EXPERIMENT 1: EMULSION POLYMERIZATION OF STYRENE

Abstract

In this experiment, styrene is polymerized by the emulsion polymerization technique at

about 70 °C. High molecular weight polymer can be produced by this polymerization
technique. The film synthesized is bright and yellow in color due to the poor yield.
However, due to the used of surfactant, the impurity of the emulsion polymer is higher
than the other technique. The control of reaction condition is crucial to produce a high
quality and desired polymeric products. FTIR analysis shows the type of bond that
indicates the content in the polymeric product that synthesized. Impurities and monomer
were shown in the spectrum due to the environment and contamination of surrounding.
This causes a low percentage yield of polystyrene.

1.0 Introduction

Polymerization reactions may be classified as homogeneous, where a single phase

exists, and heterogeneous systems, where multiple phases are present. Homogeneous
polymerizations include bulk and solution system while heterogeneous polymerizations
include suspension, emulsion, gas phases and solution systems where one or more
components are insoluble. (Young& Lovell, 1997)

Free radical polymerizations can be readily performed using bulk, solution, suspension
and emulsion techniques, and all four techniques are used commercially. As ionic and
coordination systems are generally inactivated by water, these polymerization are
usually confined to bulk or suspension methods only. Radical chain polymerization is the
main synthesis method for the emulsion polymerization technique. It involves the
polymerization of monomers in the form of emulsion for example colloidal dispersions.
(Odian, 2004)

An emulsion polymerization system must include oil-soluble monomer, water-soluble

initiator, water and surfactant (emulsifiers). The monomer is dispersed and emulsified by
the action of the surfactant in the aqueous medium. The action of the emulsifiers is due
to both hydrophilic and hydrophobic portions. The monomers will aggregate to form
spherical shape around the aqueous medium so that the hydrophilic polar heads are
pointed to the aqueous medium and long hydrophobic tails which are mainly constitute
of hydrocarbon chains is pointed away from aqueous medium. When the concentration
of surfactants exceeds its critical micelle concentration, the surfactant will aggregate to
form small colloidal clusters of micelles. (Young& Lovell, 1997)

O - Na +
S
O

hydrophobic tail hydrophilic head

Figure 1: Illustration of Surfactants (sodium lauryl sulfate)

In the emulsion polymerization technique, the initiator (oil-insoluble) is present in the

water phase and this is where initiating radicals are produced. The site of polymerization
is not located in the monomer droplets since the initiators utilized are insoluble in the
organic monomer. In most cases, polymerization takes place in the micelles. Monomer
droplets do not compete effectively with micelles in taking radicals produced in solution
since the smaller total surface area of the monomer droplets. (Painter& Coleman, 2009)

Polymerization of the monomer in the liquid phase undoubtedly takes place but does not
contributed significantly since the monomer concentration is low and the medium is not
suitable for polymerization to take place due to monomer which is oil-soluble is
resistance to its hydrophilic properties. The propagating radicals would precipitate out of
aqueous solution at very small size. Thus, the micelles are the meeting place for the oil-
soluble organic monomer and water-soluble initiator. The micelles are favored for
polymerization since high concentration of monomers in micelles compared to monomer
in aqueous medium. (Billmeyer, 1984)

As polymerization takes place, the micelle gets bigger by the free radical addition of
monomers from the aqueous solution whose concentration is replenished by dissolution
of monomer from the monomer droplets. The growing chain will terminate if they are
attacked by new initiators. The process of polymerization will occur again in new growing
chain as more initiators attack the monomers to initiate the reaction and more polymer
chain will be formed. This lead to micelle becomes larger and larger. The schematic
representation of an emulsion polymerization system is shown by figure 2. (Chern, 2005)
 Figure 2: Schematic Diagram of Emulsion Polymerization

Emulsion polymerization is presently the predominant process for the commercial

polymerizations of vinyl acetate, chloroprene, various acrylate copolymerization and
copolymerization of vinyl acetate with styrene and acrylonitrile. It is also used for the
methacrylates, vinyl chloride and some fluorinated ethylene. (Billmeyer, 1984)

1.1 Objective

The objective of this experiment is to study the emulsion polymerization of styrene, to

know the spectroscopic identification of polystyrene and to learn to analyze and interpret
the FTIR spectrum.

1.2 Apparatus

Water bath machine (70ºC),Conical flask with stopper (250ml),Measuring cylinder

(100ml), Electron-balance, Nitrogen tank , Beaker, Filter paper ,Vacuum filter , an
Aluminium foil and Stopper

1.3 Materials

Styrene monomers, Potassium persulfate(K2S2O8), Sodium hydrogen

phosphate(Na2HPO4), Sodium lauryl sulfate, Aluminum sulfate (Al2(SO4)3),Distilled
water(H2O) and Nitrogen gas(N2)
1.4 Procedures:

1. Pottasium persulfate (0.03g), sodium hydrogen phosphate (0.03g) and sodium lauryl
sulfate (0.2g) was weighted by using electronic weight scales.
2. Distilled water (60ml) was measured by using cylinder and a mixture of distilled water,
K2S2O8,Na2HPO4 and sodium lauryl sulfate was prepared in a conical flask.
3. The styrene of 20ml was added into the conical flask and the flask is stopper
immediately with glass stopper.
4. A blanket of nitrogen gas was allowed to flow into conical flask for 3 minute.
5. The flask was immersed into the water bath at 70⁰C by clamped it to the shaker and
allow to shake slowly over 1 hour.
6. While the 1 hour polymerization was carried out, 2.5g of aluminium sulphate
Al2(SO4)3 was weighted and 100ml distilled water was measured to prepare an alum
solution.
7. After 1 hour at where the polymerization was completed, the alum solution was
added separately each time with 10ml to the conical flask mixture.
8. When the precipitate formed, the polymeric product formed was filtered off through
Buchner funnel.
9. The product was dry at room temperature until the weight was constant in an
aluminium foil.
10. The weight of the aluminium foil was measured.
11. The products formed were collected by using spatula.
12. Part of the sample was dissolved by using toluene, after that a very thin film was
obtained through heating and dry vacuum.
13. The dried product was submitted for FTIR analysis.
14. The other part of the product was then summit to the instructor.
1.5 Result and Discussion

The polystyrene film that obtained from this experiment is much less (6.87%) compared
to the theoretical yield of product. This is because the film that obtained may contain
some impurities that can affect the rate of polymerization reaction and its purity. The
impurities can be due to stain stick on the wall of the reacting conical flask and other
apparatus used in this experiment. Emulsifiers also can be served as impurities.

Table 1: Weight of polymeric product

Sample Weight , g
Aluminium foil mould 1.3730g
Aluminium foil mould + Polystyrene 2.6228g
Polystyrene 1.2498g

Table 2: Theoretical yield of product and percentage yield of the product

Density of styrene,  0.909 g cm 3 0.909 g cm 3

Volume of styrene, V 20.0 ml 20.0 cm 3

Mass of styrene, M  V 18.18 g

Relative molecular mass of 8(relative atomic mass of carbon atom)+

styrene, RMM (C=12, H=1) 8(relative atomic mass of hydrogen atom) 104

No. of moles of styrene, m

0.175 mol

Percentage yield of 6.87%

product

Since 0.175 mol of styrene is used so that we can deduct that 0.175 mol of styrene
monomer is needed to produce 0.175 mol of polystyrene. Therefore, 18.18 g of styrene
is needed to produce the theoretical mass of polystyrene equivalent to 18.18 g.
Where w = Actual yield or product or mass of polymeric product, g
The function of various chemicals and reaction condition used in this experiment

Styrene acts as monomer and is the small repeating unit that has vinyl- substituted
benzene ring used for polymerization to form polystyrene. Propagation can only occur
with the present of double bond in styrene monomer. In this polymerization, styrene acts
as monomers that undergo radical polymerization and are poorly soluble in water.
Monomer which is insoluble in water will form emulsion. Monomers will diffuse into
micelles to form polymer during polymerization. Styrene monomer consist double bond
that are invaded by initiators which are required in free radical polymerization since
double bond is an active site for all almost reaction. (Odian, 2004)

Figure 3: Monomer – Styrene

Pottasium Persulfate, K2S2O8 act as a radical-generating initiator that produces

SO4ˉ· free radicals as a result of bond scission. The activation energy is quite high, thus
persulfate is usually conducted at high temperature (50˚C or higher), the side product of
decomposition of persulfate, produce by reaction of S2O82- with water are HSO4¯. (Young
and Lovell, 1997)

 Potassium Persulphate (K2S2O8) will dissolve into persulphate ions:

K2S2O8 2K+ + S2O82-

 S2O82- ion then homolitically split into two free radicals at about 50°C:

 The radical then react with styrene to form radical carrier:

Figure 4: The schematic mechanism of radical formation from initiator

Sodium Hydrogen Phosphate act as a buffer solution to control pH in the solution (since
HSO4¯ will alter pH of solution) to prevent hydrolysis of surfactants and may also be
necessary to ensure reasonable initiator efficiency. Another reason is at lower pH value
will result precipitation of insoluble acid and the all stabilizing function is lost.
(Chern, 2005)

Sodium Lauryl Sulfate is a surfactant or emulsifier that used to impart colloidal stability to
the latex particles. The surfactant is used to stabilize the monomers in colloidal
suspension, forming the primary sites for nucleation. The surfactant is making up with
hydrophilic head and hydrophobic tail. Hydrophilic head is water soluble whereas
hydrophilic is non- soluble in water thus forming micelle where hydrophilic pointing
outward and hydrophobic pointing inward in water when it reaches critical micelle
concentration. (Chern, 2005)

Aluminum Sulfate act as a coagulate agent. Aluminum sulfate added into solution after
polymerization to coagulate the polymer formed inside the solution to allow filter out of
polymer from solution. The alum solution that added into the polystyrene can cause the
coagulation of the particles to form a white precipitate. (Billmeyer, 1984)

Distilled water acts as the aqueous medium that provides the site for polymerization.
Most organic liquids, including monomer, are non-polar; their activities in water are
limited. This aqueous medium allows the dispersion of discrete monomer droplets.
Water have has a high heat capacity, which allowing polymerization process to dissipate
large quantities of heat energy without problem if heat control is well developed. The low
viscosity of the water medium allows rapid mixing and heat transfer. (Odian, 2004)

The following shows several reaction conditions that are important to the emulsion
polymerization of styrene so that high yield product is achieved.

1. A blanket of N2 gas was allowed into flask for 3 minute to allow the flask purged
out the atmosphere so that the reaction can occur in inert condition.
2. The flask was stopper immediately so that the inert condition will be maintained.
3. The aluminum foil is used to prevent stopper react with solution because the
solution is corrosive.
 4. This flask was immersed into the water bath which was set at 70 °C. This is
because the melting temperature of polystyrene is 240°C, and the glass
transition temperature of polystyrene is 95°C. 70°C can make sure the reaction
occur in solution state.
5. The flask was begun shaked slowly over 1 hour to start polymerization. The 1
hour is just enough for the products formed. This will control the molecular weight
of the product so that the product formed will not be too long or too short.
6. The product was dried to constant weight in vacuum oven at 80°C overnight. This
is because the boiling point of water is 100°C, in vacuum condition, the 80°C is
enough for the water to be dried off.

Emulsion polymerization: Advantages and disadvantages

The physical state of emulsion is colloidal system, which make it easy to control the
process. The thermal and viscosity problem are not encountered in this system if
compared with bulk polymerization which tend to face auto-accelerate problem in the
polymerization. Emulsion does not require a vigorous mechanical separation which is
necessary for suspension polymerization to keep the monomer bubbles from coming
together to form one phase. (Young & Lovell, 1997)

For a given temperature, emulsion polymerization is more rapid than either bulk or
solution polymerization. For emulsion polymerization, the molecular weight of polymer
can be increased without alter the polymerization rate, only by increased monomer
concentration in the system. This cause a very high molecular weight polymer can be
produced quickly. Emulsion able to simultaneously attained both high molecular weight
and high reaction rates. However, due to the surfactant is a soap, it contaminates the
polymer. (Young & Lovell, 1997)

The molecular weight of the polymers can be reduced without altering the polymerization
rate but only by using chain-transfer agent. However, from the other way, the molecular
weight of polymer can only be increased by decrease the polymerization rate by
lowering the initiator concentration or lowering the reaction temperature.
(Painter& Coleman, 2009)
Interpret the FTIR spectrum that obtained

FTIR (Fourier Transform Infrared) Spectroscopy, or simply FTIR Analysis, is a failure

analysis technique that provides information about the chemical bonding or molecular
structure of materials, whether organic or inorganic. (Solomon, 2011)

The technique works on the fact that bonds vibrate at characteristic frequencies. A
molecule that is exposed to infrared rays absorbs infrared energy at frequencies which
are characteristic to that molecule. During FTIR analysis, a spot on the specimen is
subjected to a modulated IR beam. The specimen's transmittance and reflectance of the
infrared rays at different frequencies is translated into an IR absorption plot consisting of
reverse peaks. The resulting FTIR spectral pattern is then analyzed and matched with
known signatures of identified materials in the FTIR library. (Solomon, 2011)

Table 3: Aromatic Ring and Methylene Group Data from FTIR Analysis
Frequency Functional group Symmetry/
Range adsorption region Shape Intensity asymmetry
(cm-1)
3025.82 C-H Broad Medium Asymmetry
Aromatic ring
stretching region.

2921.08 Aliphatic C-H Broad Strong Asymmetry

stretching region.

1601.39 Aromatic C=C Broad Weak Asymmetry

stretching region.

1492.57 Aromatic C-C Sharp Medium Symmetry

stretching region.

695.48 Aromatic C-H Sharp Strong Asymmetry

bending region.

Table 4: Impurities found by FTIR Analysis

Wave number Functional group Symmetry/ Impurities
(cm-1) adsorption Shape Intensity asymmetry
region
Alcohol
O-H
trapped
908.41 Bending Broad Medium Sharp
inside during
region
washing
1.6 Conclusion

Emulsion polymerization is a unique process employed for some radical chain

polymerization. It involves polymerization of monomer (styrene) in the form of emulsions
to produce polymer particle (polystyrene). Emulsion polymerization is a process
polymerization where the dispersion monomer is emulsified by surfactant or emulsifier in
the water medium. The polymerization takes place in the micelle. If the condition of takes
place without emulsifier then the polymerization is regarding as suspension
polymerization. Various chemicals and reaction condition used in this experiment are
functioned to facilitate the emulsion polymerization process properly.

Emulsion polymerization can used to produce high molecular weight polymer at the fast
polymerization rate. Polymerization reactions are easier to control in emulsion
polymerization because stirring is easier and the removal of exothermic heat of
polymerization is facilitated. The heat transfer problems are also minimized as the
viscosity of the reaction mass never rises to a very high value. The final product does
not generally need to be processed so it can help industries to save the cost.

1.6 Reference

Billmeyer, F.W. (1984). Textbook of Polymer Science. New York: John Wiley & Sons

Chern, C.S. (2005). Emulsion polymerization mechanisms and kinetics. Journal of

Progress in Polymer Science (8), 443-486

Odian, G. (2004). Principle of Polymerization. New York: John Wiley & Sons

Painter, P.C. & Coleman, M.M. (2009) Essentials of Polymer Science and Engineering.
USA: DEstech Publications, Inc.

Solomons, T.W.G & Fryhle, C.B. (2011). Organic Chemistry. New York: John Wiley &
Sons

Young, R.J & Lovell, P.A. (1997). Introduction to Polymer. London: Chapman & Hall
Appendix
101
100

90 1373.57cm-1

3060.26cm-1 1601.39cm-1 840.15cm-1

2851.13cm-1
80 3025.82cm-1 906.41cm-1

1028.09cm-1
1066.35cm-1
2921.08cm-1 1492.57cm-1
1452.21cm-1
70
%T

60 748.38cm-1

50

40

30
695.48cm-1

23
4000 3500 3000 2500 2000 1500 1000 550
cm-1
Name Description
ps k7 Sample 119 By User Date Tuesday, March 26 2013

Figure 5 Spectrum of FTIR for experimental sample