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

✍ Scribed by Jiang Lu; Masami Kamigaito; Mitsuo Sawamoto; Toshinobu Higashimura; Yun-Xiang Deng

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 223 KB
• Volume: 35
• Category: Article
• ISSN: 0887-624X
• DOI: 10.1002/(sici)1099-0518(199706)35:8<1423::aid-pola11>3.0.co;2-9

✦ Synopsis

a-End-functionalized polymers and macromonomers of b-pinene were synthesized by living cationic isomerization polymerization in CH 2 Cl 2 at 040ЊC initiated with the HCl adducts [1; CH 3 CH(OCH 2 CH 2 X)Cl; X Å chloride (1a), acetate (1b), and methacrylate ( 1c)] of vinyl ethers carrying pendant substituents X that serve as terminal functionalities. In conjunction with TiCl 3 (OiPr) and nBu 4 NCl, these functionalized initiators led to living b-pinene polymerization where the carbon-chlorine bond of 1 was activated by TiCl 3 (OiPr). Similarly, end-functionalized poly( p-methylstyrene)block-poly( b-pinene) were also obtained. 1 H-NMR analysis showed that the polymers possess controlled molecular weights (DP n Å [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(b-pinene) or poly( p-methylstyrene)-block-poly(b-pinene) as graft chains attached to a PMMA backbone.