The reversible formation and cleavage of disulfide bonds under physical/chemical stimuli make it a valuable motif in constructing dynamically cross-linked materials. In the present work, the block copolymer bearing pendent dithiolanes was synthesized and fabricated into isoporous membranes by the combination of self-assembly and nonsolvent-induced phase separation strategy. The cross-linking within the membrane was realized by the thiol-initiated ring-opening cascades of cyclic disulfides. Successful formation of disulfide bond networks within the isoporous membranes was proved by the Raman spectra, UV–vis diffuse reflectance spectroscopy, differential scanning calorimetry, and rheological analysis. The cross-linking in membranes was further demonstrated by the notably improved toughness and obviously enhanced swelling resistance to acid/alkaline solution as well as organic solvents. Importantly, the cross-linked isoporous membranes were fully dissolvable in solution containing dithiothreitol, which enabled the complete cleavage of disulfide bonds and successful recovery of the block copolymer that was able to be repeatedly fabricated into isoporous membranes with pore sizes identical to membranes prepared from the freshly synthesized copolymer. Our results indicate that dynamically cross-linked isoporous membranes with improved durability and good recyclability can be custom-made by simply incorporating active dithiolane moieties into self-assembling block copolymers.

中文翻译：

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带有二硫戊环侧基的可回收嵌段共聚物制备的可逆交联等孔膜

在物理/化学刺激下二硫键的可逆形成和断裂使其成为构建动态交联材料的有价值的基序。在目前的工作中，通过自组装和非溶剂诱导相分离策略的结合，合成了带有侧链二硫戊环的嵌段共聚物并将其制成等孔膜。膜内的交联是通过硫醇引发的环状二硫化物的开环级联实现的。拉曼光谱、紫外可见漫反射光谱、差示扫描量热法和流变分析证明了等孔膜内二硫键网络的成功形成。膜的交联进一步证明了膜的韧性显着提高，并且对酸/碱溶液以及有机溶剂的抗溶胀性明显增强。重要的是，交联的等孔膜完全溶解在含有二硫苏糖醇的溶液中，这使得二硫键完全断裂并成功回收嵌段共聚物，该嵌段共聚物能够重复制造成等孔膜，其孔径与由二硫苏糖醇制备的膜相同。新合成的共聚物。我们的结果表明，通过简单地将活性二硫戊环部分掺入自组装嵌段共聚物中，可以定制具有改进的耐用性和良好可回收性的动态交联异孔膜。