Synthesis of a Bifunctional Initiator for Controlled Kumada Catalyst-Transfer Polycondensation/Nitroxide-Mediated Polymerization and Preparation of Poly(3-hexylthiophene)−Polystyrene Block Copolymer Therefrom
Synthesis of a Bifunctional Initiator for Controlled Kumada Catalyst-Transfer Polycondensation/Nitroxide-Mediated Polymerization and Preparation of Poly(3-hexylthiophene)−Polystyrene Block Copolymer Therefrom
复制标题
用于受控熊田催化剂转移缩聚/硝基氧介导聚合的双功能引发剂的合成及聚(3-己基噻吩)·聚苯乙烯嵌段共聚物的制备
作者：
Senkovskyy;Tkachov R;Bocharova;Komber
在此，我们提出了一种新的方法，通过连续Kumada催化转移缩聚（KCTP）和双功能引发剂TIPNO - Ph - Ni(dppp) - Br （TIPNO = 2,2,5-三甲基-4-苯基-3-扎己烷-3-硝基氧化物）介导的自由基聚合（NMP）合成棒-盘状嵌段共聚物，dppp =丙烷-1,3-二基双（二苯基膦）。该方法的应用实例是制备了一种模型嵌段共聚物聚（3-己基噻吩）-嵌段聚苯乙烯（P3HT-b-PS），其分子量分布相对较窄，为1.33。双功能引发剂的合成是通过二乙基联吡啶镍与易于获得的前驱体TIPNO - Ph - Br反应完成的，然后将联吡啶配体原位取代到双齿磷1上。
Herein, we present a new approach to synthesize rod−coil block copolymers via consecutive Kumada catalyst-transfer polycondensation (KCTP) and nitroxide-mediated free radical polymerization (NMP) performed from a bifunctional initiator, TIPNO−Ph−Ni(dppp)−Br (TIPNO = 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide; dppp = propane-1,3-diylbis(diphenylphosphane). The utility of the method was exemplified in a preparation of a model block copolymer, poly(3-hexylthiophene)-block-polystyrene (P3HT-b-PS) with a relatively narrow molecular weight distribution of 1.33. Synthesis of the bifunctional initiator was accomplished by a reaction of diethylbipyridylnickel with a readily accessible precursor, TIPNO−Ph−Br, followed by in situ replacement of the bipyridyl ligand onto bidentate phosphorus one.