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

New graft copolymers of beta-pinene with methyl methacrylate (MDAA) or butyl acrylate (BA) were synthesized by the combination of living cationic polymerization and atom transfer radical polymerization (ATRP). beta-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)/nBu(4)NCl initiating system, and the resultant polymers were brominated quantitatively by N-bromosuccinamide in the presence of azobisisobutyronitrile, yielding poly(beta-pinene) macroinitiators with different bromine contents (Br/beta-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 beta-pinene with (methyl)methacrylate were confirmed by H-1 NMR spectra. (C) 2003 Wiley Periodicals, Inc.