Semifluorinated, kinked polyarylenes via direct arylation polycondensation,Polymer Chemistry

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Semifluorinated, kinked polyarylenes via direct arylation polycondensation
Polymer Chemistry ( IF 4.1 ) Pub Date : 2020-10-07 , DOI: 10.1039/d0py00973c
Fabian Kempe _{1,

2,

3} , Felix Riehle _{3,

4,

5,

6} , Hartmut Komber _{3,

7,

8} , Rukiya Matsidik _{1,

2,

3} , Michael Walter _{3,

5,

9,

10} , Michael Sommer _{1,

2,

3}

Affiliation

Semifluorinated, amorphous polyarylenes PmmpF4 with kinked backbone structure were prepared from a meta-substituted, biphenol-based monomer with varying alkoxy substituents R and 1,2,4,5-tetrafluorobenzene (pF4) via direct arylation polymerization (DAP). The chemistry employed is simple, scalable and does not rely on tedious purification techniques. Polycondensation occurs cleanly without major side reactions. Despite the clean polycondensation reaction, very high molar mass materials are difficult to obtain, which is ascribed to an unusual solubility behavior compared to non-fluorinated analogs, and similar, yet more linear tetrafluorobenzene copolymers based on fluorene or carbazole. In order to investigate this phenomenon further, the side chain-dependent properties PmmpF4 are investigated using linear, branched and cyclic side-chains. While the glass transition temperature of PmmpF4 is a strong function of R and can be varied between 35 °C and 197 °C for constant backbone structure and molecular weight, solubility cannot be improved by using longer linear or branched side chains. Density functional theory calculations suggest significant polarization-type non-covalent interactions between tetrafluorobenzene and the biphenol-based monomer as origin for the observed limited solubility, which guide the design of both kinked and straight conjugated polymers with high molar mass and solubility.

中文翻译：

通过直接芳基化缩聚反应的半氟化扭结聚亚芳基

半氟化，无定形聚芳撑P MMP F4与来自制备扭结骨架结构的元取代的，基于双酚的单体有不同的烷氧基取代基R和1,2,4,5-四氟苯（PF4）经由直接芳基化聚合（DAP）。所采用的化学方法简单，可扩展且不依赖乏味的纯化技术。干净地发生缩聚反应，而没有重大的副反应。尽管进行了干净的缩聚反应，但仍难以获得非常高的摩尔质量的材料，这与非氟化类似物以及基于芴或咔唑的类似但更线性的四氟苯共聚物相比，具有异常的溶解性。为了进一步研究该现象，使用直链，支链和环状侧链研究了侧链依赖性特性P mmp F4。而玻璃化转变温度为P mmpF4是R的强大功能，对于恒定的骨架结构和分子量，可以在35°C至197°C之间变化，使用更长的线性或支链侧链无法提高溶解度。密度泛函理论计算表明，四氟苯和双酚类单体之间存在明显的极化型非共价相互作用，这是观察到的有限溶解度的来源，这指导了具有高摩尔质量和溶解度的扭结和直链共轭聚合物的设计。

更新日期：2020-11-03

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