# US 10,865,516 B2 · Waterproof and breathable, porous membranes > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,865,516 B2 - Document ID: US10865516B2 - Status: Granted - Kind: B2 - Application number: 16/060,067 - Filed: 2016-12-06 - Published: 2018-12-27 - Granted: 2020-12-15 - Earliest claimed: 2015-12-08 - Assignees: ETH Zurich - Applicants: ETH Zurich - Inventors: Wendelin Jan Stark; Mario Stucki - Web page: https://patentgrep.com/patent/US10865516B2 ## CPC - D06N 3/0052: {obtained by leaching out of a compound, e.g. water soluble salts, fibres or fillers; obtained by freezing or sublimation; obtained by eliminating drops of sublimable fluid} - B01D 67/003: {by selective elimination of components, e.g. by leaching} - C08J 5/18: Manufacture of films or sheets - C08J 9/26: by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out - C08J 2375/08: from polyethers - D06N 2209/123: Breathable - D06N 2209/128: Non-permeable - D06N 2211/10: Clothing - D06N: WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR - 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 The invention relates to manufacturing processes for waterproof and breathable porous polymer membranes by coating a substrate with a dispersion comprising polymer, coated particles and diluent and removing the particles by dissolution, wherein the particles are made of organic salts, metal salts or metal oxides and the coating material is selected from carboxylic acids and alkoxy silanes. The invention further relates to dispersions to obtain such membranes, to polymer membranes obtained, to shaped articles containing such membranes; to the use of such membranes, shaped articles and intermediates. ## Claims ### Claim 1 A method of manufacturing a porous polymer membrane having a pore size of 5-1000 nm, comprising the steps of a) providing a dispersion comprising one or more diluents in an amount of at least 40 wt. %, one or more polymers dissolved therein, one or more coated particles dispersed therein, optionally one or more additives dissolved therein whereby the ratio (wt %) of polymer: coated particles is in the range of 2:1 to 0.01:1, and whereby the coated particles are pre-manufactured, are selected from the group consisting of organic salts, metal salts, metal oxides and combinations thereof, the coating material is selected from the group of carboxylic acids, aryl-alkoxy-silanes alkyl-aryl-alkoxy-silanes and alkyl-alkoxy-silanes, and have a particle size in the range of 5-1000 nm; b) coating a substrate with said dispersion; c) optionally subjecting the obtained material to a drying step; d) optionally subjecting the thus obtained material to a polymerisation or cross-linking step; e) removing said one or more particles by a dissolution step; f) optionally removing the obtained polymer membrane from said supporting material. ### Claim 2 (depends on 1) The method of claim 1, wherein said method does not involve a phase separation step; and/or one or more of said steps a) to f), are performed continuously; and/or said coating step (b) is selected from the group consisting of spraying, painting, roll-to-roll processes, and dip-coating; and/or said step (f) is performed prior to step (e); and/or said dissolution (e) is performed in 90 min or less. ### Claim 3 (depends on 1) The method according to claim 1, wherein said metal salts are selected from the group consisting of carbonates, hydrogencarbonates, sulphates, halogenides, nitrates and phosphates and said metal oxides are selected from ZnO and MgO; and/or said coating material is selected from the group of natural fatty acids, particularly stearic acid; and/or said diluents are selected from the group consisting of organic solvents with a b.p. below 200° C.; and/or said polymers are selected from the group of soluble polymers, pre-polymers that can be polymerized and pre-polymers that can be cross-linked; and/or said supporting material is selected from the group consisting of polymers, metals, ceramics and paper, each coated or uncoated. ### Claim 4 (depends on 1) The method according to claim 1, wherein said soluble polymers/pre-polymers that can be polymerized/prepolymer that can be cross-linked are selected from the group consisting of polysulfones, polyethersulfones, polycarbonates, polystyrenes, polyacrylates, polysiloxanes, polyarylates, polyurethanes, ethyl-vinylacetates, artificial and natural rubbers, polyesters, polyether, polyaryletherketones, polyamides, polyacrylates, polyarylates, cyclo-olefin-copolymers and polyolefins. ### Claim 5 (depends on 1) The method according to claim 1, wherein said polymer membrane: has a thickness of 0.01-1000 μm; and/or has a porosity of 10-90%; and/or has a poremouth size of 5-2000 nm; and/or has a water column (WC) of at least 4.8 m; and/or has a water vapour transmission rate of at least 500 g/m2 per day (WVTR, measured according to the ASTM Standard E96 B); and/or has a water contact angle of at least 50°. ### Claim 6 (depends on 1) The method according to claim 1, wherein said dispersion contains: from 40 to 99 wt.-% diluents; from 1 to 20 wt.-% polymers; from 0.5 to 40 wt.-% coated particles; and from 0 to 5 wt.-% additives. ### Claim 7 (depends on 1) The method according to claim 1, wherein said coated particles have an average size of 5-500 nm; and/or the coating amounts to 1-10 wt % of the coated particle; and/or were coated under conditions in which the coating material does not alter the particle size or particle shape. ### Claim 8 (depends on 2) The method according to claim 2, wherein all of steps a) to f) are performed continuously. ### Claim 9 (depends on 2) The method according to claim 2, wherein said metal salts are selected from the group consisting of carbonates, hydrogencarbonates, sulphates, halogenides, nitrates and phosphates and said metal oxides are selected from ZnO and MgO; and/or said coating material is selected from the group of natural fatty acids, particularly stearic acid; and/or said diluents are selected from the group consisting of organic solvents with a b.p. below 200° C.; and/or said polymers are selected from the group of soluble polymers, pre-polymers that can be polymerized and pre-polymers that can be cross-linked; and/or said supporting material is selected from the group consisting of polymers, metals, ceramics and paper, each coated or uncoated.