SYNTHESIS OF COPOLYMERS OF β-PINENE BY THE COMBINATION OF LIVING CATIONIC POLYMERIZATION AND ATRP

Abstract

Graft copolymers of β-pinene with methyl methacrylate(MMA),butyl acrylate(BA) or styrene(St) were synthesized by the combination of living cationic polymerization and atom transfer radical polymerization(ATRP).β-Pinene polymers with predetermined molecular weights and narrow molecular weight distributions(MWDs) were prepared by living cationic polymerization with the 1-phenylethyl chloride /TiCl_4/Ti(OiPr)_4/nBu_4NCl initiating system,and the obtained polymers were brominated quantitatively by N-bromosuccinamide in the presence of AIBN,yielding poly(β-pinene) macroinitiators with 50% of bromine contents(Br/β-pinene unit molar ratio=0.5).The macroinitiator,in conjunction with CuBr and 2,2′-bipyridine,was used to initiate ATRP grafting of BA,MMA and St.All of the grafting polymerizations induced linear first-order kinetic plots and gave graft copolymers with controlled molecular weights and MWDs,suggesting that these polymerizations are controllable.The structures of the obtained graft copolymers of β-pinene with(methyl)methacrylate or styrene were confirmed by()~1H-NMR spectra.