Study on ketalization reaction of polyvinylalcohol by ketones. I. Reaction between polyvinylalcohol and acetone

Abstract

Abstract Ketalization reaction of polyvinylalcohol (PVA) by acetone, dimethylsulfoxide (DMSO) as solvent, under the presence of acidic catalyst, in homogeneous system was carried out and the synthesis of polyvinylketal with any ketalization degree was successfully performed. This reaction proceeds in bimolecular reaction, the equilibrium constant is ca. 0.07 at 40°C and roughly 10 −5 less compared with the acetalization reaction between PVA and aldehydes. Synthesis in aqueous media is difficult. However, the heat of reaction for both cases is 7.5 kcal/mol and both reactions are considered to proceed in an identical reaction mechanism. Ketalization reaction starts from isotactic OH portion and proceeds finally to syndiotactic OH portion, however, 100% ketalization is extremely difficult. The effects of water on reaction was confirmed both from theoretical and experimental viewpoints, and even though the presence of water lowers the degree of ketalization, it was observed that the presence of water below 0.1 mol against 1 mol of PVA will not significantly affect final ketalization degree. Polyvinylketals thus obtained are soluble in DMSO, dimethylformamide (DMF), and alcohols.