Synthesis and polymerization of optically active itaconamate bearing an (R)-α-methylbenzyl group

✍ Scribed by Tsutomu Oishi; Tetsuji Kawamoto; Hiromori Tsutsumi

• Publisher: Elsevier Science
• Year: 1996
• Tongue: English
• Weight: 729 KB
• Volume: 37
• Category: Article
• ISSN: 0032-3861
• DOI: 10.1016/s0032-3861(96)00388-6

✦ Synopsis

Two types of optically active itaconamates, a-ethyl 3-N-((R)-a'-methylbenzyl)itaconamate (MBEI) and a-N-((R)-a'-methylbenzyl)/3-ethyl itaconamate (EMBI) were synthesized from itaconic anhydride, (R)-amethylbenzylamine and ethanol. Radical polymerizations of MBEI and EMBI were performed in bulk and in several solvents at 50 to 130°C. But only bulk polymerization gave appreciably optically active polymers. It was found that MBEI has higher polymerization reactivity than EMBI. Radical copolymerizations of MBEI (M1) (EMBI (M1)) were performed with styrene (ST, M2), methyl methacrylate (MMA, M2), or Nphenylmaleimide (PhMI, M2) in benzene at 60°C. The monomer reactivity ratios (rx, r2) and Alfrey-Price Q e values were determined as follows: r 1 = 0.35, r 2 = 0.14 (MBEI/ST), r I = 0.03, r2 = 1.12 (EMBI/ST), rl = 0.02, r2 = 2.39 (EMBI/MMA), r 1 = 4.35, r 2 = 0.17 (MBEI/PhMI), r I = 1.04, r2 = 0.13 (EMBI/PhMI), Q = 1.80, e = 0.94 for MBEI, Q = 0.21, e = 1.04 for EMBI, Chiroptical properties of homopolymers and copolymers were also investigated.