Physical, Electrochemical, and Solvent Permeation Properties of Amphiphilic Conetwork Membranes Formed through Interlinking of Poly(vinylidene fuoride)-Graft-Poly[(2-dimethylamino)ethyl Methacrylate] with Telechelic Poly(ethylene glycol) and Small Molecular Weight Cross-Linkers Anuradha, Anupam Das, Sandip Pal, and Suresh K. Jewrajka* Cite This: Langmuir 2022, 38, 15340-15352 Read Online ACCESS Metrics & More Article Recommendations * sı Supporting Information ABSTRACT: We report the preparation of dense and porous amphiphilic conetwork (APCN) membranes through the covalent interconnection of poly(vinylidene fuoride)- graft-poly[(2-dimethylamino)ethyl methacrylate] (PVDF-g-PDMAEMA) copolymers with telechelic poly(ethylene glycol) (PEG) or α,α-dichloro-p-xylene (XDC). The dense APCN membranes exhibit varying solvent swelling and mechanical properties depending on the compositions and overall crystallinity. The crystallinity of both PVDF (20−47%) and PEG (9−17%) is signifcantly suppressed in the dense APCNs prepared through the interconnection of PVDF-g-PDMAEMA with reactive PEG as compared to the APCN membranes (48−53%) prepared with XDC as well as mechanical blend of PVDF-g-PDMAEMA plus nonreactive PEG. The dense APCN membranes exhibit a good transport number of monovalent ions and ionic conductivity. The APCN membrane interconnected with PEG and containing binary ionic liquids exhibits a room-temperature lithium ion conductivity of 0.52 mS/cm. On the other hand, APCN ultrafltration (UF) membranes exhibit organic solvent-resistant behavior. The UF membrane obtained by interconnecting PVDF-g-PDMAEMA with telechelic PEG shows low protein fouling propensity, higher hydrophilicity, and water fux as compared to membranes prepared using XDC as the interconnecting agent. The signifcant efect of the covalent interconnection of the amphiphilic graft copolymers with telechelic PEG or XDC on the overall properties provides a good opportunity to modulate the properties and performance of APCN membranes. ■ INTRODUCTION Amphiphilic conetworks (APCNs) have attracted tremendous attention in the feld of soft contact lens, 1,2 drug delivery, 2−8 tissue engineering, 9,10 and immunoisolation membrane. 11 APCNs are used as a template for making nanohybrids, 12 super-absorbent gels for organic solvents, 13 and selective swelling materials. 14 APCN and amphiphilic materials are also used for the construction of electrodialysis, 15, 16 thermosensitive, 17 chiral separation, 17,18 and fuel cell 19,20 membranes. Specially designed APCN matrices were used as gas sensors, 21 biosensors, 22 and carriers of lipase in organic solvent. 23 APCNs with a fuorophilic phase showed nanophase morphology and varying solvent swelling depending on the composition. 24 APCN-based coatings enhance antifouling and antimicrobial behaviors of the surfaces. 25, 26 The wide applicability of APCNs is attributed to their swelling in both polar and nonpolar solvents, 27 nanophase morphology, 24,28,29 solubilizing ability of both hydrophobic and hydrophilic guest molecules, and good mechanical properties even in a swollen state. 30,31 PVDF is a high-performance polymer applied for the preparation of membranes, 32,33 coating materials, 34 capacitive energy storage applications, 35 and scafold for bone regener- ation. 36 Hence, construction of APCNs from a commercially available PVDF may be an attractive option for incorporating specifc properties by retaining the properties of the parent polymer. Graft copolymers of commercially available PVDF and PEG, 37 poly[(2-dimethylamino)ethyl methacrylate] (PDMAEMA), 38 poly(acrylic acid), 39 and poly(N-isopropyl acrylamide) (PNIPAM) 40 were reported for the construction of water fltration membranes. Graft copolymers of PVDF and PDMAEMA (PVDF-g-PDMAEMA) were applied for the preparation of pH- and temperature-responsive membranes 38 and glue. 41 Nevertheless, there are very few reports on PVDF- based APCNs. Apostolides et al. synthesized APCNs by cross- linking benzaldehyde group-terminated four-arm star PVDF and benzaacylhydrazide group-terminated four-arm star PEG. The PVDF-PEG-based APCN containing binary ionic liquid Received: September 16, 2022 Revised: November 15, 2022 Published: December 2, 2022 Article pubs.acs.org/Langmuir © 2022 American Chemical Society 15340 https://doi.org/10.1021/acs.langmuir.2c02553 Langmuir 2022, 38, 15340−15352 Downloaded via UNIV OF HYDERABAD on December 16, 2022 at 18:54:42 (UTC). See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.