Appold Michael, Rangou Sofia, Glass Sarah, Lademann Brigitte, Filiz Volkan
Institute of Membrane Research, Helmholtz-Zentrum Hereon, Max-Planck-Str.1, 21502, Geesthacht, Germany.
Adv Sci (Weinh). 2024 Sep;11(33):e2403288. doi: 10.1002/advs.202403288. Epub 2024 Jul 1.
Amphiphilic block copolymers are promising candidates for the fabrication of ultrafiltration membranes with an isoporous integral asymmetric structure. The membranes are typically fabricated by the combination of block copolymer self-assembly and the non-solvent-induced phase separation (SNIPS) process resulting in isoporous integral asymmetric membranes. Certainly, all these membranes lack thermal and chemical stability limiting the usage of such materials. Within this study, the fabrication of completely cross-linked isoporous integral asymmetric block copolymer membranes is demonstrated by UV cross-linking resulting in chemical and thermal stable ultrafiltration membranes. The UV cross-linking process of PVBCB-b-P4VP (poly(4-vinylbenzocyclobutene)-b-poly(4vinylpyridine)) block copolymer membranes in dependency of irradiation time, intensity, distance between membrane and UV source and the wavelength is investigated. Furthermore, it is shown that the penetration depths can be increased by soaking the membranes in wave-guiding solutions before UV cross-linking is carried out. Moreover, a completely new and easy cross-linking strategy is developed based on isorefractive solvents resulting in thermal and chemically stable membranes that are cross-linked through the whole membrane thickness. Finally, the new cross-linking strategy in isorefractive solutions is transferred to commercial PVDF and PAN-co-PVC polymer membranes paving the way for more stable and sustainable ultrafiltration membranes.
两亲性嵌段共聚物是制备具有等孔整体不对称结构超滤膜的有前途的候选材料。这些膜通常通过嵌段共聚物自组装和非溶剂诱导相分离(SNIPS)工艺相结合来制备,从而得到等孔整体不对称膜。当然,所有这些膜都缺乏热稳定性和化学稳定性,限制了此类材料的使用。在本研究中,通过紫外线交联展示了完全交联的等孔整体不对称嵌段共聚物膜的制备,从而得到化学和热稳定的超滤膜。研究了聚(4-乙烯基苯并环丁烯)-b-聚(4-乙烯基吡啶)(PVBCB-b-P4VP)嵌段共聚物膜在紫外线交联过程中,交联时间、强度、膜与紫外线源之间的距离以及波长对交联效果的影响。此外,研究表明,在进行紫外线交联之前,将膜浸泡在波导溶液中可以增加渗透深度。此外,基于等折射溶剂开发了一种全新且简便的交联策略,可得到在整个膜厚度范围内都交联的热稳定和化学稳定的膜。最后,将等折射溶液中的新交联策略应用于商用聚偏氟乙烯(PVDF)和聚丙烯腈-共-聚氯乙烯(PAN-co-PVC)聚合物膜,为制备更稳定、更可持续的超滤膜铺平了道路。