Abstract
α-chloro-alkyl-phosphorus dichlorides have been synthesized by γ-irradiating mixtures of various olefines with phosphorus trichloride. The G-values are of the order of several hundreds. The effects of the structure of the olefine on the yields at various temperatures are described. A polymer which contains small amounts of phosphorus is formed in mixtures of styrene and PCl3. Phosphorus trichloride decreases the molecular weight as well as the rate of polymerization of styrene. The decrease in molecular weight can be described by a telomerization mechanism, the transfer constant at room temperature being equal to 0.24. However, the phosphorus content of the polymer is higher than expected from this simple mechanism. The polymerization of α-methylstyrene is accelerated by phosphorus trichloride.
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