准聚轮烷复合薄膜的制备及其在分离领域的应用

doi:10.6023/A25030085

摘要/Abstract

准聚轮烷复合薄膜具有独特的刺激响应性和优异的功能可拓展性, 具有重要的实际应用价值. 基于1,4-二乙氧基柱[5]芳烃(DEP5A)和聚己内酯嵌段聚四氢呋喃嵌段聚己内酯(PCL-b-PTHF-b-PCL)构建出嵌段结构的准聚轮烷(PPR). 通过优化聚合物浓度、柱芳烃含量、制膜湿度和溶剂等静电喷雾技术条件, 成功制备出表面形貌均匀、疏水性强且对竞争性客体1,4-二溴丁烷(DBrBu)具有响应性的PPR褶皱微球薄膜. 最后, 通过静电纺丝和静电喷雾相结合的制膜技术, 制备出PPR微球和聚苯乙烯(PS)纤维组成的复合薄膜. 由于薄膜中微球/纤维复合结构为有机污染物提供了更丰富的吸附位点, 该复合薄膜在水中染料吸附分离的实验中获得了良好的效果. 这为智能薄膜的研究和开发提供了一种新策略.

关键词: 柱芳烃, 准聚轮烷, 静电喷雾, 静电纺丝, 复合薄膜

The polypseudorotaxane (PPR) composite membrane exhibits unique stimuli-responsive properties and excellent functional extensibility, demonstrating significant practical application value, making them promising candidates for smart materials in environmental management, biomedical engineering and next-generation energy storage solutions. This study presents a systematic approach to design and fabricate advanced PPR composite membrane with tailored structures and desired performances. Firstly, a block-structured PPR was constructed by threading 1,4-diethoxy pillar[5]arene (DEP5A) macrocycles onto a triblock copolymer backbone of polycaprolactone block polytetrahydrofuran block polycaprolactone (PCL-b-PTHF-b-PCL) via host-guest interactions. Subsequently, through systematic optimization of the electrospraying parameters including polymer concentration, pillararene content, ambient humidity, and solvent selection, we successfully fabricated PPR wrinkled microsphere membrane with uniform surface morphology, strong hydrophobicity, and responsiveness to the competitive guest molecule 1,4-dibromobutane (DBrBu). To further enhance functionality, we developed composite membrane composed of PPR microspheres and polystyrene (PS) fibers by combining electrospinning and electrospraying techniques. The microsphere/fiber composite architecture provides abundant adsorption sites for organic pollutants, enabling the membrane to achieve remarkable performance in aqueous dye adsorption and separation experiments. The structural characteristics and performance advantages of composite membrane were systematically investigated through scanning electron microscopy, contact angle measurements, and UV-vis spectroscopy. The stimuli-responsive behavior was attributed to the host-guest interaction between DEP5A and the polymer chains, while the enhanced separation efficiency originated from the synergistic effects of the microsphere-fiber composite architecture. This research presents a novel strategy for the investigation and development of smart membrane. The advanced membrane-making technology opens up new possibilities for creating multifunctional separation membranes, smart coatings, and environmental remediation materials.

Key words: pillararene, polypseudorotaxane, electrospraying, electrospinning, composite membrane

引用此文

禚可欣, 丁琦伟, 牟蔚鑫, 闫益恺, 陈健壮, 林绍梁. 准聚轮烷复合薄膜的制备及其在分离领域的应用[J]. 化学学报, 2025, 83(6): 602-607.

Kexin Zhuo, Qiwei Ding, Weixin Mou, Yikai Yan, Jianzhuang Chen, Shaoliang Lin. Preparation of Polypseudorotaxane Composite Membrane and Its Application in Separation Field[J]. Acta Chimica Sinica, 2025, 83(6): 602-607.

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图/表 6

图1. 嵌段结构准聚轮烷的构建、温度和竞争性客体响应过程及利用静电喷雾技术制备PPR薄膜过程示意图

Figure 1. The construction of block structured PPR, its thermo and competitive guest response processes, and the schematic diagram of the process of preparing PPR membranes by electrospraying

图2. 加入不同物质的量比DEP5A后PCL-b-PTHF-b-PCL (10 mg• mL-1)的1H NMR谱图(600 MHz, CDCl3, 20 ℃); 放大图显示了PCL链段中H4的变化

Figure 2. 1H NMR spectra (600 MHz, CDCl3, 20 ℃) of PCL-b- PTHF-b-PCL (10 mg•mL-1) upon the addition of DEP5A. The enlarged view reveals the shifts of H4 in PCL block

图3. PPR薄膜竞争性客体响应性实验流程示意图

Figure 3. Schematic illustration of competitive guest responsing experiment on PPR membrane

图4. 在竞争性客体中浸泡不同时间的PPR (10 mg•mL-1, 10 equiv. DEP5A)薄膜的SEM图: (a1) 0 s, (b1) 10 min. (a2), (b2)分别为(a1), (b1)的放大图, (a1), (b1)的插图为对应的接触角数据

Figure 4. SEM images of PPR membranes soaked in competitive guests for different times (a1) 0 s, (b1) 10 min. (a2), (b2) are enlarged views of (a1), (b1), respectively. The insets (a1), (b1) are contact angle data

图5. 利用静电纺丝和静电喷雾结合法制备PPR/PS复合薄膜过程示意图

Figure 5. The process diagram of preparing PPR/PS composite membranes by electrospinning and electrospraying

图6. 过滤含罗丹明溶液前后溶液及薄膜的照片对比. (a) PS纤维膜; (b) PPR/PS复合薄膜; (c)含罗丹明溶液及经PS纤维膜和PPR/PS复合薄膜过滤后溶液的紫外-可见吸收光谱图

Figure 6. Comparative photographs of the solution color and film before and after filtration of Rhodamine-containing solution using membranes. (a) PS membrane; (b) PPR/PS composite membrane; (c) UV-vis absorption spectra of the Rhodamine-containing solution and the solutions filtered through PS membrane and PPR/PS composite membrane

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