Grafting copolymerization of vinyl monomers on polyimide macroinitiators by the method of atom transfer radical polymerization

Graft copolymers with the main polyimide chain and side chains of poly(n-butyl acrylate), poly(tert-butyl acrylate), poly(methyl methacrylate), poly(tert-butyl methacrylate), polystyrene, and polystyrene-block-poly(methyl methacrylate) were synthesized by atom transfer radical polymerization on the multicenter polyimide macroinitiators in the presence of the halide complexes of univalent copper with nitrogen-containing ligands. Polymerization of metha-crylates is most efficiently developed on the polyimide macroinitiators. The obtained graft copolymers initiate the secondary polymerization (“post-polymerization”) of methyl methacrylate. The conditions of detachment of side chains of graft polymethacrylates that do not involve the ester groups of their monomeric units were found. The molecular mass characteristics of the graft copolymers and isolated polymers, being the detached side chains of the copolymers, were determined. The detached side chains of different chemical structures have low values of the polydispersity index. The procedure developed was used for the preparation of new graft polyimides with side chains of poly-4-nitro-4′-N-methylacryloyloxyethyl-N′-ethyl]amino-azobenzene that cause the nonlinear optical properties and with the side chains of poly(N,N-dimethylaminoethyl methacrylate) that cause the thermosensitive properties of the copolymers.