Synthesis of Fluorinated Poly(phenyl-alkane)s of Intrinsic Microporosity by Regioselective Aldehyde (A2) + Aromatics (B2) Friedel–Crafts Polycondensation,Macromolecules

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Synthesis of Fluorinated Poly(phenyl-alkane)s of Intrinsic Microporosity by Regioselective Aldehyde (A2) + Aromatics (B2) Friedel–Crafts Polycondensation
Macromolecules ( IF 5.1 ) Pub Date : 2021-06-22 , DOI: 10.1021/acs.macromol.1c00468
Shengyang Zhou _{1,

2} , Jiayu Guan _{1,

2} , Ziqin Li _{1,

2} , Qifeng Zhang ₁ , Jifu Zheng ₁ , Shenghai Li _{1,

2} , Suobo Zhang _{1,

2}

Affiliation

The design of functionalized porous materials is an important research direction in material science, especially for fluorine-containing materials with enhanced thermal/oxidative stability, lower dielectric constants, and better gas-selective permeation. In this work, a series of poly(phenyl-alkane)s of intrinsic microporosity (PIM-xR) were synthesized by the methanesulfonic acid-catalyzed Friedel–Crafts hydroxyalkylation polycondensation of contorted and rigid multibenzene and benzaldehyde derivatives. The PIM-xR exhibited good thermal stability, excellent solution processability, and high Brunauer–Emmett–Teller (BET) surface areas (400–1200 m² g^–1). The physicochemical properties and applications of PIM-xR could be tuned by the type, quantity, distribution, and postmodification of substituents on the benzaldehyde derivatives. Unlike other contorted and rigid multibenzene derivatives, only electron-rich spirobiindane derivatives directly produced soluble, linear, high-molecular-weight polymers without cross-linking because spirobiindane possesses three t-butyl-like structural units that provide large steric hindrance at potential reactive sites. Subsequently, a series of fluorinated PIMs (PIM-xF) with different fluorine contents and distributions were explored, and the relationship between the microporosity of PIM-xR and degrees of rotational freedom of the polymer chains was analyzed using these PIM-xF. Flexible and transparent PIM-xF membranes were easily obtained by solution processing and exhibited high gas permeabilities and moderate permeability selectivity. In particular, the CO₂/N₂ separation performance of the PIM-5F membrane exceeded the 2008 Robeson’s upper bound (P_CO₂ = 3240 barrer and α_(CO₂/N₂) = 27.9). This work provides a facile method for the precise design and preparation of fluorinated or other functionalized porous materials for environmental and energy applications.

中文翻译：

通过区域选择性醛 (A ₂ ) + 芳烃 (B ₂ ) Friedel-Crafts 缩聚反应合成具有固有微孔的氟化聚（苯基-烷烃）

功能化多孔材料的设计是材料科学的一个重要研究方向，特别是对于具有增强的热/氧化稳定性、更低的介电常数和更好的气体选择性渗透的含氟材料。在这项工作中，通过甲磺酸催化的扭曲和刚性多苯和苯甲醛衍生物的 Friedel-Crafts 羟烷基化缩聚反应合成了一系列具有固有微孔性 (PIM- x R)的聚（苯基-烷烃）。PIM- x R 表现出良好的热稳定性、出色的溶液加工性和高布鲁诺-埃米特-特勒 (BET) 表面积（400-1200 m ² g ^–1）。PIM- x的理化性质及应用R 可以通过苯甲醛衍生物上取代基的类型、数量、分布和后修饰来调整。与其他扭曲和刚性多苯衍生物不同，只有富含电子的螺联茚衍生物才能直接产生可溶性、线性、高分子量聚合物而无需交联，因为螺联茚具有三个类似叔丁基的结构单元，可在潜在反应位点提供大的空间位阻. 随后，探索了一系列具有不同氟含量和分布的氟化 PIM（PIM- x F），并使用这些 PIM- x F分析了 PIM- x R的微孔率与聚合物链旋转自由度之间的关系. 灵活透明的 PIM-x F 膜很容易通过溶液处理获得，并表现出高气体渗透性和中等渗透选择性。特别是PIM-5F膜的CO ₂ /N ₂分离性能超过了2008年Robeson的上限（P _{CO ₂} = 3240 barrer和α _{(CO ₂ /N ₂ )} = 27.9）。这项工作为精确设计和制备用于环境和能源应用的氟化或其他功能化多孔材料提供了一种简便的方法。

更新日期：2021-07-13

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