Rate Constant for Long-Chain Branch Formation in Free-Radical Polymerization of Ethylene

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Abstract
Quantitative measurements on the rate constant for long-chain branching in radical polymerization of ethylene have not yet been cited. This paper presents a convenient method of calculating the ratio of the rate constant for long-chain branching to that for propagation, by means of polymerization parameters, average degrees of polymerization (Xn and Xw), and amount of total unsaturation. The results of calculation based on our experimental data show that the activation energy Etrp -Ep, and the activation volume ΔV trp ∗-ΔV ∗p were 3.6 kcal/mole and 24 cc/mole, respectively, in radical polymerization of ethylene. The validity of these values is discussed.