Castillo Grace E, Thompson Barry C
Department of Chemistry, Loker Hydrocarbon Research Institute, University of Southern California, Los Angeles, California 90089-1661, United States.
ACS Macro Lett. 2023 Oct 17;12(10):1339-1344. doi: 10.1021/acsmacrolett.3c00396. Epub 2023 Sep 18.
While a major improvement to the sustainability of conjugated polymer synthesis, traditional direct arylation polymerization (DArP) still requires high temperatures (typically >100 °C), necessitating a significant energy input requirement. Performing DArP at reduced or ambient temperatures would represent an improvement to the sustainability of the reaction. Here we describe the first report of a well-defined conjugated polymer synthesized by DArP at room temperature. Previous efforts toward room temperature DArP relied on the use of a near-stoichiometric silver reagent, an expensive coinage metal, which makes the reaction less cost-effective and sustainable. Here, room temperature polymerizations of 3,4-ethylenedioxythiophene (EDOT) and 9,9-dioctyl-2,7-diiodofluorene were optimized and provided molar mass () up to 11 kg/mol PEDOTF, and performing the reaction at the standard ambient temperature of 25 °C provided up to 15 kg/mol. Model studies using other C-H monomers of varying electron density copolymerized with 9,9-dioctyl-2,7-diiodofluorene provided insight into the scope of the room temperature polymerization, suggesting that performing room temperature DArP is highly dependent on the electron richness of the C-H monomer.
尽管传统的直接芳基化聚合反应（DArP）对共轭聚合物合成的可持续性有了重大改进，但仍需要高温（通常>100°C），这需要大量的能量输入。在降低的温度或环境温度下进行DArP将是该反应可持续性的一项改进。在此，我们报道了首例通过DArP在室温下合成的结构明确的共轭聚合物。之前实现室温DArP的努力依赖于使用近化学计量的银试剂，这是一种昂贵的货币金属，使得该反应的成本效益和可持续性较低。在此，对3,4-亚乙基二氧噻吩（EDOT）和9,9-二辛基-2,7-二碘芴进行了室温聚合优化，得到了高达11 kg/mol的聚（3,4-亚乙基二氧噻吩-共-9,9-二辛基芴）（PEDOTF）摩尔质量，在25°C的标准环境温度下进行反应得到的摩尔质量高达15 kg/mol。使用其他具有不同电子密度的C-H单体与9,9-二辛基-2,7-二碘芴进行共聚的模型研究，深入了解了室温聚合的范围，表明进行室温DArP高度依赖于C-H单体的电子丰富度。
