Homolytic Decomposition of Sulfonyl Chlorides

The products, kinetic parameters, and activation entropy of thermal decomposition of sulfonyl chloride groups in chlorosulfonated polyethylene (CSPE) have been studied for the first time, and it has been demonstrated that the decomposition mechanism involves simultaneous cleavage of two bonds (carbon-sulfur and sulfur-chlorine) to give an SO2 molecule and two free radicals, which can be useful in the process of polymer structuring. The radical mechanism has been confirmed by the formation of 2,3-diphenyl-2,3- dimethylbutane on heating CSPE in isopropylbenzene. The simultaneous cleavage of two bonds is supported by the low activation energy and pre-exponential factor in the Arrhenius equation, as well as by negative activation entropy values.