Université de Lyon, Univ. Lyon 1, CPE Lyon, CNRS, UMR 5265, C2P2 (Chemistry, Catalysis, Polymers, and Processes), Team LCPP, Bat 308F, 43 Bd du 11 Novembre 1918, 69616 Villeurbanne (France).
Angew Chem Int Ed Engl. 2015 Apr 7;54(15):4631-5. doi: 10.1002/anie.201411223. Epub 2015 Feb 16.
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.
端基 α,ω-碘代乙烯基聚乙烯（Vin-PE-I）是通过在[(C5 Me5 )2 NdCl2 Li(OEt2 )2 ]存在下催化乙烯聚合得到的，同时使用了一种官能化的链转移剂，即二（10-十一烯基）镁，然后用碘处理所得的二（乙烯基聚乙烯基）镁化合物((vinyl-PE)2 Mg)。碘代官能化的乙烯基聚乙烯（Vin-PE-I）通过在 95°C 的甲苯中用 tBuOK 简单处理转化为独特的二乙烯基官能化聚乙烯（Vin-PE-Vin）。然后在 AIBN 的存在下，用功能化的硫醇在 Vin-PE-Vin 上成功进行了硫醇-烯反应。在一系列同双官能团端基聚乙烯上定量地在每个链末端安装了羟基、二醇、羧酸、胺、氯化铵、三甲氧基硅基、氯或氟烷基。
