Polytriarylamine copolymers can be prepared by Suzuki-Miyaura cross-coupling reactions of bis N-methyliminodiacetic acid (MIDA) boronate ester substituted arylamines with dibromo arenes. The roles of solvent composition, temperature, reaction time, and co-monomer structure were examined and (co)polymers prepared containing 9, 9-dioctylfluorene (F8), 4-sec-butyl or 4-octylphenyl diphenyl amine (TFB), and N, N'-bis(4-octylphenyl)-N, N'-diphenyl phenylenediamine (PTB) units, using a Pd(OAc)2/2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (SPhos) catalyst system. The performance of a di-functionalized MIDA boronate ester monomer was compared with that of an equivalent pinacol boronate ester. Higher molar mass polymers were produced from reactions starting with a difunctionalized pinacol boronate ester monomer than the equivalent difunctionalized MIDA boronate ester monomer in biphase solvent mixtures (toluene/dioxane/water). Matrix-assisted laser desorption/ionization mass spectroscopic analysis revealed that polymeric structures rich in residues associated with the starting MIDA monomer were present, suggesting that homo-coupling of the boronate ester must be occurring to the detriment of cross-coupling in the step-growth polymerization. However, when comparable reactions of the two boronate monomers with a dibromo fluorene monomer were completed in a single phase solvent mixture (dioxane + water), high molar mass polymers with relatively narrow distribution ranges were obtained after only 4 h of reaction. © 2017 The Authors. Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2798-2806.

中文翻译：

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N-甲基亚氨基二乙酸硼酸酯在三芳基胺和芴单体的suzuki-miyaura交叉偶联聚合中的用途。

聚三芳基胺共聚物可通过双N-甲基亚氨基二乙酸（MIDA）硼酸酯取代的芳基胺与二溴芳烃的Suzuki-Miyaura交叉偶联反应制备。检查了溶剂组成，温度，反应时间和共聚单体结构的作用，并制备了包含9、9-二辛基芴（F8），4-仲丁基或4-辛基苯基二苯胺（TFB）的（共）聚合物N，N'-双（4-辛基苯基）-N，N'-二苯基苯二胺（PTB）单元，使用Pd（OAc）2 / 2-二环己基膦基2'，6'-二甲氧基联苯（SPhos）催化剂体系。将双官能化MIDA硼酸酯单体的性能与当量频哪醇硼酸酯的性能进行了比较。在双相溶剂混合物（甲苯/二恶烷/水）中，与二官能化的频哪醇硼酸酯单体相比，从双官能的频哪醇硼酸酯单体开始的反应生产的摩尔质量更高的聚合物。基质辅助激光解吸/电离质谱分析表明，存在与起始MIDA单体相关的残基丰富的聚合物结构，这表明必须发生硼酸酯的均相偶联，从而不利于逐步增长中的交叉偶联。聚合。但是，当两种硼酸酯单体与二溴芴单体的可比反应在单相溶剂混合物（二恶烷+水）中完成时，仅在反应4小时后即可获得分布范围相对较窄的高摩尔质量聚合物。©2017作者。高分子科学杂志A部分：高分子化学，由Wiley Periodicals，Inc.出版，J。Polym。科学，A部分：Polym。化学 2017，55，2798-2806。