J. R. Schaefgen
Mar 8, 2007
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Journal
Journal of Polymer Science Part C: Polymer Symposia
Abstract
The polymerization and copolymerization of vinyl chloroformate is described. Polymerization is initiated at 0 and −80°C. with boron alkyls, yielding high molecular weight poly(vinyl chloroformate). The polymer prepared at −80°C. is laterally ordered. The homopolymer is soluble and surprisingly stable to water and can be oriented in fiber or film form. Films of poly(vinyl chloroformate) undergo facile postreaction with compounds with labile hydrogen atoms such as alcohols, amines, and phenols. Aqueous ammonium hydroxide gives a copolymer containing approximately equal numbers of hydroxyl and urethane side groups. With gaseous ammonia a quantitative yield of poly(vinyl urethane) is obtained. Diamines react to give crosslinked polymers. Products are described briefly. The related derivatives of vinyl chloroformate (vinyl cyanoformate, vinyl t-butyl carbonate, and vinyl urethane) were prepared from vinyl chloroformate. Polymerization of the first two monomers is initiated by tri-n-butyl boron; the vinyl urethane polymerizes spontaneously at 100°C. Poly(vinyl t-butyl carbonate) is crystalline; poly(vinyl cyanoformate) and poly(vinyl urethane) are amorphous.