Living cationic isomerization polymerization of beta-pinene .3. Synthesis of end-functionalized polymers and graft copolymers

作者：Lu J; Kamigaito M; Sawamoto M; Higashimura T; Deng YX

来源：Journal of Polymer Science Part A: Polymer Chemistry , 1997, 35(8): 1423-1430.

• cationic polymerization
• living polymerization
• beta-pinene
• end-functionalized polymer
• macromonomer
• graft copolymer

alpha-End-functionalized polymers and macromonomers of beta-pinene were synthesized by living cationic isomerization polymerization in CH2Cl2 at -40 degrees 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 nBu(4)NCl, these functionalized initiators led to living beta-pinene polymerization where the carbon-chlorine bond of 1 was activated by TiCl3(OiPr). Similarly, end-functionalized poly(p-methylstyrene)-block-poly(beta-pinene) were also obtained. H-1-NMR analysis showed that the polymers possess controlled molecular weights (<(DP)over bar>(n) = [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(beta-pinene) or poly(p-methylstyrene)-block-poly(beta-pinene) as graft chains attached to a PMMA backbone.

• 出版日期1997-6
• 单位中山大学