Living and highly syndiotactic polymerization of methyl methacrylate and other methacrylates by tert-butyllithiumtrialkylaluminium in toluene

Highly syndiotactic poly(methyl methacrylate)s (PMMAs) with narrow molecular weight distribution (MWD) were prepared by polymerization of MMA in toluene at low temperatures, initiated with tert-butyllithium (t-C4H9Li) combined with trialkylaluminium compounds such as triethyl-, tributyl-, and trioctylaluminium (mole ratio Al/Li ≥ 3). Polymerization was initiated by the t-C4H9 anion and proceeded in a living manner. Several alkyl methacrylates were also polymerized with t-C4H9Li-(n-C4H9)3Al to give highly syndiotactic polymethacrylates with narrow MWD. Highly syndiotactic block and random copolymers of MMA and ethyl methacrylate were obtained by this initiator.