Abstract
It was established that under dry conditions the radiation-induced polymerizations of styrene and α-methylstyrene proceed predominantly through free cationic intermediates. The parallel measurements of electrical conductivity and rate of polymerization were carried out on these monomers. According to eq 1, (τg=r3/3Drc), the estimation of kp(+) rests on a knowledge of Rp, τ, and Ri at a particular dose rate:Rp=Riτkp[M] where kp is propagation rate constant and [M] concentration of monomer. Rp values are determined dilatometrically and Ri is based on a Gi value of 0.1 for hydrocarbons. It should be noted that the lifetime of free ions under irradiation at these dose rates is the order of 100 ms and kp values of free cationic propagation are very large, as high as 106 M−1 s−1. It was reported the estimation of free-ion lifetimes by pulse electrical conductivity measurement based on the principle of the “rotating sector method” was used for the lifetime estimation of intermediates generated by electron irradiation through bimolecular reaction. The estimated lifetimes agreed with those calculated from steady-state conductance.The initiation mechanism of radiation-induced ionic polymerization of α-methylstyrene has been elucidated by the use of pulse radiolysis technique.
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Hayashi, K. Radiation and Photo-Induced Ionic Polymerization. Polym J 12, 583–596 (1980). https://doi.org/10.1295/polymj.12.583
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DOI: https://doi.org/10.1295/polymj.12.583
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