γ-strahlenchemische Reaktionen von Phosphortrichlorid mit Olefinen

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.