Synthesis of poly(β‐pinene)‐g‐poly(meth)acrylate by the combination of living cationic polymerization and atom transfer radical polymerization

Abstract

AbstractNew graft copolymers of β‐pinene with methyl methacrylate (MMA) or butyl acrylate (BA) 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/TiCl4/Ti(OiPr)4/nBu4NCl initiating system, and the resultant polymers were brominated quantitatively by N‐bromosuccinamide in the presence of azobisisobutyronitrile, yielding poly(β‐pinene) macroinitiators with different bromine contents (Br/β‐pinene unit molar ratio = 1.0 and 0.5 for macroinitiators a and b, respectively). The macroinitiators, in conjunction with CuBr and 2,2′‐bipyridine, were used to initiate ATRP of BA or MMA. With macroinitiator a or b, the bulk polymerization of BA induced a linear first‐order kinetic plot and gave graft copolymers with controlled molecular weights and MWDs; this indicated the living nature of these polymerizations. The bulk polymerization of MMA initiated with macroinitiator a was completed instantaneously and induced insoluble gel products. However, the controlled polymerization of MMA was achieved with macroinitiator b in toluene and resulted in the desired graft copolymers with controlled molecular weights and MWDs. The structures of the obtained graft copolymers of β‐pinene with (methyl)methacrylate were confirmed by 1H NMR spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1237–1242, 2003