The rate of autoxidation of chloroprene has been measured over the range 0 to 40°C. From oxidations with an added initiator the energy of activation for propagation was found to be 9.6 kcal./mole. The oxidation product is an unstable copolymer with oxygen formed by both 1,2 and 1,4 addition, the latter predominating. The molecular weight of the polyperoxide fell throughout the oxidation, to about 1000 at 20% oxidation. The molecular weight distribution was measured by gel permeation chromatography. The rates of oxidation of some monosubstituted vinyl monomers have been correlated by the Q,e reactivity scheme.
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