Thiol-End-Functionalized Polyethylenes

Synthesis of well-defined and highly thiol-end-functionalized polyethylene (PE-SH) was performed using olefin polymerization by coordination chemistry and robust functionalization chemistries. Using a Nd-based catalyst in combination with n -butyloctylmagnesium (BOMg), dipolyethylenylmagnesium compounds (PE-Mg-PE) were first prepared by catalyzed polyethylene chain growth on magnesium. Taking advantage of the reactivity of the carbon−magnesium bonds so formed, several functionalization strategies were assessed with the main aim of producing the targeted PE-SH in the simplest and most efficient way. In particular, polysulfurs and thiothiocarbonylated-end-functionalized polyethylenes were successfully obtained and reduced by lithium aluminum hydride (LiAlH 4 ) to give the desired PE with up to 90% thiol chain end functionality.