Divinyl-end-functionalized polyethylenes: ready access to a range of telechelic polyethylenes through thiol-ene reactions.

Telechelic α,ω-iodo-vinyl-polyethylenes (Vin-PE-I) were obtained by catalytic ethylene polymerization in the presence of [(C5 Me5 )2 NdCl2 Li(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 I2 . 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 °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.