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

Synthesis of highly end-functionalized polyethylene chains was accomplished using both coordination chemistry and radical mediated thiol−ene chemistry. A vinyl end-terminated polyethylene ( M n =1440 g·mol −1, PDI = 1.8) with a functionalization rate of 100% was synthesized using a P,O-chelated catalyst [Ni{Ph 2 PC(COOEt)═C(C 6 H 5 )O}Ph(PPh 3 )]. 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%.