STEREOSPECIFIC ANIONIC-POLYMERIZATION OF CHIRAL BENZYL ALPHA-[(1-PHENYLETHOXY)METHYL]ACRYLATE

A novel chiral monomer, benzyl alpha-[(1-phenylethoxy) methyl] acrylat e was synthesized, and the stereoregularity and chiroptical property o f the polymers obtained by radical and anionic polymerizations were in vestigated. Anionic polymerization in toluene provided a polymer with high isotacticity regardless of optical purity of the monomer and diff erence of counter cations, Li+ and Mg2+, while radical polymerization appears to yield an atactic polymer. The isotactic copolymers anionica lly obtained from a mixture of (R)- and (S)-monomers showed peak split ting probably due to the triad arrangement of (R) and (S) groups of si de chains in the resonance of C-13-NMR spectra. The isotactic polymer prepared from enantiomerically pure (R)-monomer ([alpha](365)(25) = +1 57 degrees) with n-BuLi in toluene exhibited higher specific rotation ([alpha](365)(25) = +262 degrees) than that of the radical polymer ([a lpha](365)(25) = +162 degrees). This may be explained by regular arran gement of optically active groups along the polymer chain of the isota ctic polymer. (C) 1998 Wiley-Liss, Inc.