Copolymerization of ethylene with vinyl acetate. II. Effect of solvent on polymer yield and molecular weight

Abstract

AbstractIn the free‐radical solution copolymerization of ethylene and vinyl acetate, polymer yield and molecular weight were found to vary considerably with the solvent used. Solvents were toluene, benzene, hexane, heptane, and cyclohexane. Molecular weights were highest in benzene and lowest in toluene and were readily explained by different solvent chain‐transfer constants. Polymer yields were highest in aliphatic solvents and lowest in aromatic solvents including benzene. This was attributed to different types of interactions of the solvents with radical species. The saturated aliphatic solvents undergo hydrogen abstraction reactions, but these give reactive alkyl radicals which reinitiate polymer growth. Toluene also undergoes hydrogen abstraction reactions, but the resultant benzyl radical is resonance stabilized and does not readily reinitiate polymerization. Benzene does not undergo hydrogen abstraction reactions. The low yields are attributed to complex formation. A consideration of kinetic theory indicates that complex formation with both initiator and growing polymer radicals is involved. Differences in viscosity, ethylene solubility, and initiator half‐life in the different solvents, as well as induced decomposition of the initiator, were not determining factors.