Mechanistic Aspects of Copper-Mediated Living Radical Polymerization

A series of aminomethacrylate ((dimethylamino)ethyl methacrylate, (diethylamino)ethyl methacrylate and t - butylaminoethyl methacrylate) monomers and a series of methoxy[poly(ethylene glycol)] methacrylate macromonomers of different molecular weights have been copolymerized with methyl methacrylate under free radical and transition-metal mediated conditions. Significantly greater levels of comonomer incorporation were observed under transition-metal mediated conditions for all comonomers. This is attributed to complex formation between comonomer and catalyst, which is presumed to affect the reactivity of the monomer double bond.