Influence of Aliphatic and Aromatic Fluorine Groups on Gas Permeability and Morphology of Fluorinated Polyimide Films,Macromolecules

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Influence of Aliphatic and Aromatic Fluorine Groups on Gas Permeability and Morphology of Fluorinated Polyimide Films
Macromolecules ( IF 5.1 ) Pub Date : 2020-06-29 , DOI: 10.1021/acs.macromol.0c01024
Albert X. Wu ₁ , James A. Drayton ₁ , Katherine Mizrahi Rodriguez ₂ , Qihui Qian ₁ , Sharon Lin ₁ , Zachary P. Smith ₁

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Partially fluorinated polymers often exhibit exceptional membrane-based separation performance for a variety of gas pairs. While many gas transport studies focus on the incorporation of aliphatic fluorine groups (e.g., −CF₃) on the polymer backbone, few studies have systematically investigated structure–property relationships for aromatic fluorine groups. Here, the effect of aliphatic and aromatic fluorine groups on solid-state morphology and gas transport is compared for structural analogues of 6FDA-based polyimides that contain either hydrogen or fluorine functional groups on the diamine monomer. Both fluorinated analogues displayed higher gas diffusivity compared to their hydrocarbon-based counterparts. However, the aromatic fluorinated analogue displayed a larger decrease in diffusivity selectivity due to weakened secondary interchain forces and a larger increase in interchain spacing, suggesting a greater extent of packing disruption resulting from increased steric hindrance associated with aromatic fluorine groups. This study establishes guiding principles for how carbon–fluorine bonds affect macromolecular packing structure and gas separation performance.

中文翻译：

脂肪族和芳香族氟基对氟化聚酰亚胺薄膜气体渗透性和形态的影响

对于各种气体对，部分氟化的聚合物通常表现出出色的基于膜的分离性能。尽管许多气体传输研究都集中在脂肪族氟基团（例如-CF ₃）在聚合物主链上，很少有研究系统地研究芳族氟基团的结构-性质关系。在此，比较了脂肪族和芳香族氟基团对固态形态和气体传输的影响，以分析在二胺单体上含有氢或氟官能团的基于6FDA的聚酰亚胺的结构类似物。与基于碳氢化合物的同类产品相比，这两种氟化类似物均显示出更高的气体扩散率。然而，由于弱的次级链间作用力和链间间距的增加，芳族氟化类似物显示出更大的扩散选择性的降低，这表明由与芳族氟基团相关的位阻增加导致的堆积破坏的程度更大。

更新日期：2020-07-14

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