Stereospecific anionic polymerization and novel hydrogen-transfer polymerization of alpha-(aminomethyl)acrylates having unprotected amino group

Anionic polymerization of alpha-(aminomethyl)acrylates (2-8) having an unpr otected amino proton was carried out using lithium reagents at -78 degrees C. Acrylates except for 4 and 8 afforded the polymers in good yields. The p olymerization of ethyl alpha-[N-(di phenylmethyl)aminomethyl]acrylate (3) w ith n-BuLi or the Ph2NLi-N,N,N',N'-tetramethylyethylenediamine (TMEDA) comp lex in toluene afforded a polymer with a normal vinyl polymer structure and high isotacticity. Hydrogen-transfer of the amino proton hardly occurred i n the polymerization process. The anionic polymerizations of ethyl alpha-[N -(1-phenylethyl)aminomethyl]acrylate (2) using lithium reagents in toluene and tetrahydrofuran (THF) proceeded with hydrogen-transfer reaction. CH car bon generated by hydrogen-transfer in the main chain was detected by DEFT N MR measurement of poly(2). The CH-containing unit in the polymer increased up to nearly 40% when THF was used as a solvent. Monomers 4 and 8 showed lo w polymerizability.