Foster Andrew B, Yu Ming, Alshurafa Mustafa, Budd Peter M
Department of Chemistry, University of Manchester, Oxford Road, Manchester M13 9PL, U.K.
Macromolecules. 2025 Mar 13;58(8):4289-4299. doi: 10.1021/acs.macromol.4c02657. eCollection 2025 Apr 22.
An overview is provided of the influence of polymer topology on the physical aging of PIM-1 thin film composite (TFC) membranes measured in gas permeation studies. Topologically distinct PIM-1 samples are compared first with each other, then in polymeric blends, and then with other literature. Both initial permeability (1 day) and long-term aging rates (up to 1 year) can be attributed to structural components present within the overall microstructure of the polymer. The rigidity and structural regularity of a predominantly disubstituted PIM-1 polymer proved to facilitate high initial CO permeability in TFCs followed by a rapid aging rate (β = 1.0) to produce an increasingly nonselective membrane over 28 days. By contrast, TFCs prepared from branched PIM-1 polymers, which have lower glass transition temperature, exhibit lower initial permeabilities followed by much slower aging rates, remaining highly selective for up to one year. Branched PIM-1 polymers which contain a greater proportion of small loop structures show a very slow aging rate (β = 0.22-0.25), whereas those with more open branched structure tend to exhibit a faster aging rate (β = 0.67-0.69). Thin film nanocomposite (TFN) membranes cast from blends of a disubstituted PIM-1 with colloidal network (CN)-rich PIM-1 fillers can completely halt permeability aging for up to one month but then subsequently resume aging at a faster rate (β = 1.8-2.8) to more than compensate. TFNs prepared from blending a branched PIM-1 polymer with a CN-rich Cardo-PIM-1 filler can produce better long-term aging performance (up to 1 year).
本文概述了聚合物拓扑结构对在气体渗透研究中测量的PIM-1薄膜复合(TFC)膜物理老化的影响。首先将拓扑结构不同的PIM-1样品相互比较,然后在聚合物共混物中比较,最后与其他文献进行比较。初始渗透率(1天)和长期老化速率(长达1年)均可归因于聚合物整体微观结构中存在的结构成分。事实证明,主要为二取代的PIM-1聚合物的刚性和结构规则性有助于TFC中具有较高的初始CO渗透率,随后老化速率较快(β = 1.0),从而在28天内产生选择性越来越低的膜。相比之下,由玻璃化转变温度较低的支化PIM-1聚合物制备的TFC,其初始渗透率较低,随后老化速率慢得多,在长达一年的时间内保持高选择性。含有较大比例小环结构的支化PIM-1聚合物显示出非常缓慢的老化速率(β = 0.22 - 0.25),而具有更开放支化结构的聚合物往往表现出更快的老化速率(β = 0.67 - 0.69)。由二取代的PIM-1与富含胶体网络(CN)的PIM-1填料的共混物浇铸而成的薄膜纳米复合(TFN)膜,可在长达一个月的时间内完全停止渗透率老化,但随后会以更快的速率(β = 1.8 - 2.8)恢复老化,以进行更多补偿。由支化PIM-1聚合物与富含CN的Cardo-PIM-1填料共混制备的TFN可产生更好的长期老化性能(长达1年)。