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 S O

O - Na +

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 oilsoluble 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 (70C),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 70C 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 Aluminium foil mould Aluminium foil mould + Polystyrene Polystyrene Weight , g 1.3730g 2.6228g 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
8(relative atomic mass of carbon atom)+ 8(relative atomic mass of hydrogen atom)

18.18 g

Relative molecular mass of styrene, RMM (C=12, H=1)

104

No. of moles of styrene, m 0.175 mol

Percentage yield of product

6.87%

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 SO4 free radicals as a result of bond scission. The activation energy is quite high, thus persulfate is usually conducted at high temperature (50C 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 50C:

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 240C, and the glass transition temperature of polystyrene is 95C. 70C 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 80C overnight. This is because the boiling point of water is 100C, in vacuum condition, the 80C 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 Range (cm-1) 3025.82 Functional group adsorption region C-H Aromatic ring stretching region. Aliphatic C-H stretching region. Aromatic C=C stretching region. Aromatic C-C stretching region. Aromatic C-H bending region. Shape Broad Intensity Medium Symmetry/ asymmetry Asymmetry

2921.08

Broad

Strong

Asymmetry

1601.39

Broad

Weak

Asymmetry

1492.57

Sharp

Medium

Symmetry

695.48

Sharp

Strong

Asymmetry

Table 4: Impurities found by FTIR Analysis Wave number (cm-1) Functional group adsorption region O-H Bending region Shape Intensity Symmetry/ Impurities asymmetry Alcohol trapped inside during washing

908.41

Broad

Medium

Sharp

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
3060.26cm-1 2851.13cm-1 3025.82cm-1

1373.57cm-1

1601.39cm-1

840.15cm-1

80

906.41cm-1

1028.09cm-1 1066.35cm-1

2921.08cm-1

70

1492.57cm-1 1452.21cm-1

%T

60

748.38cm-1

50

40

30
695.48cm-1

23 4000 Name ps k7

3500

3000

2500

2000

1500

1000

550

cm-1
Description Sample 119 By User Date Tuesday, March 26 2013

Figure 5 Spectrum of FTIR for experimental sample