Polymerization of vinyloxyaluminum and formation of syndiotactic poly(vinyl alcohol)

Abstract

AbstractThe polymerization of diisobutylvinyloxyaluminum, CH2CHOAl(i‐Bu)2, and diethylvinyloxyaluminum, CH2CHOAlEt2, did not take place in the presence of typical radical or cationic initiators. The polymerization was realized at 60°C by the addition of tetrahydrofuran (THF) or tetrahydropyran, no conventional initiator being required. Diethyl ether, glyme, and dioxane were not effective on the polymerization. At Dry Ice–acetone temperature, polymerization did not take place, even in the presence of tetrahydrofuran, but did take place in the presence of both THF and SnCl4. The role of cyclic ethers in the polymerization was studied. Polymers were converted into poly(vinyl alcohol) (PVA) by solvolysis. All the resulting PVA was syndiotactic; particularly polymers obtained at −78°C showed syndiotactivity of 89%, which is the highest value ever reported.