Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex
Direct Synthesis of Chain‐end‐functionalized Poly(3‐hexylthiophene) without Protecting Groups Using a Zincate Complex
复制标题
使用锌酸盐配合物直接合成无保护基团的链端官能化聚（3-己基噻吩）
DOI：
10.1002/marc.202000148
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发表时间：
2020
影响因子：
4.6
通讯作者：
Higashihara Tomoya
中科院分区：
文献类型：
--
作者：
Inagaki Shin;Yamamoto Takuya;Higashihara Tomoya
利用tBu 4 ZnLi 2的锌酸盐配合物，采用Negishi催化转移缩聚法直接合成了含苯甲醇（─ PhCH 2 OH）、苯酚（─PhOH）和苯甲酸（─PhCOOH）基团的链端官能化聚（3-己基噻吩）（P3 HTs）.在该体系中，既不需要保护步骤也不需要脱保护步骤，并且还提供了活性聚合体系以控制分子量，同时保持所获得的P3 HT衍生物的低摩尔质量分散度（MRM）。实际上，可以沿着合成具有受控数均分子量（Mn= 5100-20 000）、低Mn（1.06-1.14）和高链端官能度（Fn = 46-86%）的链端官能化P3 HT。发现醇和酚基团的Fn值很高（基于1H NMR，分别为86%（对于─ PhCH 2 OH）和71%（对于─PhOH）），这也通过基质辅助激光解吸/电离飞行时间质谱法证实。易于合成的链端官能化的P3 HT将适用于含有P3 HT的嵌段和支化聚合物以及其相关的半导体聚合物链段的容易合成。
Chain‐end‐functionalized poly(3‐hexylthiophene)s (P3HTs) with benzyl alcohol (─PhCH2OH), phenol (─PhOH), and benzoic acid (─PhCOOH) groups are directly synthesized based on the Negishi catalyst‐transfer polycondensation method utilizing the zincate complex oftBu4ZnLi2. In this system, neither protection nor deprotection steps are required, and also providing a living polymerization system to control the molecular weight while maintaining a low molar mass dispersity (ÐM) of the obtained P3HT derivatives. Indeed, the chain‐end‐functionalized P3HTs can be synthesized along with controlled number‐average molecular weights (Mn= 5100–20 000), lowÐM(1.06–1.14), and high chain‐end functionality (Fn = 46–86%). The Fn values for the alcohol and phenol groups are found to be high (86% for ─PhCH2OH and 71% for ─PhOH based on1H NMR, respectively), as also confirmed by matrix‐assisted laser desorption/ionization time of flight mass spectroscopy. The easily synthesizable chain‐end‐functionalized P3HTs will be applicable for the facile synthesis of block and branched polymers containing P3HT as well as its related semiconducting polymer segments.