The infrared absorption spectra of chlorinated polyethylenes with various amounts of combined chlorine have been investigated, and some data on the mechanism of addition of chlorine to the polyethylene molecule has been studied. When polyethylene is chlorinated in carbon tetrachloride solution at 70°C. by chlorine gas, CH2CHCl and the CHClCHCl units are formed in the main carbon chain, but formation of the CCl2 units could not be detected by the present infrared spectral study.

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Suspension polymerization of vinyl chloride was carried out at temperatures of ‐30° to +30°C. with the use of a monomer‐soluble oxidation‐reduction initiator system. A typical initiator system was composed of lauroyl peroxide and ferrous n‐caproate. The effects of temperature, molar ratio of peroxide to reducing agent, and total concentration of initiator upon the rate and degree of polymerization were observed. The activation energy of the overall rate of polymerization was 6.5 kcal./mole. Experimental evidence which may serve to elucidate the mechanism of the redox reaction in the nonemulsified system is discussed.

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