Chain-Growth Polymerization (Addition Polymerization) Chain-growth polymerization produces thermoplastics such as polyacetal, polyethylene, polypropylene, polystyrene, methylmethacrylate, and

PVC. Molecular weight can range from 25,000 to millions of grams per mole. Unlike in polycondensation polymerization, no by-product such as H2O, HCl, CH3OH, NaCl, or any other by-product is produced. Also unlike in polycondensation polymerization, chain-growth polymerization is extremely rapid and oligomers do not exist very long, if at all. Complete polymers can form in less than 0.1 s. Three events are involved with chain-growth polymerization: catalytic initiation, propagation, and termination [3]. Monomers with double bonds (C==CR1R2) or sometimes triple bonds, and R1 and R2 additive groups, initiate propagation. The sites can be anionic or cationic active, free-radical. Free-radical catalysts allow the chain to grow when the double (or triple) bonds break. Types of free-radical polymerization are solution freeradical polymerization, emulsion free-radical polymerization, bulk free-radical polymerization, and free-radical copolymerization. Free-radical polymerization consists of initiation, termination, and chain transfer. Polymerization is initiated by the attack of free radicals that are formed by thermal or photochemical decomposition by initiators. When an organic peroxide or azo compound free-radical initiator is used, such as t-butyl peroxide, benzoyl peroxide, azo(bis)isobutylonitrile, or diazo- compounds, the monomers double bonds break and form reactive free-radical sites with free electrons. Free radicals are also created by UV exposure, irradiation, or redox initiation in aqueous solution, which break the double bonds [3].