ATRP of allyl methacrylate with alkyl methacrylates -: Crosslinking of poly(methaerylate)s with allyl ester side groups

Random copolymers of methyl methacrylate (MMA) butyl methacrylate (BMA) and allyl methacrylate (AMA) were prepared via atom transfer radical polymerization (ATRP). AMA is a bifunctional monomer with two double bonds of different reactivity: a highly reactive methacrylate double bond and an allyl ester double bond of lower reactivity. In order to obtain linear polymers with pendant allyl ester groups, the copolymerization conditions have to be optimized with respect to the concentration of AMA, the catalyst system applied - especially the ligand - and the temperature. By means of kinetic studies the reaction parameters for a controlled polymerization were determined. The results obtained show that the higher the temperature and the amount of AMA is the higher is the probability of irregular chain growth and side reactions induced by the pendant allyl ester groups such as hydrogen abstraction from the allyl position or radical addition to the allyl ester double bond. The random copolymers were photochemically crosslinked by using 2,2-dimethoxy-2-phenylacetophenone as photoinitiator. The thermal properties of linear and crosslinked polymers were determined. The glass transition temperatures of both show no significant difference at low AMA content and thus low crosslinking densities.