Synthesis and Polymerization Studies of Cyano Epoxides

Abstract

The polar epoxides β-cyanoethyl glycidyl ether, cyanomethyl glycidyl ether, β-chloro-β-cyanoethyl glycidyl ether, and 3,4-epoxy valeronitrile were prepared, characterized, and their polymerization reactions studied. Novel cyanoethyla-tion of glycidol produced the β-cyanoethyl glycidyl ether in a quantitative yield. Reported is the first practicable synthesis of epicyanohydrin, which failed to polymerize. Homo-, co-, and terpolymerizations of the polar β-epoxy nitriles with various alkylene oxides were achieved by employing a complex catalyst obtained from an aluminum alkyl, acetyl acetone, and water. The polymers produced a series of vulcanizable elastomers which displayed an ex-cellent balance of solvent resistance and low temperature flexibility, as well as good ozone resistance. The presence of a third monomer such as allyl glycidyl ether was required to facilitate rubber vulcanization. However, it was possible to vulcanize homo- and copolymers of β-chloro-βyanoethyl glycidyl ether through the pendant chlorine atom. Catalyst efficiency in all cases was poor due to the complexing of the aluminum catalyst by the nitrile function.