Copolymerization of trioxane with styrene catalyzed by BF3·O(C2H5)2

Abstract

AbstractIt was determined whether trioxane, a cyclic formal, can copolymerize with styrene, a vinyl monomer, in the presence of BF3·O(C2H5)2 catalyst at 30°C. The methanol‐in‐soluble fraction after extraction with benzene was found to contain the copolymer of styrene and trioxane, thus demonstrating that trioxane can copolymerize with styrene In this case the amount of the methanol‐insoluble polymer was less than that of the total monomer consumed, as determined by gas chromatography. This was found to be caused partly by the formation of the cyclic oligomer, 4‐phenyl‐1,3‐dioxane. The relative reactivity of styrene was qualitatively found to be larger than that of trioxane, not only from the rate of monomer consumption but also from the composition of the methanol‐insoluble polymer obtained. In a nonpolar solvent the reactivity of trioxane increased, and the difference in reactivity between the two monomers decreased. Indeed, an apparent monomer reactivity ratio might be obtained from the relationship between the monomer composition and the monomer consumption rate or the composition of the methanol‐insoluble polymer, but it did not have a quantitative meaning because of the complexity of the copolymerization reaction.