Department of Chemistry

Integrated Laboratory
Lab Report Data Sheet

Name:
Student No:
Section:
Group No:
Date :

Thor Waygen
13201247
02001
2
20 September 2016

Title:
Experiment 1 - Emulsion Polymerization
Objective:
1. To synthesis copolymers of Styrene and Ethyl Metacrylate (EMA) with
different composition by using emulsion polymerization method.
2. To determine the chemical composition of styrene and EMA by using Infrared
Spectroscopy.
3. To determine the adhesive strength of the copolymer films by tensiometer.
4. To determine the relationship between the composition of styrene and EMA
with its adhesive strength.
Introduction and Theory:
In this experiment, in order to study the chemical composition and the
adhesive strength of the copolymer, Styrene and EMA with different ratio were
prepared by emulsion polymerization. A series of copolymers were prepared using
free-radical polymerization with Potassium Persulfate as an initiator. Since we will be
using emulsion polymerization, sodium lauryl sulfate would be used as emulsifier.
The composition of the product will be determined using IR spectrum. The
appearance of benzene in styrene and carbonyl bond in EMA will have an appearance
of absorption peaks between 1600cm-1 and 1720cm-1 respectively. By using
tensiometer, the adhesive strength can be determined.
Polymer is a macromolecule, which consists of mixture of compounds
consisting of repeating structural units, combining through a process called
polymerization. Polymers can be categorized into different categories, for example
homopolymer and copolymer. Homopolymer describes polymer that formed from one
monomer, whereas copolymer is polymer formed from two or more monomers. The
manufactures of copolymers give rise to a wide variety of application of plastics,
since modifying the composition of the monomers and the properties of the plastic
can be customized to meet different needs, such as reducing crystallinity, modifying
glass transition temperature or the solubility. Hence, the plastic or copolymers today
are useful to mankind, which is important in the process of making clothing, shelter,
transportation, communication as well as other modern living application.
In order to prepare polymer, there are different ways of synthesis. Addition
polymerization is one of the most commonly method with vinyl monomer like

styrene, acrylonitrile. Addition polymerization is making use of active center which

can be coordination, cationic, anionic and free radical. Although the kinetic reaction
and equation is different, they are more or less the same which consist of three basic
reaction steps: initiation, propagation and termination. Initiation is the step that the
molecules or reactants is decomposed by thermal or photo to radicals, and followed
by reaction of radicals to formed monomers. Propagation steps is the steps where the
monomer radical would react with other monomers for multiple times in order to
produce a long polymer radical chain. In the termination step, two radical chains will
come together, and hence terminated by either disproportionation or combination.
There are still different types of polymerizing systems, and with different
polymerizing systems they offer practical advantages in industrial applications. One
of the polymerizing systems is emulsion polymerization, which is a heterogeneous
system. Emulsion polymerization consist of two immiscible liquid phases, which is an
aqueous continuous phase and a non-aqueous discontinuous phase consisting
monomer and polymer. Since the initiation step in emulsion polymerization is located
in the aqueous phase, the monomer-polymer particles are quite small, with diameter
around 0.1m. The polymer with higher molecular weight can be produced at higher
rates.
The emulsion polymerization will start with an emulsion with water,
monomer, soap mix together with a water soluble initiator. The whole emulsion
polymerization can be divided into multiple steps. First, the monomer will be
dispersed in a solution of soap and water to aggregate, with a formation of relatively
large droplet of monomer. When more soap is added, part of monomers enters
micelles. With satisfied amount of soap added to form micelles, the concentration is
called critical micelle concentration. Soap, which is also the emulsifier, contains both
hydrophobic tail and hydrophilic head, which the hydrophilic head is facing the
aqueous phase and hydrophobic tail facing the oily phase. Hence, the two phases can
be connected through the soap. Typical micelles in aqueous solution aggregate with
hydrophilic head with surrounding solvent, and all the hydrophobic tail region
clustered in the center region. According to the like-dissolve-like theory, the micelles
can then have dissolved in the aqueous medium. Hence, a favorable environment for
the free radicals generated in the aqueous phase due to the relative abundance of
monomers and the high surface area to volume ratio of micelles compared to the
monomer droplets.

Fig 1. Diagram of Micelles.

The polymerization is initiated by the diffusion by water soluble initiator. For
example, In order to prevent polymerization process in big monomer droplets,
peroxides and persulfates are commonly used. Regarding kinetics, the concentration
of initiator should keep lower so as to keep both the rate of termination and radical
concentration low. As a polymer is formed, the micelles grow by the addition of
monomer from the aqueous phase. Each micelle would then polymerize to high
molecular weight as a single macromolecule in which polymer is formed in the

hydrophobic head of micelles. The monomer droplets will then form at the beginning
acts as a reservoirs of monomer, by diffusion through the aqueous phase, the polymer
particles are growing. Since there is one radical per micelle, that means the polymers
formed with more or less the same molecular weight, and the final products collected
directly can be used without any purification. The final product is a dispersion of
polymers particles in water.
There are a lot of advantages and benefits that emulsion polymerization over
traditional free-radical polymerization. In traditional free-radical polymerization,
there is a tradeoff between molecular weight and polymerization rate. On the other
hand, the emulsion polymerization will provide high molecular weight polymers with
faster rates since the concentration of growing chains within each polymer particles is
very low. In emulsion polymerization, it allows ease of stirring during reaction and
ready thermal control. Emulsion could then be use directly with narrow molecular
weight distribution.
In this experiment, Sodium Lauryl Sulfate would be used an emulsifier or soap
to assist the monomer to form micelles. Sodium phosphate dibasic was used as a
buffer solution to maintain the pH value of the system. Potassium persulfate was used
as Initiator, two Sulphate radicals would be formed from one persulfate ion, to initiate
the monomer as radical. Six of different composition of polymer solution with
different feeding ratio of monomer would be prepared first. Nitrogen was used to
ensure the polymerization taking place in an inert environment. After the
polymerization, the polymer would be coagulated by Al2(SO4)3 solution. The
copolymer product would then be filtrated, washed with particular solvent and dried.
After a week, the polymer product would be weighed so as to calculate the yield. On
the other hand, certain amount of each would be dissolved in chloroform and toluene
solution to determine chemical composition and adhesive strength respectively. In the
chemical composition determination, the polymer solution would be prepared as a
thin film to measure by IR spectroscopy and micrometer. According to the Beer
Lambert Law, the concentration of each monomer could be indicated and calculated
from their corresponding absorption peaks as early mentioned. The composition is
then calculated.
The adhesive strength of each polymer would be expressed as stress with unit Nm2
. The polymer solution in toluene was poured in-between 2 aluminum bars. After
drying, it would be pull by the tensiometer so as to measure the breaking force, then
the adhesive strength.
Procedures and Observations:
1. Copolymerization of Styrene and Ethyl Methacrylate
1

Procedures
90ml of styrene and 70 ml of ethyl
methacrylate were put in two
separating funnel in a fume hood. 20
ml of 10% aqueous sodium
hydroxide solution prepared by
dissolving 4g sodium hydroxide
pellets into 40 ml D.I. water was
added to remove the inhibitor.
Each solution mixture was washed
with D.I. water thoroughly until pH
paper displayed a colour of pH 7.

1.434 g of Na2HPO4, 1.477g of

K2S2O8, 2.714g of Sodium Lauryl

Observations
Both styrene and EMA were colourless
liquid with pungent smells.
Sodium hydroxide was white pellets and a
colourless solution was formed after
dissolved in water.

Two layers of solution were formed in

separating funnel, where organic layer was
on top and aqueous layer at the bottom.
After a few washes, the aqueous layer
turned from alkaline to neutral using pH
paper and indication.
Na2HPO4, K2S2O8 and Sodium Lauryl
Sulfate were all in white powder form.

Sulfate were dissolved into D.I.

Water with 250 ml Volumetric Flask.
The solutions were then diluted to
the graduation mark with D.I. Water.
6 polymer solutions with different
composition were prepared
according to the following table.
Bottle
Styrene
EMA
(ml)
(ml)
1
20
0
2
20
0
3
15
5
4
10
10
5
5
15
6
0
20

For bottle 2-6, 5 ml of Na2HPO4, 5

ml of K2S2O8, 20 ml of Sodium
Lauryl Sulfate and 10 ml of D.I.
water were added. For bottle 1, only
10 ml of Na2HPO4, 10 ml of K2S2O8,
20 ml of Sodium Lauryl Sulfate were
added.
5 Nitrogen gas was bubbled to each
bottle for about 5 minutes. The
bottles were closed tightly.
6 The bottles were placed in a shaking
water bath with 70 with shaking
rate of 150/min. The bottle was
heated in bath for 90 mins.
7 The reaction mixtures were allowed
to cool for in the fumehood. The
bottles was then opened in the
fumehood. 10 ml of coagulant,
prepared by dissolving 29.251 g of
Al2(SO4)3.18H2O in 100 ml of water
was added into each bottle.
8 The coagulated materials were
cooled to room temperature and the
polymer solids were filtered out with
three pieces of filter paper using
vacuum filtration.
9 The solids were washed with 30 ml
hot water twice to remove Al2(SO4)3
solution. Then, they were washed
with 20 ml methanol twice to remove
unreacted monomers. 20 ml of
acetone was then used to wash the
polymer. The samples were poured
onto a weighed wash glasses.
12 After a week, the dried samples were
weighed and their yields were
determined.

Colorless solution was formed when

Na2HPO4 and K2S2O8 were dissolved in
D.I. Water.
All solution are colourless.

Bubbles were given off in each bottle.

There were two layers formed.
The solution became milky white solution
with some yellow solids.
White emulsion was formed after adding
coagulant, which is milky solution.

White powder product was collected. The

filtrate was milky white solution.

2. Properties Determination
Chemical Composition Determination
Procedures

Observations

0.2g of each product were weighed

accurately in 20 ml chloroform. The
solution was heated to dissolved all
the product.
A flat glass plate was divided into 6
rectangular area with dimension of
1 x 1. Each rectangle was marked
with a number corresponding to one
of the bottle number at the back.
The solution was poured on the glass
plate to a depth of 1-2 mm. The
solvent was evaporated gently to
dryness and avoid foaming heating
only below boiling temperature of
the solvent.
The thin films were carefully peeled
off and IR spectroscopy was used to
determine the composition of the
copolymer. The thickness of each
sample was then measured by the
micrometer.

The chloroform was colourless liquid.

The powder dissolved with heating and
stirring.
-

The solution was colourless and viscous.

The transparent film was formed on the
plate with some cloudy white region.

Mechanical Properties Determination

1

2
3

Procedures
0.7 g of each product was weighed
accurately in 10 ml toluene. The
polymer product was heated and
stirred on a heater to be dissolved.
24 aluminum bars with clear surface
were cleaned with fine sand paper.
Some of the polymer solution was
poured on the edge of one aluminium
bar, then be covered it with another as
below.

Observations
The toluene was colourless liquid with
pungent smell.
The powder dissolved by heating and
stirring forming a viscous colourless
solution.
-

weight

aluminium bars

copolymer

4
5

The aluminium bars were tied using

rubber band and kept for a week.
A tensometer was used to determine
the adhesive strength (in lb/width of
the Al bar) of the copolymers films
with a constant cross-section area at a
constant cross-head speed.
All the thin film plastics in a pair of
aluminum bar were tested by
tensometer as step 5.

A pop sound was heard when the polymer

was broken.

Data:
Emulsion Polymerization
Copolymer
1
2
3
4
5
6

Weight of products (g)

13.940
14.512
7.284
8.836
12.344
13.242

Density of EMA: 0.917 g/ml

Density of Styrene: 0.906 g/ml
Chemical Composition Determination (Infrared Spectroscopy)
Copolymer

Thickness (mm)

1
2
3
4
5
6

0.038
0.031
0.015
0.013
0.028
0.043

Absorption peak at 1600

cm-1
T
0.15833
0.44583
0.62083
0.76666
0.80000
N/A

Absorption peak at
1700 cm-1
T
N/A
N/A
0.37083
0.25000
0.12500
0.01000

Mechanical Properties
Copolymer
1
2
3
4
5
6

Overlapping Area ( cm x cm)

Trial 1
Trial 2
6.3 x 2.4
6.4 x 2.4
6.3 x 2.5
6.3 x 2.4
6.3 x 2.5
6.3 x 2.4
6.3 x 2.4
6.3 x 2.4
6.3 x 2.4
6.4 x 2.4
6.3 x 2.4
6.3 x 2.5

Peak Height (unit)

2.5
N/A
2.9
2.9
7.5
7.0
9.5
9.5
6.5
6.5
6.0
4.1
2.5
N/A

Data Treatment:
1. Calculate the molar absorptivity of each polymer sample.
According to Beers law,
= log =
Where A = absorbance
T = transmittance of light
a = molar absorptivity
b = thickness of polymer thin film
c = concentration of polymer
Copolymer

Thickness
(mm)

1
2
3
4
5
6

0.038
0.031
0.015
0.013
0.028
0.043

Absorption peak at 1600

cm-1
T
0.15833
0.44583
0.62083
0.76666
0.80000
N/A

Absorption peak at 1700

cm-1
T
N/A
N/A
0.37083
0.25000
0.12500
0.01000

For copolymer 1, c = 1 since it is a pure styrene,

Therefore,
= log =
log 0.15833 = (0.031)(1)
= 21.064 9: 9:
For copolymer 2, c = 1 since it is a pure styrene,
Therefore,
= log =
log 0.44583 = (0.031)(1)
= 11.317 9: 9:
Hence, the average molar absorptivity of styrene is 16.1905 9: 9:
For copolymer 6, c = 1 since it is a pure EMA,
Therefore,
= log =
log 0.01000 = (0.043)(1)
= 46.511 9: 9:
Hence, the molar absorptivity of EMA is 46.511 9: 9:
For copolymer 3, 4 and 5,
By using the molar absorptivity of styrene and EMA are 16.1905 9: 9: and
46.511 9: 9: respectively,
Consider copolymer 3,
The peak at 1601.613 represents styrene,
= log =
log 0.62083 = (16.1905)(0.015)
= 0.85246
The peak at 1723.972 represents EMA,
= log =
log 0.37083 = (46.511)(0.015)
= 0.61752
Percentage composition of styrene
0.85246
=
100% = 57.991%
(0.85246 + 0.61752)
Percentage composition of EMA
= 100% 57.9901% = 42.008%
For copolymer 4 and 5, the calculation is as copolymer 3 as tabulated as below,
Copolymer
4

Concentration of
Styrene
log 0.76666 =
(16.1905)(0.013)
= 0.54826
log 0.80000 =
(16.1905)(0.028)
= 0.21377

Concentration of
EMA
log 0.25000 =
(45.611)(0.013)
= 1.0153
log 0.12500 =
(45.611)(0.015)
= 1.31998

Percentage of
Styrene
A.BCDEF

(A.BCDEFG:.A:BH)

Percentage
of EMA
64.936%

100% = 35.063%
A.E:HII
(A.E:HIIG:.H:JJD)

100% = 13.937%

86.062%

The concentration and percentage composition of each monomer is tabulated:

Copolymer
1
2
3

Monomer
Styrene
Styrene
Styrene
EMA
Styrene
EMA
Styrene
EMA
EMA

4
5
6

Concentration (M)
1
1
0.85246
0.61752
0.54826
1.0153
0.21377
1.31998
1

Composition of each monomer (%)

100
100
57.991
42.008
35.063
64.936
13.937
86.062
100

2. Calculate the stress of each polymer sample.

1 unit of peak height = 5 mV = 0.05 kN = 50N
Copolymer

Overlapping Area ( cm x cm)

Trial 1
Trial 2
6.3 x 2.4
6.4 x 2.4
6.3 x 2.5
6.3 x 2.4
6.3 x 2.5
6.3 x 2.4
6.3 x 2.4
6.3 x 2.4
6.3 x 2.4
6.4 x 2.4
6.3 x 2.4
6.3 x 2.5

1
2
3
4
5
6

Peak Height (unit)

Trial 1
Trial 2
2.5
N/A
2.9
2.9
7.5
7.0
9.5
9.5
6.5
6.5
6.0
4.1

For each copolymer trials,

E = 109H
= 5
= 0.05 1000
fghijklm nogph
9E =
qrhgsittklm ughi ov wotosxyhg
z{gh|| ov {gkis :Gz{gh|| ov {gkis E
9E

The overlapping area, voltage, breaking force and stress are calculated and tabulated:
Copolymer Trial
1
2
3
4
5
6

1
2
1
2
1
2
1
2
1
2
1
2

Overlapping
Area (m2)
0.001512
0.001536
0.001575
0.001512
0.001575
0.001512
0.001512
0.001512
0.001512
0.001536
0.001512
0.001575

Peak
height
(unit)
2.5
N/A
2.9
2.9
7.5
7
9.5
9.5
6.5
6.5
6
4.1

Voltage
required to
break (mV)
12.5
N/A
14.5
14.5
37.5
35
47.5
47.5
32.5
32.5
30
20.5

Breaking
force
(N)
125
N/A
145
145
375
350
475
475
325
325
300
205

Stress (Nm-2)
82671.95767
N/A
92063.49206
95899.4709
238095.2381
231481.4815
314153.4392
314153.4392
214947.0899
211588.5417
198412.6984
130158.7302

Therefore, the average stress of the copolymer is then calculated and tabulated:

Copolymer
1
2
3
4
5
6

Average Stress (Nm-2)

82671.95767
93981.48148
234788.3598
314153.4392
213267.8158
164285.7143

3. Calculate the percentage yield of each polymer sample.

The Density of EMA = 0.917 g/mL
The Density of Styrene = 0.906 g/mL
For each of the copolymer sample,
=
= 0.917
= 0.906
= +

=
up{is i|| ov wotosxyhg
=
100%
hogh{kpis i|| ov wotosxyhg

The masses of copolymers are therefore calculated and tabulated as below,

Copolymer
1
2
3
4
5
6

EMA added
(mL)
0
0
5
10
15
20

Styrene added
(mL)
20
20
15
10
5
0

Mass of EMA
added (g)
0.0000
0.0000
4.5850
9.1700
13.7550
18.3400

Mass of styrene
added (g)
18.1200
18.1200
13.5900
9.0600
4.5300
0.0000

The percentage yield of the copolymers is therefore calculated and tabulated as below,
Copolymer
1
2
3
4
5
6

Actual mass of product

(g)
13.9400
14.5120
7.2840
8.8360
12.3440
13.2420

Theoretical mass of
product (g)
18.1200
18.1200
18.1750
18.2300
18.2850
18.3400

Percentage yield of
copolymer (%)
76.932
80.088
40.077
48.470
67.509
72.203

Questions:
1. How is the thermal transitional behavior varying with the copolymer
composition?
The factor affecting the thermal transitional behavior is Glass Transitional
Temperature (Tg). Since different polymers would have different glass transitional
temperature, they would have different thermal transitional behavior. For thermal
polymer that has Tg lower than room temperature, they are soft polymer which are in
rubbery state like plastics such as PP or PE. While for the polymers with have higher
Tg than room temperature, they are called hard polymer which are in glassy state in
room temperature like PS, PMMA and PET. These hard polymers are usually brittle
and easy to be break at room temperature. Generally, the glass transitional
temperature could be related to the equation below:

m = : m: + E mE
where : and E are weight fraction of monomer 1 and 2 respectively
m: and mE are Glass Transitional Temperature of homopolymer 1 and 2
respectively.
Generally, the Glass Transitional Temperature of a copolymer lies between Tg of the 2
polymers.
In this experiment, its determined that the property of the polymers would be
affected by the composition of the monomer. The composition is related to the
reactivity ratio and the feed ration of the monomers forming the polymers.
However, Tg is not affected by the structure itself, hence, there is no direct
relationship between Tg and the crystal lattice structure. The structure is affecting the
melting temperature instead of Tg.
Hence, it can be concluded that random copolymer would have relatively low
ratio of Tm to Tg. For block or grafted copolymer, they might be having similar
properties to the homopolymer involved rather than the intermediate properties due to
the long homogenous chain segment. Therefore, a block copolymer would have
higher softening point and lower brittle temperature.
2. What are the precautions required to cast a good polymer thin film?
There are a few precautions in order to have good polymer in thin film. Since it is
a free-radical chain polymerization, free radical is very reactive and difficult to
control. Hence, it is better to carry out the experiment in an inert environment. Hence,
the glasswares that being used in the experiment should be washed and dried
thoroughly to get rid of any contamination. Besides, it is crucial to bubbled nitrogen
into the polymer as to remove oxygen that formed radical easily inside the polymer.
Besides, it is crucial to wash the monomer using Sodium Hydroxide in order to
remove the inhibitor in the stock solution. The pH of the polymer should be neutral
too hence a lot of washing should be done. Besides, in order to provide an even
environment for the whole experiment, the reaction mixture should be mixed by
shaking thoroughly at constant temperature.
During the preparation of thin film, it is important to dissolve polymer solid in
solvent with gently heating. Since the thickness of the film is inclined with the
amount of solvent and polymer used, a thinner film can be obtained in smaller amount
of polymer used. It is important to stir the polymer during the heating process to
ensure all the polymer solids can be dissolved and avoid the burning of polymer. The
solvent used must be a non-volatile solvent to prevent escape of solvent during
heating. Besides, using a less viscous polymer is better since a more viscous polymer
would produce a relatively thick polymer film. Lastly, it is important to pour the
polymer with constant pouring rate so the thickness of the film over the whole
polymer would be constant and even.
3. What are the effects of polymer molecular weight on its mechanical
properties?
Mechanical properties of polymer include the stiffness, hardness, viscosity,
toughness temperature, strength and others. However, not all mechanical properties
are relating to Tg, but polymer molecular weight since it determines many physical
properties. For lower molecular weight, the Tg and the mechanical properties will be
relatively low for polymer material that are useful for commercial applications. For
some useful polymers, it is required to have Tg above room temperature to have
stronger mechanical properties to bear loads.
The mechanical properties, S can be related to the equation below:
Therefore


l
Where is the mechanical properties at infinite molecular weight
A is the constant depending on the type of polymer
l is the number average molecular weight of polymers
=

Therefore, the strength of the polymer increases with molecular weight and
eventually saturated to the infinite molecular weight, in the result of . l can be
modify too according to the properties we desired.
4. Find out an ASTM or other standard testing methods (BS, ISO) that can be
used to determine the strength of an adhesive. Please enclose reference
material.
If a coating is to fulfill its function of protecting a substrate, it must adhere for the
expected service life. Since the substrate and surface preparation have a drastic effect
on the adhesion of coatings, evaluation to the adhesion of coating or surface treatment
is considerable in industry.
From the website of American Society for Testing and Materials (ASTM), it can
be found that there is a standard test method for evaluating adhesion by knife. This
method covers the procedure for assessing the adhesion of coating films to substrate
by using a knife. Substrate relates to the basic surface which the coating adheres. This
method is to establish whether the adhesion of coating to substrate is generally at an
adequate level. (http://www.astm.org/Standards/D6677.htm)
Besides, another test which is using tape test, for assessing the adhesion of coating
films to metallic substrates by applying and removing pressure-sensitive tape over
cuts made in the film. (http://www.astm.org/Standards/D3359.htm)
Lastly, for some organic coatings, a method namely standard test method for
tensile properties of organic coatings is used, which covers the determination of the
elongation, tensile strength, stiffness of organic coatings when tested as free film.
(http://www.astm.org/Standards/D2370.htm)
Discussion:
In this experiment, series of copolymer of styrene and ethyl methacrylate was
prepared through emulsion of polymerization, a technique for free-radical addition
polymerization. By preparing the copolymer solid and the transmission of the
absorption peak, the chemical compositions can then be calculated. The carboncarbon bond found in benzene ring in styrene can be found at 1600cm-1 and the
carbon-oxygen bond in ethyl methacrylate can be located at 1720cm-1. Since the
transmission of the absorption peaks is related to the concentration, the concentration
of the monomers of the copolymers can be determined by using Beer-Lambert law.
The relative chemical composition of the two monomers can then be determined.
The mechanical strength of the polymer, can be determined by measuring the
adhesive strengths using tensiometer. The viscous polymers that prepared was poured
on a rectangular aluminum bar and covered by another aluminum cover. After the
films were dried, the tensiometer was pulled to measure the adhesive strength. The
peak height obtained was directly proportional to the breaking force.
During the preparation, we need to separate the pure monomer from the inhibitor
that used to prevent the monomer to undergo polymerization. Sodium Hydroxide was
used to remove inhibitors, and water was used to neutralize the monomer solution.
Potassium persulfate, Sodium phosphate dibasic and Sodium lauryl sulfate were
added as initiator, buffer solution and emulsifier respectively. Emulsifier contains
hydrophilic tail directed to the aqueous phase and hydrophobic tail to the oil phase.

Hence, two phases can come together. The buffer solution is important as persulfate
initiators decompose to form radicals, they will lower the pH of the aqueous phase.
The pH of the aqueous phase decreases, the decomposition rate of persulfate initiators
increases, leading to the premature consumption of the initiator. To remove oxygen
gas that easily converted to free radicals, nitrogen gas is pumped into the polymers.
After reaction, coagulant is added and to precipitate the polymer.
There are a few advantages in this experiment. The chemical composition can be
measured easily and accurately by using IR spectroscopy and preparation of the
polymer thin film. Emulsion polymerization takes advantage of using multiphase
polymerization, which water can be used as coolant to remove heat to prevent the
overheat of the polymer. Besides, emulsion polymerization can undergo rapid
reaction, hence the reaction can be carry out in few hours instead of long time. The
viscosity of the polymer can have good control with less viscous reaction medium.
Since the polymer is formed within micelles, the viscosity of reaction mixture will not
increase with increasing molecular weight because the auto-acceleration would not be
easily occurred.
The polymer formed could then be separated by filtration, the man power and time
can be separated without any processing and modification,
However, there are still some disadvantage. First, the emulsifier and the reactant
maybe be difficult to remove since there are yellow particles inside the product.
Emulsifier leave some degree of water sensitivity. In order to investigate the chemical
composition and mechanical properties, a thin film of polymer should be prepared but
the polymer may not be easily dissolved in the organic solvent. Besides, a longer time
is needed to wait for the polymer thin film to dry, and there exist difficulties to
achieve a thin film and may not be able to give rise to an accurate result. Since
emulsion polymerization was used to produce high conversion polymerization, chain
transfer may have occurred easily to produce different type of polymer chain rather
than a linear chain.
There are few errors in this experiment. First, oxygen may not be completely
removed during the preparation step, some may have remained dissolved in the
reaction mixture and undesired product may not produce due to the formation of
oxygen radicals. The inhibitor may not be completely removed by sodium hydroxide,
so the yield of the polymerization may be lower than expected. The pH value of the
reaction mixture may not be neutral and hence affecting the product too. Coagulant
used may not completely removed too, so a higher yield is expected.
During the separation process, some polymer might dissolve in organic solvent
such as methanol and acetone. Hence, loss of polymer may occur too, resulting in the
smaller yield of product.
In the preparation process, the thickness of the glass polymer may not be even,
even in the small area. There may be some air bubbles inside the thin film and the
polymer particles might not be completely dissolved in the chloroform solution,
resulting in the inaccurate measurement in IR spectroscopy. Besides, the thickness of
the polymer between the aluminum bars may not be the same, and not dried enough,
the tensiometer would give a board peak with relative low peak height. The
overlapping area of the polymers may not completely cover the aluminum bar, and the
aluminum bar may not be fine and clean enough, hence, the tensiometer would
deviate from expected.
In order to improve the experiment, it is better to bubble the reaction with nitrogen
for a longer period of time to ensure there exist no oxygen in the reaction mixture.
Hence, in order to ensure there are no impurities in the reaction mixture, the
glasswares used in this experiment should be wash and clean thoroughly. Excess

amount of sodium hydroxide should be used to remove all the inhibitors. The washing
process of the reaction mixture should be carry out more to ensure the pH of the
reaction mixture is neutral.
During the filtration process, the product can be washed with more hot water so
the coagulant can be removed completely. On the other hand, lesser amount of
methanol and acetone should be used to reduce the amount of loss of polymer formed.
Each polymer should have two or more trial bottles in order to obtain more accurate
result.
Before the measurement, adequate time should be provided in order to provide the
polymer film to be dry thoroughly before measurement in order to measure the
accurate adhesive strength using tensiometer. Besides, by preparing more trials and
obtain the average peak height would increase the accuracy of the result. On the other
hand, it would be better to heat and stir the solution gently before apply to the glass
plate to form polymer thin film to dissolve the polymer solid completely and prevent
overheating by stirring. Furthermore, the usage of relatively transparent and thinner
film for IR spectroscopy is better than those thick and less transparent. In order to
ensure the polymer formed is a linear polymer chain, it is better to use mass
spectroscopy to investigate the linkage of monomer in polymer to investigate whether
chain transfer is involved.
There are a lot of application for emulsion polymerization, for instances, it can be
used to produce three common usage of polymers: synthetic rubber (nitrile rubber and
acrylic rubber), plastics (acrylonitrile-butadiene-styrene terpolymer and polyvinyl
fluoride) and dispersions (polymers sold as aqueous dispersions). Emulsion polymers
are usually compounded to varying degrees with other components but to in their
original form in order to tailor them to their intended purposes. For instances,
pigments and thickeners and often added to the latexes to modify their rheological
properties.
For copolymers, with different chemical composition, different usage of polymer
can be synthesis so a wide variety of application can be meet.
Conclusion:
The chemical composition and mechanical composition of each monomer in
copolymer is tabulated as shown.
Copolymer
1
2
3
4
5
6
Copolymer
1
2
3
4
5
6

Monomer
Styrene
Styrene
Styrene
EMA
Styrene
EMA
Styrene
EMA
EMA

Concentration (M)
1
1
0.85246
0.61752
0.54826
1.0153
0.21377
1.31998
1
Average Stress (Nm-2)
82671.95767
93981.48148
234788.3598
314153.4392
213267.8158
164285.7143

The percentage yield is tabulated as shown

Composition of each monomer (%)

100
100
57.991
42.008
35.063
64.936
13.937
86.062
100

Copolymer
1
2
3
4
5
6

Actual mass of product

(g)
13.9400
14.5120
7.2840
8.8360
12.3440
13.2420

Theoretical mass of
product (g)
18.1200
18.1200
18.1750
18.2300
18.2850
18.3400

Percentage yield of
copolymer (%)
76.932
80.088
40.077
48.470
67.509
72.203

Reference:
1. Billmeyer , Fred W, Textbook Of Polymer Science, A Wiley-lnterscience
Publication, 1984, P3, 128-131
2. C.S. Chern, Emulsion polymerization mechanisms and kinetics, Prog. Polym.
Sci. 31 (2006) 443486
3. A. Aymonier, E. Papon, J.-J. Villenave, Ph. Tordjeman, R. Pirri, and P.
Gerard, Design of Pressure-Sensitive Adhesives by Free-Radical Emulsion
Copolymerization of Methyl Methacrylate and 2-Ethylhexyl Acrylate. 1.
Kinetic, Chem. Mater. 2001, 13, 2562-2566
4. http://en.wikipedia.org/wiki/Emulsion_polymerization
5. http://en.wikipedia.org/wiki/Polymer