Stereospecific polymerization of alpha-substituted acrylates

alpha-Substituted acrylates having various functional groups, such as alkox ymethyl, aminomethyl and alkylthiomethyl groups, on the alpha-position were synthesized and polymerized by radical and anionic methods, and stereoregu larity of the obtained polymers was investigated. In the anionic polymeriza tion using lithium reagents, highly isotactic polymers were obtained regard less of the polarity of solvents. Strong intra- and intermolecular coordina tion of the polar groups to counter-cation (Li+) may be the main factor in controlling the stereochemistry. On the other hand, stereocontrol in the ra dical polymerization of alpha-(alkoxymethyl)acrylates was attained in the p resence of zinc salts (ZnBr2 and ZnCl2), which may coordinate to the growin g polymer and monomers.