Low‐molecular‐weight species from high‐pressure polyethylene

Abstract

Abstract A partial analysis is given of the low‐molecular‐weight “oil” fraction produced in the high‐pressure free‐radical–initiated polymerization of ethylene. These oils are shown to constitute a separate family of compounds whose molecular weight distribution can be clearly distinguished from that of the remainder of the polymer. The mechanisms of formation of oils as a class, and of individual compounds found in the oil fraction, are discussed in some detail. The structures of the oils are used to inter steps in the mechanism of polymerization that lead to the formation of short‐chain branches and unsaturation. It is concluded that the data are consistent with the extended Roedel mechanism with the provisions that (1) secondary radicals are probable products of radical scission, (2) cyclic intermediates of other than six members lead to the formation of three, five, and possibly six carbon branches, and (3) clusters of ethyl groups separated by single methylene groups are unlikely side chains.