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This article reports new ring-opening reactions of oxetane compounds with certain reagents such as acyl chlorides, carboxylic esters, phenols, and carboxylic acids using certain quaternary onium salts as catalysts. Reaction behavior of oxetanes was investigated based on kinetic study. These new reactions of oxetanes were also successfully applied to polymer synthesis. Polymers containing pendant reactive groups were obtained by polyaddition of bis (oxetane) s with certain difunctional monomers such as dicarboxylic chlorides, bis (phenol) s, or dicarboxylic acids. The reaction of oxetanes with cyclic carboxylic anhydrides proceeded in alternating ring-opening copolymerization mode to give copolymers with A-B sequence. The authors found new anionic ring-opening polymerization of oxetanes containing pendant hydroxyl groups using appropriate catalyst system. Hyperbranched polymers containing hydroxyl groups were prepared by the reactions of oxetanes. Alkali developable photopolymers were also obtained by the chemical modification of the hyperbranched polymers. The reactions of oxetanes with certain reagents were also useful for thermal curing reaction providing oxetane resins.

Synthesis of Polymers with Well-defined Structures by Novel Ring-opening Reactions of Oxetanes