Polyisobutylene Stars and Polyisobutylene-<i>b</i><i>lock</i>-Poly(<i>tert</i>-Butyl Methacrylate) Block Copolymers by Site Transformation of Thiophene End-Capped Polyisobutylene Chain Ends
作者:Nemesio Martinez-Castro、Michael G. Lanzendörfer、Axel H. E. Müller、Jae Cheol Cho、Metin H. Acar、Rudolf Faust
DOI:10.1021/ma034350s
日期:2003.9.1
2-polyisobutylenyl-thiophene (PIB−T). PIB−T was quantitatively metalated with n-butyllithium in THF at −40 °C. 1H NMR spectroscopic and GC studies of the corresponding model compound, 2-(1,1,3,3-tetramethylbutyl)thiophene, clearly verified quantitative metalation. The resulting stable macrocarbanion (PIB−T-,Li+) was used to initiate living anionic polymerization of tert-butyl methacrylate (tBMA) yielding PIB-b-PtBMA
通过结合活性碳阳离子和阴离子聚合,开发了一种新的合成路线,用于合成聚异丁烯(PIB)星和PIB-聚(甲基丙烯酸酯)嵌段共聚物。快速和噻吩定量单加成到活性PIB链已经结合观察到用TiCl 4 4作为路易斯酸在Ñ正己烷/ CH 2氯2在-78 60/40 V / V℃下导致2- polyisobutylenyl-的形成噻吩(PIB-T)。PIB-T在-40°C下用正丁基锂在THF中定量金属化。1个相应的模型化合物2-(1,1,3,3-四甲基丁基)噻吩的1 H NMR光谱和GC研究清楚地证明了定量金属化作用。将得到的稳定macrocarbanion(PIB-T - ,李+)用于启动的活性阴离子聚合叔丁基甲基丙烯酸酯(吨BMA),得到PIB- b -P吨具有高阻挡效率BMA的嵌段共聚物。通过稳定的大碳双阴离子与SiCl 4的偶联反应制备了PIB星作为偶联剂。这些嵌段共聚物和PIB星的表征是通过尺寸