Abrasion resistance
4. Stiffness
5. Road wear resistance

39
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 Polymer synthesis and characterization

Experiment (10):

Preparation of Rayon

Introduction:

Cellulose is a nature’s own giant molecule. It can be found in three types of in

nature:
α-cellulose, β-cellulose and ϒ-cellulose,
α-cellulose: It is the type, which dissolve in 18% sodium hydroxide (NaOH). It is called
(pure) real cellulose. It has high molecular weight and long chain.
β-cellulose: It is the type, which solves in 18% NaOH. It could be precipitated by the
acidification.
ϒ-cellulose: It is the type, which solves in 18%NaOH. It is not precipitated by the
acidification.
It is the fibrous material that every plant from seaweed to the sequoia
makes by baking glucose molecules in long chains; the chains are bound together in
the fibers that give plants their shape and strength. Wood has now become the main
source of cellulose. Since it contains only 40% to 50% cellulose, the substance
must be extracted by ‘pulping’. The logs are flaked, and then simmered in chemicals
that dissolve the tarry lignin, resins and minerals. The remaining pulp, about
93% cellulose, is dried and rolled into sheets-raw material for paper, rayon and other
products.
It can be obtained in two ways:

1. Viscose Process: Cellulose is soaked in 30% caustic soda solution for about 3 hrs.
The alkali solution is removed and the product is treated with CS2. This gives
cellulose xanthate, which is dissolved in NaOH solution to give viscous solution. This
is filtered and forced through a spinneret into a dilute H2SO4 solution, both of which
harden the gum-like thread into rayon fibers. The process of making viscose was
discovered by C.F.Cross and E.J.Bevan in 1891.

2. Cuprammonium Rayon: Cuprammonium rayon is obtained by dissolving pieces of

filter paper in a deep blue solution containing tetra-ammine cupric hydroxide. The
latter is obtained from a solution of copper sulphate. To it, NH4OH solution is added
to precipitate cupric hydroxide, which is then dissolved in excess of NH3.

40
40
 Polymer synthesis and characterization

Reactions:
CuSO4 + 2NH4OH → Cu(OH)2 + (NH4)2SO4
Pale blue ppt

Cu(OH) 2 + 4NH4OH → [Cu(NH3) 4](OH) 2 + 4H2O

[Cu(NH3) 4](OH) 2 + pieces of filter paper left for 10-15 days give a viscous solution
called VISCOSE.

Rayon is a synthetic fiber produced from cellulose. Developed in an attempt to

produce silk chemically, it was originally called artificial silk or wood silk. Rayon is a
regenerated fiber, because cellulose is converted to a liquid compound and then
back to cellulose in the form of fiber. For example, cuprammonium rayon is made by
dissolving cellulose in an ammonia copper sulphate solution.

The characteristics of rayon fibers are:

1. They are highly absorbent,
2. Soft and comfortable,
3. Easy to dye &
4. Drape well.

Apparatus:

1. Conical flask (preferably 250 ml)

2. Funnel
3. Glass rod
4. Beaker (preferably 250 ml)
5. Water bath
6. Filter paper (Whitman paper or ordinary filter paper sheets.
Preferably, Whitman)

41
41
 Polymer synthesis and characterization

Reagent & material:

1. CuSO4.5H2O
2. NaOH solution
3. ammonia solution
4. Dilute H2SO4
5. Whitman Paper
6. Distilled H2O

Procedure:

A. Preparation of Schweitzer’s Solution:

1. Weight 10g of CuSO4.5H20.
2. Transfer this to a beaker having 50ml distilled water and add 7.5ml of dilute
H2SO4 to prevent hydrolysis of CuSO4.
3. Stir it with a glass rod until a clear solution is obtained. Add 6ml of liquor
ammonia drop by drop with slow stirring. The precipitate of cupric hydroxide is
separated out.
4. Filter the solution containing cupric hydroxide through a funnel with filter
paper.
5. Wash the precipitate of cupric hydroxide with water until the filtrate fails to
give a positive test for sulphate ions with barium chloride solution.
6. Transfer the precipitate to a beaker that contains 25ml of liquor ammonia or
wash it down the funnel. The precipitate when dissolved in liquor ammonia
gives a deep blue solution of tetra-ammine cupric hydroxide. This is known as
SCHWEITZER’S SOLUTION.
B. Preparation of Cellulose material
1. After weighing 1g of filter paper divide it into very fine pieces and then transfer
these pieces to the tetra-ammine cupric hydroxide solution in the beaker.
2. Seal the flask and keep for 10 to 15 days, during this period the filter paper is
dissolved completely.

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42
 Polymer synthesis and characterization

C. Formation of Rayon Thread

1. Take 25ml of distilled water in a glass container. To this, add 5ml of concH2SO4
drop by drop. Cool the solution under tap water. In a big glass container, pour
some of the solution.
2. Fill the syringe with cellulose solution prepared before.
3. Place the big glass container containing H2SO4 solution produced before in ice
(the reaction being spontaneous results in excess release of energy in the form
of heat, which makes the fibers weak and breaks them).
4. Immerse the tip of the syringe in the solution and press gently. Notice the
fibers getting formed in the acid bath. Continue to move your hand and keep
pressing the syringe to extrude more fibers into the bath.
5. Leave the fibers in solution until they decolorize and become strong enough.
6. Filter and wash with distilled water.

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 Polymer synthesis and characterization

References:

1. C. Walling, "Free Radicals in Solution." Wiley, New York. 1957.

2. J. C. Bevington, "Radical Polymerization," Academic Press, New York, 1961.
3. M. Szwarc, "Carbanions, Living Polymers and Electron Transfer Processes,"
Wiley (Interscience), New York, 1968.
4. L. J. Fetters, /. Polym. Sci. Polym. Sym. 26, 1 (1969).
5. P. J. Flory, "Principles of Polymer Chemistry," p. 149ff. Cornell Univ. Press,
Ithaca, NY, 1953.
6. H. P. Wiley, /. Chem. Ed. 25, 204 (1948).
7. D. P. Hart, Macromol Syn. 1, 22 (1963).
8. "Emulsion Polymerization of Acrylic Monomers," Bull. CM-104 A/cf Rohm
and Haas Company, Philadelphia, PA.
9. P. W. Morgan, "Condensation Polymers: By Interfacial and Solution Methods,"
Wiley (Interscience), New York, 1965.
10.I. Goodman, Encycl Polym. Sci. Eng. 12, 1 (1988).
11.E. Chiellini and G. Galli, Faraday Discussions Chem. Soc. 79, 241 (1985).
12.A. Blumstein, ed., "Polymeric Liquid Crystals," Plenum, New York, 1985.
13."Comprehensive Polymer Science: The Synthesis, Characterization Reactions
and Applications of Polymers" (G. Allen and J. C Bevington, eds.), Vol. 1,
Chaps. 17, 18, and 19 and references therein, Pergamon Press, New York, 1989.
14.R. Norris Shreve, Joseph A. Brink, (1977), Chemical Process Industries.
15.Harold A. Witcoff, Bryan G. Reuben, (2004), Industrial Organic Chemicals.
16.Introduction of polymer science and technology, ManasChanda, (2006).

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