Abstract: | The course of intermolecular reactions induced by peroxide decomposition in linear polyethylene has been determined and compared with similar reaction systems in which the substrate is a lowmolecular-weight alkane. Efficiency of intermolecular coupling is 40% for an alkane and 25–30% for the polymer system. Competing reactions, which reduce coupling efficiency, are mainly disproportionation of the initially formed radicals and to a minor extent further reactions involving the products from the peroxide decomposition. The low efficiencies found are similar to those well studied when initial radicals are produced by radiolysis in polymer and alkane systems. |