Polyethylene End Functionalization Using Radical-Mediated Thiol−Ene Chemistry: Use of Polyethylenes Containing Alkene End Functionality

International audienceSynthesis of highly end-functionalized polyethylene chains was accomplished using both coordination chemistry and radical mediated thiol?ene chemistry. A vinyl end-terminated polyethylene (Mn =1440 g·mol?1, PDI = 1.8) with a functionalization rate of 100% was synthesized using a P,O-chelated catalyst [Ni\Ph2PC(COOEt)═C(C6H5)O\Ph(PPh3)]. Thiol?ene reactions were subsequently undertaken between vinyl-terminated polyethylene and the thiol-containing molecules thioglycolic acid, 2-mercaptoethanol, 1-thioglycerol, chloropropanethiol, and methyl thioglycolate. A range of end-functionalized polyethylenes was thus prepared using simple reaction conditions and exhibiting degrees of functionalization higher than 93%