PST 522E Synthesis and Characterization of Macromolecules

CHAPTER 1
EMULSION AND SUSPENSION POLYMERIZATION OF STYRENE

1. THEORETICAL PART 1.1. Emulsion Polymerization In emulsion polymerization two immiscible liquid phases are present, an aqueous continuous phase and a non-aqueous discontinuous phase consisting of monomer and polymer. The initiator is located in the aqueous phase. And the monomer-polymer particles are quite small, of the order of 0.1 m in diameter. Emulsion systems allow higher-molecular-weight polymer to be produced at higher rates than do bulk or suspension systems. The soap plays an important role in emulsion polymerization. At the beginning of the reaction it exists in the form of micelles, aggregates of 50-100 soap molecules. Part of the monomer enters the micelles, but most of it exists as droplets a micrometer or more in diameter. In the ideal case no polymer is formed in the monomer droplets. Polymerization can take place (at a very low rate) in the homogeneous phase in the absence of soap, but this cannot account for the bulk of the polymer formed. At the beginning of the reaction, polymer is formed in the soap micelles; these represent a favorable environment for the free radicals generated in the aqueous phase, because of the relative abundance of monomer and the high surface / volume ratio of the micelles compared to the monomer droplets. As polymer is formed, the micelles grow by the addition of monomer from the aqueous phase (and ultimately from the monomer droplets.) Soon (2-3% polymerization) the polymer particles much larger than the original micelles and absorb almost all the soap from the aqueous phase. Any micelles not already activated disappear; further polymerization takes place within the polymer particles already formed. The monomer droplets are unstable at this stage; if agitation is stopped, they coalesce into a continuous oil phase containing no polymer. The droplets act as reservoirs of monomer, which is fed to the growing polymer particles by diffusion through the aqueous phase. The polymer particles may contain about 50% monomer up to the point at which the monomer droplets disappear, at 60-80 % polymerization. The rate of polymerization is constant over most of the reaction up to this point, but then falls off as monomer is depleted in the polymer particles. Rate increases soap (and initial micelle) concentration. Emulsion polymerization has three stages. 1.1.1. Stage I The monomer diffuses to the empty micelle from droplets. Polymerization initiated in micelles to become polymer particles. New particles are generated as micelles are consumed. This stage lasts for conversion ~ 0-15%.

-1-

Chapter 1 - Emulsion and Suspension Polymerization of Styrene

Figure 1: Stage I 1.1.2. Stage II No more surfactant available to generate new particles. Monomer diffuses into now a constant number of particles to maintain some equilibrium [M] with the particle. The monomer reservoir drops get slowly consumed.

Figure 2: Stage II An equilibrium between increasing interfacial tension within micelle and monomer/polymer dilution leads to a constant volume fraction where 2 is the volume fraction of the polymer and 1 is the volume fraction of the monomer.

[M ] = [M ]0 (1 2 )
1.1.3. Stage III This stage occurs when conversion ~ 40-60%. All the monomers exist in particles.

Table 1: Common properties of emulsion polymerization Common Emulsion Polymers styrene + copolymers vinyl chlorides ex. Pleather butadiene vinylidene chloride vinyl acetate vinyl acrylates (acrylics) methyl acrylates Advantages - low (viscosity) - great T control - final product fine powder or water form coatings Disadvantages - a lot of soap as impurity ex. In medical applications, can be irritant

-2-

Chapter 1 - Emulsion and Suspension Polymerization of Styrene

1.1.4. Smith-Ewart kinetics In an ideal emulsion system, free radicals are generated in the aqueous phase at a rate of about 1013 per cubic centimeter per second. There are about 1014 polymer particles per cubic centimeter. Simple calculation show that termination of the free radicals in the aqueous phase is negligible and that diffusion currents are adequate for the rapid diffusion of free radicals into the polymer particles- on the average, about one per particle every 10 sec. It can also be calculated from the known termination rate constants that two free radicals within the same polymer particle would mutually terminate within a few thousands of a second. Therefore each polymer particle must contain most of the time either one or no free radicals. At any time half of the particles (on the average) contain one free radical, the other half none. The rate of polymerization per cubic centimeter of emulsion is Vp=kp[M] N / 2 [M]: Monomer concentration kp: propagation rate constant N: the number of polymer particles per cubic centimeter Since the monomer concentration is approximately constant, the rate depends principally on the number of particles present and not on the rate of generation of radicals. The degree of polymerization also depends upon the number of particles: Xn=kpN [M] / : the rate of generation radicals Unlike vp, xn is a function of the rate of free-radical formation. In bulk polymerization rate can be increased only by increasing the rate of initiation; this, however, causes a decrease in the degree of polymerization. In emulsion polymerization the rate may be increased by increasing the number of polymer particles. If the rate of initiation is kept constant, the degree of polymerization increases rather than decreases as the rate rises. Since the number of polymer particles is determined by the number of soap micelles initially present, both rate and molecular weight increase with increasing soap concentration. The Smith-Ewart kinetics require that Vp N, [I] N [I]
0.4 0.6

, [E]

0.4

, [E]

0.6 0.6

xn N, [I] [E] is the soap or emulsifier concentration 1.2. Suspension Polymerization

-0.6

, [E]

Hoffman and Delbruch first developed suspension polymerization in 1909. In suspension polymerization the initiator is soluble in the monomer phase, which is dispersed by

-3-

Chapter 1 - Emulsion and Suspension Polymerization of Styrene

comminuting into the dispersion medium (usually water) to form droplets. The solubility of the dispersed monomer (droplet) phase and also the resultant polymer in the dispersion medium are usually low. The volume fraction of the monomer phase is usually within the range 0.10.5. Polymerization reactions may be performed at lower monomer volume fractions, but are not usually economically viable. At higher volume fractions, the concentration of continuous phase may be insufficient to fill the space between droplets. Polymerization proceeds in the droplet phase and in most cases occur by a free radical mechanism. Suspension polymerization usually requires the addition of small amounts of a stabilizer to hinder coalescence and break-up of droplets during polymerization. The size distribution of the initial emulsion droplets and, hence, also of the polymer beads that are formed, is dependent upon the balance between droplet break-up and droplet coalescence. This is in turn controlled by the type and speed of agitator used the volume fraction of the monomer phase, and the type and concentration of stabilizer used. If the polymer is soluble in the monomer, a gel is formed within the droplets at low conversion leading to harder spheres at high conversion. If the polymer is insoluble in the monomer solution, precipitation will occur within the droplets, which will result in the formation of opaque, often irregularly shaped particles. If the polymer is partially soluble in the monomer mixture, the composition of the final product can be difficult to predict. Polymer beads find applications in a number of technologies, such as molding plastics. However, their largest application is in chromatographic separation media (as ion exchange resin and as supports for enzyme immobilization). Such applications frequently require large particle surface areas, which necessitates the formation of pores (of the required dimensions) in the bead structure. The polymer beads may be made porous by the inclusion of an inert diluent (or porogen) to the monomer phase, which may be extracted after polymerization. Other additions to the monomer phase can include UV stabilizers (aromatic ketones and esters), heat stabilizers (ethylene oxide derivatives and inorganic metal salts), molding lubricants and foaming agents (porogens). 1.2.1. Polymeric stabilizers Typical polymeric stabilizers used for oil-in-water suspension polymerization reactions are poly (vinyl alcohol) -co- (vinyl acetate) (formed from the partial hydrolysis (80-90%) of polyvinyl acetate), poly (vinyl-pyrrolidone), salts of acrylic acid polymers, cellulose ethers and natural gums. Polymeric stabilizers used in inverse suspension polymerization reactions include block copolymers poly (hydroxy-stearic acid) -co-poly) ethylene oxide). Surfactants used for oil-inwater suspensions include spans and the anionic emulsifier (sodium 12-butinoyloxy-9octadecenate).

Figure 3: Suspension polymerization

-4-

Chapter 1 - Emulsion and Suspension Polymerization of Styrene

Figure 4: Batch reactor within organic droplets (~1 m 1 cm) Drop size determined by impeller speed within each droplet, have initiator monomer

Kinetics is identical to typical large scale free radical polymerization. initiation propagation termination steady state assumption

Figure 5: Suspension polymerization 1.2.2. Products Glassy rigid beads often called latex beads Very uniform Nice spherical shapes

-5-

Chapter 1 - Emulsion and Suspension Polymerization of Styrene

Figure 6: x-linked network

Figure 7: Vary surface chain

1.2.3. Polymerization conditions and kinetics Extensive studies have shown that, in general, reaction kinetics in suspension polymerization is found to show good agreement with bulk phase kinetics (in absence of any monomer diluent). This observation suggests that in suspension polymerization, the emulsification conditions (agitation conditions, emulsion droplet size and concentration / type of stabilizer) appear to have little effect on reaction kinetics. Moreover, it can be concluded that any mass transfer between two phases in the emulsion does not affect the overall reaction rate. The major challenge in designing a suspension reaction is therefore the formation of a stable emulsion, preferably having a uniform size distribution. The monomer droplets are large enough to contain a large number of free radicals (may be as many as 105) and this is why the polymerization in general proceeds with a similar mechanism to that of bulk polymerization, particularly when the polymer is soluble in the monomer.

-6-

Chapter 1 - Emulsion and Suspension Polymerization of Styrene

2.

EXPERIMENTAL

2.1. Emulsion Polymerization 2.1.1. Materials Styrene, potassium persulphate, soap solution, potassium-aluminum sulfate distilled water. 2.1.2. Procedure To a resin kettle equipped with a mechanical stirrer, condenser and nitrogen inlet tube, is added 128.2 g. of distilled water, 71.2 g. of styrene, 31.4 mL of 0.68 % potassium persulfate, and 100 mL of 3.56% soap solution (sodium stearate one can use 1g of either sodium dodecyl benzenesulfonate or sodium lauryl sulfate). The system is purged with nitrogen to remove dissolved air. Then the temperature is raised to 50 0C and kept there for 2 hour to afford a 90% conversion of polymer. The polymer is isolated by freezing thawing or by adding potassium-aluminum solution and boiling the mixture. The polystyrene is filtered, washed with water and methanol and dried in vacuum at 50 0C. The total yield, and the limiting viscosity number (degree of polymerization) of one sample is determined by using [] = km . M

equation. km and for polystyrene in benzene at 20 0C are 12.3 10-3 and 0.72 respectively. 2.2. Suspension Polymerization 2.2.1. Materials Styrene, 1, 4-divinylbenzene, poly (vinyl alcohol), dibenzoyl peroxide, methanol. 2.2.2. Procedure Styrene and 1, 4-divinylbenzene (the latter as 50-60% solution in ethyl benzene) are destabilized and distilled. A three-necked flask, fitted with stirrer (preferably with revolution counter), thermometer, reflux condenser and nitrogen inlet, is evacuated and filled with nitrogen three times. 250 mg of poly (vinyl alcohol) are placed in the flask and dissolved in 150 mL of de-aerated water at 50C. A freshly prepared solution of 0.25g (1.03 mmol) of dibenzoyl peroxide in 25 mL (0.22 mmol) of styrene and 2 mL (7 mmol) of 1, 4-divinylbenzene is added with constant stirring so as to produce an emulsion of fine droplets of monomer in water. This is heated to 90C on a water bath while maintaining a constant rate of stirring and passing a gentle stream of nitrogen through the reaction vessel. After about 1 h (about 5% conversion) the cross-linking becomes noticeable (gelation). Stirring is continued for another 7 h at 90 C, the reaction mixture then being allowed to cool to room temperature while stirring. The supernatant liquid is decanted from the beads, which are washed several times with methanol and finally stirred for another 2 h with 200 ml of methanol. The polymer is filtered off and dried overnight in vacuum at 50 C. Yield: practically quantitative.

-7-

Chapter 1 - Emulsion and Suspension Polymerization of Styrene

3.

REFERENCES

[1] Billmeyer, F.W., (1984). Textbook Polym. Sci., 3rd Edition, John Wiley&Sons. [2] Braun, D., Cherdonron, H., Kern, W., (1984). Practical Macromolecular Organic Chem., Harwood Academic Publisher. [3] Dowding, P.J., Vincent, B., (2000). Colloids and Surfaces, 161-259.

-8-