Optimization of the Reaction Conditions for Direct Arylation Polymerizations in a Sustainable Solvent,Macromolecular Chemistry and Physics

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Optimization of the Reaction Conditions for Direct Arylation Polymerizations in a Sustainable Solvent
Macromolecular Chemistry and Physics ( IF 2.5 ) Pub Date : 2020-05-13 , DOI: 10.1002/macp.202000041
Daniele Conelli ₁ , Roberto Grisorio ₁ , Gian Paolo Suranna _{1,

2}

Affiliation

Direct arylation polymerization (DArP) relieves the synthesis of conjugated polymers from the use of hazardous and toxic reagents typical of the traditional protocols. However, the compatibility with environmentally benign, nonhazardous, and low‐cost solvents still represents the critical aspect for projecting DArP as an industrial‐scale method for the preparation of conjugated polymers. In this study, a “green” solvent (i.e., cyclopentyl methyl ether) is implemented for the obtainment of poly(3‐hexylthiophene) by DArP reaction, in order to explore sustainable reaction conditions also regarding the catalytic system and the base quantity, which equally undermine the sustainability of the DArP protocol. Considering the molecular weights as the indicator of precatalyst performance in determined conditions, it is established that the cheapest palladium source (i.e., PdCl₂) combined with two equivalents of (o‐anisyl)₃P is able to yield the best results in the green ethereal solvent. Furthermore, it is found how, with respect to the common DArP protocols, the quantity of the expensive base (i.e., Cs₂CO₃) can be reduced in these reaction conditions without compromising molecular weights and regioregularity of the resulting polymer. These optimized reaction conditions can be extended to the copolymerization of other monomer units with satisfactory results in terms of molecular weights.

中文翻译：

可持续溶剂中直接芳基化聚合反应条件的优化

直接芳基化聚合（DArP）可避免使用传统规程中常见的危险和有毒试剂来合成共轭聚合物。但是，与环境友好，无害和低成本溶剂的相容性仍然代表着将DArP投影为制备共轭聚合物的工业规模方法的关键方面。在这项研究中，为通过DArP反应获得聚（3-己基噻吩），使用了一种“绿色”溶剂（即环戊基甲基醚），以探索关于催化体系和碱量的可持续反应条件。同样破坏了DArP协议的可持续性。考虑到分子量是确定条件下预催化剂性能的指标，₂）与两个当量的（邻-茴香基）₃ P结合可以在绿色醚溶剂中产生最佳结果。此外，发现相对于常见的DArP方案，如何在这些反应条件下减少昂贵的碱（即，Cs ₂ CO ₃）的量而不损害所得聚合物的分子量和区域规则性。这些优化的反应条件可以扩展到其他单体单元的共聚，就分子量而言令人满意的结果。

更新日期：2020-05-13

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