Tailoring Thermoresponsive Polymer Architecture to Enhance Antifouling and Fouling Reversibility of Membranes.

Cleaning a fouled membrane using warm water, instead of commonly used fouling control chemicals, is an approach advocated in resource-limited settings, where small-scale membrane filtration is used to provide clean water. Thermoresponsive polymers coated onto membranes undergo a conformational change across their lower critical solution temperature (LCST), enabling foulant removal during such temperature-swing cleaning. However, their intrinsic hydrophobicity above the LCST poses a fundamental material challenge. In this study, we examine how thermoresponsive polymers can be optimally copolymerized with hydrophilic polymers by precisely manipulating monomer arrangement of thermoresponsive N-isopropylacrylamide and hydrophilic 2-[2-(2-methoxyethoxy)ethoxy]ethyl acrylate. We successfully grafted these copolymers with different monomer arrangements onto poly(ether sulfone) ultrafiltration membranes while maintaining other polymer characteristics, such as the degree of polymerization and grafting density, constant. We found that placing hydrophilic polymer blocks at the outermost surface above the thermoresponsive polymer blocks is critical to achieving high surface hydrophilicity while preserving the thermoresponsive functionality. We demonstrate enhanced fouling resistance and efficient temperature-swing cleaning with optimized copolymer design based on their interaction with bovine serum albumin during static adsorption, filtration, and cleaning processes. These findings emphasize the importance of accurately tailoring the polymer architecture to enable more efficient filtration with reduced fouling and the capability to effectively clean the fouled membrane by simply using warm water.