Divinyl-End-Functionalized Polyethylenes: Ready Access to a Range of Telechelic Polyethylenes through Thiol-Ene Reactions

Telechelic ,-iodo-vinyl-polyethylenes (Vin-PE-I) were obtained by catalytic ethylene polymerization in the presence of [(C5Me5)(2)NdCl2Li(OEt2)(2)] in combination with a functionalized chain-transfer agent, namely, di(10-undecenyl)magnesium, followed by treatment of the resulting di(vinylpolyethylenyl)magnesium compounds ((vinyl-PE)(2)Mg) with I-2. The iodo-functionalized vinylpolyethylenes (Vin-PE-I) were transformed into unique divinyl-functionalized polyethylenes (Vin-PE-Vin) by simple treatment with tBuOK in toluene at 95 degrees C. Thiol-ene reactions were then successfully performed on Vin-PE-Vin with functionalized thiols in the presence of AIBN. A range of homobifunctional telechelic polyethylenes were obtained on which a hydroxy, diol, carboxylic acid, amine, ammonium chloride, trimethoxysilyl, chloro, or fluoroalkyl group was installed quantitatively at each chain end.