Abstract
AbstractRadiation‐induced free‐ionic polymerization of isobutyl vinyl ether in bulk system has been studied by dilatometry and electrical conductivity measurement. Some refinements in kinetic treatment of estimate the propagation rate constant kp from the rate of polymerization and steady‐state conductivity were attempted. Polymerization of superdried monomer which gave a half‐power dose‐rate dependence of Rp was carried out at 0, 25, and 50°C. The kp value obtained at 25°C and an activation energy for propagation were estimated as 1.2 ± 0.4 × 105 I./mole‐sec and 9.6 ± 2.8 kcal/mole, respectively. In isobutyl vinyl ether, a propagation reaction in free‐ionic mechanism was found to be characterized with a high frequency factor and presumably higher activation energy, compared with ion‐pair mechanism. Discussions were also made as to several contrasting behaviors between the polymerization of alkyl vinyl ethers and other vinyl monomers as styrene both in free‐ion and ion‐pair mechanisms.
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