Chain -Growth Polymerization of Styrene and Methyl Methacrylate Polymer - a very large molecule composed of smaller repeating units

(monomers) bonded together Addition Polymer - result from addition of one molecule at a time to a growing polymer chain, usually by a reactive intermediate (e.g., cation, anion, radical) at growing end
H2 Rad C CH G H2C CH G H2 H2 Rad C CH C CH G G H2C CH G

Rad

H2C CH G

Rad

H2 H2 H2 H C CH C CH C C G G n G

Repeat Unit

n = degree of polymerization (chain length) number of repeating units

Emulsion Polymerization: polymerization process which takes place in a colloidal dispersion of two immiscible liquids (monomer and solvent) in the presence of an emulsifying agent (which allows for partial mixing of the two). Solution Polymerization: polymerization process carried out in water without the use of an emulsifying agent so as to produce the polymer in small granules. Bulk Polymerization: polymerization carried out without the use of a solvent. Polymerization Initiator: A compound that disassociates to produce free radicals which begin a polymerization reaction. Scheme A: (Emulsion polymerization of styrene)
H2C CH Rad H2C CH + H2C CH H3C H2 C CH CH H2C CH

Rad

Styrene

n Polystyrene (PS)

Mechanism: Step 1: Initation (disassociation of peroxydisulfate) Step 2: Free-radical addition to monomer and subsequent additions Step 3: Termination

Procedure: (Begin this part first.) 1) In a 125 mL flask, add 5 g of styrene. Add 50 mL of water, 0.1 g of sodium peroxydisulfate, 0.35 g of sodium laurylsulfate and a stir bar. 2) Wrap the top of the flask with parafilm and warm the mixture for 2 h with vigorous stirring. 3) Add 10 mL of saturated alum to the mixture, boil gently for 2 min. and collect the polystyrene product on a filter. 4) Transfer the sample to a 25 mL beaker, add 5 mL of methanol, swirl the mixture for 30 sec and decant. Repeat this procedure until the sample is no longer sticky, collect the product on a filter and dry (with the vacuum on). 5) Weigh the product and obtain an IR spectrum as follows: dissolve a few mg of sample in about 1 mL of tetrahydrofuran in a small beaker and place the solution dropwise on a microscope slide. Allow the solvent to evaporate, carefully remove the resulting clear film with a razor blade and pass the beam through the film. Scheme B: (Bulk polymerization of methyl methacrylate)
CH3 H2C C CO2Me Initiator CH3 H CH3 H CH3 H H2 2 2 2 C C C C C C C C O C O C O OMe OMe OMe

Mechanism: Step 1: Initiation (disassociation of t-butylperoxybenzoate as well as breakdown of benzoate radical to CO2 and phenyl radical) Step 2: Free-radical addition to monomer and subsequent additions Step 3: Termination Procedure: 1) To 10 mL of methyl methacrylate in a test tube, add 5 drops of t-butylperoxybenzoate and mix. 2) Place the tube in a hot water bath and heat until the contents begin to boil. With short-wave radiation, hold an ultraviolet lamp above the top of the tube so that the light shines directly onto the surface of the solution and continue boiling until the solution becomes a solid. Repeating exposure to UV light may be necessary. 3) Wrap the tube in a paper towel and CAUTIOUSLY break it up. Carefully remove any glass that may stick to the polymer using forceps. 4) Weigh the sample and obtain an IR spectrum as with polystyrene using acetone as the solvent.