Synthesis of graft copolymer by coupling reaction of living poly(methyl methacrylate) with bromomethylated polystyrene

Abstract

A novel, well-defined graft copolymer (polystyrene (PS)-g-poly(metthyl methacrylate) (PMMA)) with control over the length of both the backbone and the side chain was synthesized by the coupling reaction living PMMA with bromomethylated PS. The backbone polymer was prepared by the anionic polymerization of styrene with n-butyllithium followed by bromomethylation using C 8H 17OCH 2Br/SnCl 4. The living PMMA was prepared by the group transfer polymerization of MMA. Graft copolymers with a narrow molecular weight distribution, D = 1.2 ∼ 1.4 at an M¯ n of around 3 × 10 4−7 × 10 4 were obtained. The reactivity of the bromomethylated PS and the living PMMA decreased with increase in their molecular weight; the favoured reaction temperature was −20°C. Characterization of the product was performed by methods including 1H n.m.r., g.p.c. and d.s.c.. Compared with the homopolymers PS and PMMA, the copolymer had a lower glass transition temperature.