Addition Copolymerization

Most direct copolymerizations of equimolar mixtures of different monomers give statistical copolymers, or if one monomer is much more reactive a nearly homopolymer of that monomer. The copolymerization of styrene with methyl methacrylate, for example, proceeds differently depending on the mechanism. Radical polymerization gives a statistical copolymer. However, the product of cationic polymerization is largely polystyrene, and anionic polymerization favors formation of poly(methyl methacrylate). In cases where the relative reactivities are different, the copolymer composition can sometimes be controlled by continuous introduction of a biased mixture of monomers into the reaction.

Formation of alternating copolymers is favored when the monomers have different polar substituents (e.g. one electron withdrawing and the other electron donating), and both have similar reactivities toward radicals. For example, styrene and acrylonitrile copolymerize in a largely alternating fashion.

A terpolymer of acrylonitrile, butadiene and styrene, called ABS rubber, is used for high-impact containers, pipes and gaskets.