Abstract In this work, poly(ethylene oxide)-block-poly(methyl methacrylate) (PEO-b-PMMA) diblock copolymers were established as functional additive for polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes, originally with the intention to increase their hydrophilicity and thereby decrease fouling. Additionally, however, it was found that copolymer micelles can be induced by complexing the PEO block of PEO-b-PMMA with specific metal salts. The formation of micelles as function of specific solution compositions was observed in dynamic light scattering and rheology experiments; the formation of PEO-metal ion complexes was shown via proton nuclear magnetic resonance (1H NMR) spectroscopy. Integration of micelle-forming compositions into typical PVDF-based casting solutions for UF membranes could lead to a higher surface porosity and a more regular barrier pore structure through microphase separation during the nonsolvent induced phase separation process used for membrane preparation. It was found that membranes containing small amounts of PEO-b-PMMA show a significantly higher permeance than membranes made from an otherwise equal casting solution without the copolymer, while maintaining the solute rejection properties. By using different types and amounts of metal salts to complex the PEO block it was possible to tailor the molecular weight cut-off of the membranes between 30 kDa and 110 kDa. Fouling studies in lab-scale cross-flow filtration cells showed an increased relative flux recovery compared to membranes without the functional copolymer additive. The results of this study are relevant because small fractions of a tailored diblock copolymer and metal salt as additives allow tailoring the barrier and separation properties at significantly higher overall performance within an otherwise unchanged membrane manufacturing process.

中文翻译：

---

聚（环氧乙烷）-嵌段-聚（甲基丙烯酸甲酯）二嵌段共聚物作为具有定制分离性能的聚（偏二氟乙烯）超滤膜的功能添加剂

摘要 在这项工作中，聚（环氧乙烷）-嵌段-聚（甲基丙烯酸甲酯）（PEO-b-PMMA）二嵌段共聚物被建立作为聚偏二氟乙烯（PVDF）超滤（UF）膜的功能添加剂，最初是为了增加它们的亲水性，从而减少污垢。然而，此外，还发现可以通过将 PEO-b-PMMA 的 PEO 嵌段与特定金属盐络合来诱导共聚物胶束。在动态光散射和流变学实验中观察到胶束的形成作为特定溶液组成的函数；PEO-金属离子络合物的形成通过质子核磁共振（1H NMR）光谱显示。在用于膜制备的非溶剂诱导相分离过程中，通过微相分离，将形成胶束的组合物整合到典型的基于 PVDF 的超滤膜浇铸溶液中，可以导致更高的表面孔隙率和更规则的阻隔孔结构。发现含有少量 PEO-b-PMMA 的膜比由没有共聚物的其他相同流延溶液制成的膜显示出显着更高的渗透性，同时保持溶质排斥特性。通过使用不同类型和数量的金属盐来络合 PEO 嵌段，可以将膜的截留分子量调整为 30 kDa 和 110 kDa 之间。实验室规模的错流过滤池中的污垢研究表明，与不含功能性共聚物添加剂的膜相比，相对通量回收率增加。这项研究的结果是相关的，因为小部分的定制二嵌段共聚物和金属盐作为添加剂允许在原样不变的膜制造过程中以显着更高的整体性能定制阻隔和分离性能。