| Abstract: | The effect of a range of 10 organic nitriles on the radiation-induced polymerization of styrene was studied. A dose rate of 4.4 rad s?1 was used. A rate of polymerization of styrene (1.744 mol L?1 of toluene solution) of 5.0 × 10?7 mol L?1 s?1 was found. With organic nitriles present (styrene:nitrile ratio of 1:0.28) the rate of polymerization increased. Rates in the range of 5.5 × 10?7 ?5.2 × 10?6 mol L?1 s?1, depending on the nitrile present, were obtained. The polymers were partially characterized and evidence of involvement of each of the nitriles in the polymer chains was revealed. The increase in rate of polymerization has been attributed to the part played by nitrile radicals in the initiation of styrene polymerization. Radical yield values [as G(nitrile radical)] were derived from the relevant rate expressions. Values ranged from 2.7 to 49.5, depending on the particular nitrile. Corresponding values of G(nitrile radical) in the range of 5.1–129.4 were obtained by the manipulation of number-average molar mass data. Values of kpkt of approximately 2 × 10?5 L mol?1 s?1 were found. Trommsdorff types of effect are absent from these systems. |
