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Divinyl‐End‐Functionalized Polyethylenes: Ready Access to a Range of Telechelic Polyethylenes through Thiol–Ene Reactions
Author(s) -
Norsic Sebastien,
Thomas Coralie,
D'Agosto Franck,
Boisson Christophe
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201411223
Subject(s) - polymer chemistry , telechelic polymer , chemistry , chain transfer , polymerization , magnesium , ene reaction , end group , radical polymerization , organic chemistry , polymer
Telechelic α,ω‐iodo‐vinyl‐polyethylenes (Vin‐PE‐I) were obtained by catalytic ethylene polymerization in the presence of [(C 5 Me 5 ) 2 NdCl 2 Li(OEt 2 ) 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 t BuOK 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.