STEREOSPECIFIC POLYMERIZATION OF BENZYL ALPHA-(ALKOXYMETHYL) ACRYLATES

alpha-(Alkoxymethyl) acrylates, such as methyl alpha-(phenoxymethyl) a crylate, benzyl alpha-(methoxymethyl) acrylate (BMMA), benzyl alpha-(b enzyloxymethyl) acrylate, and benzyl alpha-(tert-butoxymethyl) acrylat e, were synthesized, and their polymerizability and the stereoregulari ty of the polymers obtained by radical and anionic methods were invest igated. The radically obtained polymers were found to be atactic by C- 13- and H-1- NMR analyses, but the polymers obtained with lithium reag ents in toluene at -78 degrees C were highly isotactic. Further, it is noteworthy that isotactic polymers were also produced with lithium re agents even in tetrahydrofuran. Effects of polymerization temperature and counter cation on stereoregularity were clearly observed in the po lymerization of BMMA, and a potassium reagent afforded an almost atact ic polymer. (C) 1997 John Wiley & Sons, Inc.