# US 12,109,541 B2 · Chemically resistant isoporous crosslinked block copolymer structure > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,109,541 B2 - Document ID: US12109541B2 - Status: Granted - Kind: B2 - Application number: 16/772,074 - Filed: 2018-09-19 - Published: 2020-11-19 - Granted: 2024-10-08 - Earliest claimed: 2017-09-19 - Assignees: TeraPore Technologies, Inc. - Applicants: TeraPore Technologies, Inc. - Inventors: Jae C. Cho; Nanetta Pon; Spencer William Robbins; Rachel M. Dorin - Web page: https://patentgrep.com/patent/US12109541B2 ## CPC - B01D 71/80: Block polymers - B01D 67/0006: {by chemical reactions (in-situ polymerisation, polycondensation, cross-linking or reaction for manufacturing composite membranes B01D69/125)} - B01D 67/009: {with wave-energy, particle-radiation or plasma} - C08J 5/18: Manufacture of films or sheets - C08J 9/0061: {characterized by the use of several polymeric components} - B01D 2323/30: Cross-linking - B01D 2323/345: UV-treatment - C08J 2300/10: Polymers characterised by the presence of specified groups, e.g. terminal or pendant functional groups - C08J 2300/20: Polymers characterized by their physical structure - B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28) - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) ## Abstract Isoporous block copolymers of cross-linked structures, and methods of preparing, which are resistant to harsh solvent conditions from organic, acidic or basic materials are disclosed. ## Claims ### Claim 1 A method of preparing a self-assembled multiblock crosslinked polymer material, comprising: a) forming an isoporous structure comprising macropores and mesopores, from a multi-block copolymer material, wherein the multi-block copolymer material comprises polymer chains, wherein polymer chain comprises a first distinct block which is a poly(4-vinylpyridine); and wherein the forming includes allowing the multi-block copolymer material to self assemble into a bulk layer having a thickness of 2 microns to 500 microns and a second layer having a thickness of 5 nm to 500 nm, wherein the bulk layer comprises macropores having a size of 200 nm to 100 microns, wherein the second layer comprises mesopores having a size of 1 nm to 200 nm, and wherein a portion of macropores and/or mesopores are isoporous; and b) then crosslinking a portion of the first distinct block with a second distinct block which is a poly(4-vinylpyridine); wherein the first and second distinct blocks are on different polymer chains; and wherein the crosslinking agent is selected from the group consisting of (a) a molecule having two α,β-unsaturated carbonyl groups, bonded through their respective β-carbons, to a C1-C12 unsaturated or saturated carbon chain; and (b) a molecule having one α,β-unsaturated carbonyl group bonded from the β carbon to a C1-C12 unsaturated or saturated carbon chain comprising a CH2—I group. ### Claim 2 A self-assembled multi-block cross-linked polymer material, comprising polymer chains, wherein each polymer chain comprises distinct blocks, wherein a portion of a first distinct block is a poly(4-vinylpyridine), wherein the portion of the first distinct block is crosslinked to a poly(4-vinylpyridine) on a second distinct block on a different polymer chain, wherein the cross-linking agent is selected from the group consisting of (a) a molecule having two α,β-unsaturated carbonyl groups bonded from their respective beta carbons to a C1-C12 unsaturated or saturated carbon chain; and; (b) a molecule having an α,β-unsaturated carbonyl group bonded from the β carbon to a C1-C12 unsaturated or saturated carbon chain comprising a CH2—I; wherein the first distinct block and second distinct block are on different polymer chains; wherein the self-assembled multi-block cross-linked polymer material has a bulk layer having a thickness of 2 microns to 500 microns and a second layer of thickness of 5 nm to 500 nm; wherein the bulk layer comprises macropores having a size of 200 nm to 100 microns; and wherein the second layer comprises mesopores having a size of 1 nm to 200 nm; and wherein at least a portion the macropores and/or a portion of the mesopores are isoporous and wherein the self-assembled multi-block cross-linked polymer material is resistant to non-aqueous liquid. ### Claim 3 (depends on 2) A pleated pack, flat sheets in a crossflow cassette, a spiral wound module, hollow fiber, a hollow fiber module, or a sensor comprising the material of claim 2. ### Claim 4 (depends on 2) The material of claim 2, wherein the material further comprises a porous support onto which the material is self-assembled. ### Claim 5 (depends on 2) The material of claim 2, wherein the material is formed into a three-dimensional structure. ### Claim 6 (depends on 2) The material of claim 2, wherein both the macropores of the bulk layer and the mesopores of the second layer are crosslinked. ### Claim 7 (depends on 2) The material of claim 2, wherein the at least two polymer chains comprise poly(isoprene)-b-(styrene)-b-(4-vinylpyridine) (ISV). ### Claim 8 (depends on 2) The material of claim 2, wherein the material is used as a separation media, or as a fabric. ### Claim 9 (depends on 2) The material of claim 2, wherein the cross-linked polymer material exhibits increased resistance to harsh media compared to the uncross-linked material. ### Claim 10 (depends on 2) The material of claim 2, wherein the cross-linked polymer material exhibits increased resistance to temperature compared to the uncross-linked material. ### Claim 11 (depends on 1) The method of claim 1, wherein the self-assembled multi-block cross-linked polymer material is formed by a) dissolving the multi-block polymer in at least one chemical solvent to form a polymer solution; b) dispensing the polymer solution onto a substrate or mold, or through a die or template; c) removing of at least a portion of chemical solvent from the dispensed polymer solution; d) exposing the remaining polymer solution to a non-solvent causing precipitation of at least a portion of the polymer; and e) exposing the precipitated multiblock polymer to a cross-linking agent. ### Claim 12 (depends on 11) The method of claim 11, wherein the polymer solution is dispensed through a die. ### Claim 13 (depends on 11) The method of claim 11, wherein the multi-block polymer comprises at least one block comprising at least one aromatic ring that crosslinks upon UV radiation exposure. ### Claim 14 (depends on 13) The method according to claim 13, wherein the at least one block comprising at least one aromatic ring that crosslinks upon UV radiation exposure crosslinks in the presence of a UV-activated radical initiator.