Polymerisability of different lactones and methyl methacrylate in the presence of various organoaluminum catalysts

Polymerisation experiments of methyl methacrylate (MMA) and various lactones have been performed in bulk and in solution in the presence of different anionic initiators, such as diethylaluminium sulphate (DEAS), triisobutylaluminium (TIBA) and TIBA/H2O, at room temperature and at 100 degrees C. Results are presented on the relative tendency of the investigated lactones and methyl methacrylate to polymerise in the presence of the different catalytic systems. Five member ring lactones are refractory to the polymerisation under the adopted conditions, whereas the inferior and superior homologues and MMA provide homopolymers in fairly high yield and respectable average molecular weight, with monomodal distribution and fairly narrow polydispersity index. It is claimed for the first time the ability of DEAS to provide poly(methyl methacrylate) with a prevailingly syndiotactic microstructure. Copolymerisation experiments of MMA with various lactones give rise to either hybrid block copolymers or in situ prepared polymer alloys as substantiated by NMR and GPC analysis.