Physical, Electrochemical, and Solvent Permeation Properties of Amphiphilic Conetwork Membranes Formed through Interlinking of Poly(vinylidene fluoride)-Graft-Poly[(2-dimethylamino)ethyl Methacrylate] with Telechelic Poly(ethylene glycol) and Small Molecular Weight Cross-Linkers

Abstract

We report the preparation of dense and porous amphiphilic conetwork (APCN) membranes through the covalent interconnection of poly(vinylidene fluoride)-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 significantly 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 ultrafiltration (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 flux as compared to membranes prepared using XDC as the interconnecting agent. The significant effect 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.

Model Amphiphilic Polymer Conetworks in the Bulk: Dissipative Particle Dynamics Simulations of Their Self-Assembly and Mechanical Properties

“…However, the presence of the cross-links or/and the nonideal structure of the APCN building blocks lead to the formation of frustrated/distorted morphologies, with much less regularity than the morphologies observed with (non-cross-linked) linear block copolymers . Thus, the APCN electron micrographs or atomic force micrographs usually exhibit morphologies with spheroidal domains, and the corresponding small-angle X-ray scattering (SAXS) or small-angle neutron scattering (SANS) profiles present a single broad peak. − ,,− However, recent synthetic developments, involving sparser and more regular cross-linking, e.g., end-linking, as well as the utilization of near-ideal building blocks (well-defined linear or star polymers), resulted in APCN nanophase-separated morphologies of high regularity, e.g., wavy lamellae, and SAXS and SANS profiles with a number of higher order peaks. , The experimental recording of these more regular morphologies in self-assembled APCNs renders their modeling/simulation more worthwhile. In particular, current state-of-the-art simulations and self-consistent field theories (SCFT) very successfully reproduce the experimentally observed morphologies of linear diblock melts and are, consequently, expected to accurately predict the morphologies formed by APCNs comprising well-defined building blocks .…”

Structurally Heterogeneous Amphiphilic Conetworks of Poly(vinyl imidazole) Derivatives with Potent Antimicrobial Properties and Cytocompatibility

“…This class of crosslinked networks swells both in water and organic solvents and maintains cocontinuous morphology. Structural investigation revealed that the components in an APCN matrix form nanophase morphology. − APCNs find applications in controlled release of drugs, − immunoisolatory devices, , ion exchange membranes, , Li ion transport membranes, specific protein binding matrices, antibiofouling/antifouling coating, − and controlled release of antimicrobial agents. , APCNs are capable of activating biocatalysts in organic solvents …”