In situ pegylated (PEGylated) microporous membranes have been extensively reported using poly(ethylene glycol) (PEG)-based polymers as blending additives. Alternatively, free standing PEGylated polysulfone (PSf) membranes with excellent hydrophilicity and antifouling ability were directly fabricated from polysulfone/poly(ethylene glycol) methyl ether methacrylate (PSf/PEGMA) solutions after in situ cross-linking polymerization without any treatment via vapor induced phase separation (VIPS) process for the first time. The microstructures and performances of the resulting membranes shifted regularly by adjusting exposure time of the liquid film in humid air. With increasing exposure time, plenty of worm-like networks formed and distributed on membrane surfaces, meanwhile cross-sectional morphology changed from asymmetric finger-like microporous structure to symmetric cellular-like structure, resulting in better mechanical stability. As the exposure time raised from 0 to 5 min, the surface coverage of carboxyl groups increased from ∼1.1 to 4.0 mol%, leading to the decrease in water contact angle from ∼63 to 27° and the increase in water flux from ∼110 to 512 L m⁻² h⁻¹. In addition, at prolonged exposure time, increasing hydrophilic PEG chains migrated to membrane surfaced and repelled the adsorption and deposition of protein, resulting in better antifouling ability. The findings of this study offer a facile and high efficient strategy for flexible design and fabrication of the in situ PEGylated membranes with desirable structures and performances in large scale.

使用基于聚乙二醇（PEG）的聚合物作为共混添加剂，已广泛报道了原位聚乙二醇化（PEG化）微孔膜。或者，在原位后由聚砜/聚乙二醇甲基醚甲基丙烯酸酯（PSf / PEGMA）溶液直接制备具有优异的亲水性和防污能力的自立式聚乙二醇化聚砜（PSf）膜。无需任何处理即可通过蒸汽诱导相分离（VIPS）工艺进行交联聚合。通过调节液膜在潮湿空气中的暴露时间，所得膜的微观结构和性能会定期发生变化。随着暴露时间的增加，大量的蠕虫状网络形成并分布在膜表面，同时横截面形态从不对称的手指状微孔结构变为对称的细胞状结构，从而获得了更好的机械稳定性。随着暴露时间从0到5分钟的增加，羧基的表面覆盖率从约1.1摩尔％增加到4.0 mol％，导致水接触角从约63降低到27°，水通量从约110增长到110 mol。 512立方米^-2 小时^-1。另外，在延长的暴露时间下，增加的亲水性PEG链迁移到膜表面并排斥蛋白质的吸附和沉积，从而产生了更好的防污能力。这项研究的发现为灵活设计和制造具有所需结构和大规模性能的原位聚乙二醇化膜提供了一种简便而高效的策略。