Effect of oxygen on the polymerization of vinyl chloride. I. Kinetic features

Wiley - Tập 11 Số 9 - Trang 2153-2167 - 1973
Andrew Garton1, M. H. George1
1Department of Chemistry Imperial College of Science and Technology London SW7 2AY, England

Tóm tắt

AbstractThe effect of oxygen on the liquid‐phase polymerization of vinyl chloride at 55°C in the presence of an added initiator, bis(4‐tert‐butylcyclohexyl) peroxydicarbonate (Perkadox 16), has been studied by the technique of tumbled dilatometry. With this method, at constant initiator concentration, the induction period showed a half‐order dependence on the initial oxygen concentration. At a constant initial oxygen concentration, the induction period varied inversely as the square root of the initiator concentration. Under the experimental conditions empolyed, the polyperoxy radicals with chloroalkyl (∼CH2ĊHCl) endgroups were not wholly scavenged by molecular oxygen but could undergo various decomposition reactions. The degree of conversion of the initial oxygen to peroxidic compounds did not exceed 30% by weight and was dependent on the shape of the reaction vessel empolyed. The existence of other oxidation products has been demonstrated. At 55°C, the average velocity constant for decomposition of the peroxide products from vinyl chloride, measured in dichloromethane solution, was found to be 8 × 10−5 sec−1. A kinetic scheme involving a predominant cross‐termination reaction is proposed to explain the experimental results.

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Wiley

Tập 11 Số 9

2153-2167

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