Living cationic isomerization polymerization of ?-pinene. III. Synthesis of end-functionalized polymers and graft copolymers

α-End-functionalized polymers and macromonomers of β-pinene were synthesized by living cationic isomerization polymerization in CH2Cl2 at −40°C initiated with the HCl adducts [1; CH3CH(OCH2CH2X)Cl; X = chloride (1a), acetate (1b), and methacrylate (1c)] of vinyl ethers carrying pendant substituents X that serve as terminal functionalities. In conjunction with TiCl3(OiPr) and nBu4NCl, these functionalized initiators led to living β-pinene polymerization where the carbon–chlorine bond of 1 was activated by TiCl3(OiPr). Similarly, end-functionalized poly(p-methylstyrene)-block-poly(β-pinene) were also obtained. 1H-NMR analysis showed that the polymers possess controlled molecular weights (DPn = [M]0/[1]0) and number-average end functionalities close to unity. The end-functionalized methacrylate-capped macromonomers form 1c were radically copolymerized with methyl methacrylate (MMA) to give graft copolymers carrying poly(β-pinene) or poly(p-methylstyrene)-block-poly(β-pinene) as graft chains attached to a PMMA backbone.