US20150291843A1 - Solvent resistant polymeric membranes - Google Patents
Solvent resistant polymeric membranes Download PDFInfo
- Publication number
- US20150291843A1 US20150291843A1 US14/386,909 US201314386909A US2015291843A1 US 20150291843 A1 US20150291843 A1 US 20150291843A1 US 201314386909 A US201314386909 A US 201314386909A US 2015291843 A1 US2015291843 A1 US 2015291843A1
- Authority
- US
- United States
- Prior art keywords
- group
- membrane
- radiation curable
- curable composition
- hydrophobic monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 142
- 239000002904 solvent Substances 0.000 title claims description 45
- 230000005855 radiation Effects 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 28
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 239000004642 Polyimide Substances 0.000 claims abstract description 23
- 229920001721 polyimide Polymers 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 150000003254 radicals Chemical class 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 10
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000002033 PVDF binder Substances 0.000 claims abstract description 7
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical group OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims abstract description 6
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- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims abstract description 6
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- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 3
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- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000009285 membrane fouling Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- UYDLBVPAAFVANX-UHFFFAOYSA-N octylphenoxy polyethoxyethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCO)C=C1 UYDLBVPAAFVANX-UHFFFAOYSA-N 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005373 pervaporation Methods 0.000 description 1
- 238000000614 phase inversion technique Methods 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/00091—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching by evaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D181/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Coating compositions based on polysulfones; Coating compositions based on derivatives of such polymers
- C09D181/06—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Definitions
- the present invention relates to solvent resistant polymeric membranes and to methods for manufacturing these membranes.
- Polymeric membranes are widely used in separation technologies and the field of application is continuously expanding towards ever more demanding applications.
- the use of harsh solvents in different applications requires highly solvent resistant polymeric membranes.
- Conventional polymeric membranes using polymers such as polyimides and polyaryl sulfones are not sufficiently resistant towards heat and harsh solvents.
- Cross-linking is a process during which two or more polymer chains are connected to each other by joints, called cross-links.
- Cross-linking can be physical with the cross-links being part of an intrinsic physical property of a crystalline, a semi-crystalline polymer or block copolymer, where crystallites or domains of the dispersed phase act as physical cross-links.
- polymeric membranes having physical cross-links exhibit poor solvent resistance.
- WO2007/125367 A1 discloses membranes formed from polyimides by phase inversion which are then crosslinked by addition of amine crosslinking agents that react with the imide groups of the polyimide creating amide bonds. The authors claim the membrane to be stable in DMF, NMP, DCM and 1,4-dioxane. A similar approach is disclosed by WO2008/138078 A1 (KU Leuven).
- WO2010/111755 A2 discloses a simplified method for the preparation of crosslinked polyimide nanofiltration membranes, by adding the cross-linking agent to the polyimide polymer cast solution or to the phase inversion coagulation medium.
- UV irradiation has been used in membrane technology for modifying the surface of a membrane in order to enhance the performance of the membrane such as permeability and selectivity.
- U.S. Pat. No. 5,468,390 discloses a process for modifying the surface of aryl polysulfone membranes by placing an aryl polysulfone membrane into the presence of a hydrophilic vinyl monomer dissolved in a solvent and exposing it then to ultraviolet light. The resulting ultrafiltration and microfiltration membranes exhibit low fouling characteristics.
- Membrane fouling is a process where particles deposit onto a membrane surface or into membrane pores in a way that degrades the membrane's performance.
- US2003209487 A1 discloses a method for modifying a polyethersulfone membrane by immersing the membrane in a monomer solution and exposing it to UV irradiation having a wavelength of 280 nm to 300 nm.
- U.S. Pat. No. 5,885,456 discloses a method for the preparation of a UF or MF membrane comprising a blend of a polysulfone polymer and a graft copolymer of the polysulfone polymer and a polymerized monomer.
- the graft copolymer membrane is obtained by casting a solution comprising polyethersulfone and the polymerizable monomer, and subsequently exposing the cast membrane to UV irradiation.
- the membrane obtained after coagulation exhibits a highly hydrophilic surface.
- U.S. Pat. No. 5,079,272 discloses a method for the preparation of a porous membrane formed from an interpenetrating polymer network of a hydrophobic polymer and a polymerized and crosslinked hydrophilic monomeric composition.
- a solution of the polymer and monomeric composition is cast, exposed to ultraviolet radiation, coagulated and dried.
- the resulting dried membrane is annealed in order to render its surface hydrophilic.
- UV irradiation has been used in the above described membrane technology to synthesize an interpenetrating polymer network with a hydrophilic surface, as well as to synthesize copolymer membranes.
- a hydrophilic monomer is added to the dope solution.
- the dope solution is cast, UV irradiated and finally coagulated to obtain a membrane.
- Preferred embodiments of the present invention provide a method for manufacturing polymeric membranes exhibiting improved solvent resistance, more particularly with a preparation method compatible with roll to roll coating. In the latter, a continuous production of membranes integrated in a coating line becomes possible.
- Preferred embodiments of the present invention provide highly solvent resistant polymeric membranes without affecting the filtration performance.
- actinic radiation means electromagnetic radiation capable of initiating photochemical reactions.
- alkyl means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
- the radiation curable composition according to a preferred embodiment of the present invention for manufacturing a polymeric membrane including: a) a membrane polymer selected from the group consisting of a polysulfone (PSU), a polyether sulfone (PES), a polyether etherketone (PEEK), a polyvinylchloride (PVC), a polyacrylonitrile (PAN), a polyvinylidene fluoride (PVDF), a polyimide (PI), a polyamide (PA) and copolymers thereof; b) a hydrophobic monomer or oligomer having at least two free radical polymerizable groups, preferably at least three free radical polymerizable groups, and most preferably at least four free radical polymerizable groups which are independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group,
- the membrane polymer is selected from the group consisting of a polysulfone, a polyether sulfone, a polyimide and a polyetheretherketone.
- the radiation curable composition according to a preferred embodiment of the present invention is used to manufacture a polymeric membrane with an improved solvent resistance.
- the weight ratio between the polymer and the hydrophobic monomer or oligomer is between 10 to 1 and 1 to 1.
- the weight ratio between the polymer and the at least one photoinitiator is between 12 to 1 and 1 to 1.
- the membrane polymer is selected from the group consisting of a polysulfone (PSU), a polyether sulfone (PES), a polyether etherketone (PEEK), a polyvinylchloride (PVC), a polyacrylonitrile (PAN), a polyvinylidene fluoride (PVDF), a polyimide (PI), a polyamide (PA) and copolymers thereof.
- PSU polysulfone
- PES polyether sulfone
- PEEK polyether etherketone
- PVC polyvinylchloride
- PAN polyacrylonitrile
- PVDF polyvinylidene fluoride
- PI polyimide
- PA polyamide
- the membrane polymer is preferably selected from the group consisting of a polysulfone, a polyether sulfone, a polyimide and a polyether etherketone; and even more preferably selected from the group consisting of a polysulfone and a polyether sulfone.
- the membrane polymer is a polysulfone or a copolymer thereof having repeating units according to Formula (I):
- X and Y represent an oxygen.
- Ar1 to Ar4 represent a substituted or unsubstituted 1,4-phenylene group, an unsubstituted 1,4-phenylene group being particularly preferred.
- EP0997182 A ASAHI MEDICAL
- EP1634610 A TOYO BOSEKI
- U.S. Pat. No. 6,045,899 USF
- US2006228483 A AQUASOURCE
- EP1733784 A TOYO BOSEKI
- EP1007195 A USF
- US2006076288 A 3M
- EP1609522 A MILLIPORE
- Preferred commercially available polysulfones and polyethersulfones are the UdelTM types supplied by Solvay, more specifically the P-1835, P-3500 LCD, P-3500 LCD MB3, P-3500 LCD MB7 and P-3500 LCD MB8 grades, polysulfone P-1700 LCD being most preferred.
- the organic solvent of the radiation curable composition is capable of dissolving the polymer and the hydrophobic monomer or oligomer. If present, the photoinitiator and the co-initiator is preferably also dissolved by the organic solvent.
- the organic solvent may also be a mixture of solvents as long as they are capable of dissolving the polymer and the hydrophobic monomer or oligomer.
- Preferred organic solvents are on or more organic solvents selected from the group selected of dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), tetrahydrofuran (THF), 1,4-dioxane, alcohols and ketones.
- DMF dimethylformamide
- DMAc dimethylacetamide
- DMSO dimethylsulfoxide
- NMP N-methylpyrrolidone
- NEP N-ethylpyrrolidone
- THF tetrahydrofuran
- 1,4-dioxane 1,4-dioxane
- the organic solvent is most preferably a water-miscible organic solvent.
- the coagulation bath includes one or a mixture of organic solvents and preferably also a surfactant, e.g. TritonTM X-100 (octylphenoxy-polyethoxyethanol).
- a surfactant e.g. TritonTM X-100 (octylphenoxy-polyethoxyethanol).
- TritonTM X-100 octylphenoxy-polyethoxyethanol
- the hydrophobic monomer or oligomer of the radiation curable composition has at least two, preferably at least three and most preferably at least four free radical polymerizable groups independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group, a maleate group, a fumarate group, an itaconate group, and a maleimide group.
- the free radical polymerizable groups of the hydrophobic monomer or oligomer are selected from the group consisting of an acrylate group and a methacrylate group, an acrylate group being the most preferred.
- the hydrophobic monomer or oligomer of the radiation curable composition needs to be hydrophobic because hydrophilic monomers, such as acrylic acid and 2-hydroxyethyl-methacrylate, have a too high solubility in water whereby they are largely removed by the phase inversion step during the manufacturing of polymeric membranes and no longer available in the subsequent radiation curing step for improving the solvent resistance of the polymeric membrane.
- hydrophilic monomers such as acrylic acid and 2-hydroxyethyl-methacrylate
- the hydrophobic monomer or oligomer has a solubility in water at 20° C. of less than 20 mg/l, preferably less than 10 mg/l.
- Particularly preferred hydrophobic monomers and oligomers are pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexacrylate, ethoxylated dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol pentaacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol pentaacrylate, propoxylated dipentaerythritol pentaacrylate, propoxylated dipentaerythritol
- the hydrophobic monomers and oligomers preferably have a molecular weight of less than 5000 Da, more preferably less than 3000 Da.
- the majority of the photoinitiators can be classified as Norrish type I or Norrish type II initiators.
- Norrish type I initiators generate initiating radicals by ⁇ -cleavage upon exposure to UV radiation.
- Norrish type II initiators abstract a hydrogen from a second molecule, a so called coinitiator, upon exposure to UV light.
- the initiating radicals are formed on the coinitiator.
- the radiation curable composition according to the present invention preferably includes at least one photoinitiator.
- the at least one photoinitiator preferably has an absorption maximum at a wavelength above 320 nm, more preferably above 340 nm.
- bathochromic photoinitiators are thioxanthone photoinitiators, carbazole based photoinitiators and acyl phosphineoxide based photoinitiators, acyl phosphine based initiators being particularly preferred.
- the at least one photoinitiator is selected from the group consisting of a thioxanthone photoinitiator and an acyl phosphineoxide photoinitiator.
- Typical preferred photoinitiators according to the present invention are given below in Table 2 without being limited thereto.
- Coinitiators are preferably selected from aliphatic tertiary amines and dialkylamino substituted aromatic compounds, dialkylamino substituted aromatic compounds being more preferred, 4-dialkylamino benzoic acid esters being the most preferred.
- the radiation curable composition according to a preferred embodiment of the present invention preferably includes a 4-dialkylaminobenzoic acid derivative as coinitiator.
- the polymer to initiator ratio is between 12 to 1 and 1 to 1, more preferably between 10 to 1 and 2 to 1, and most preferably between 8 to 1 and 3 to 1.
- the polymer to coinitiator ratio is between 12 to 1 and 1 to 1, more preferably between 10 to 1 and 2 to 1, and most preferably between 8 to 1 and 3 to 1.
- the radiation curable composition according to a preferred embodiment of the present invention is cast on a porous support.
- the porous support preferably has also a high resistance against organic solvents and other chemicals.
- Preferred porous supports include woven or non-woven materials such as polyester/nylon fabrics, polyphenylene sulphide fabrics, cellulose/polyester fabrics, polytetrafluoroethylene, polyvinyl chloride, Teflon, sintered glass, glass fibres, ceramic supports, and a metal mesh.
- the supporting material is a non-woven fabric, such as polyethylene, polypropylene, a polyethylene/polypropylene blend or a polyester material.
- Preferred porous supports are disclosed in EP0012557 A (ABCOR), U.S. Pat. No. 6,045,899 (USF), WO2007125367 A (IMP INNOVATIONS), US2010181253 A (EVONIK FIBRES), and WO2010111755 A (KU Leuven).
- the supporting material is preferably a polyester support, more preferably a polyethylene terephthalate porous support, such as the NovatexxTM grades available from Freudenberg Filter Technologies.
- the porous support has a thickness of at least 0.10 mm.
- a method for manufacturing a polymeric membrane according to a preferred embodiment of the present invention includes, in order, the steps of:
- the method is preferably performed by roll to roll coating.
- the manufacturing steps are performed under light conditions in which actinic radiation has been substantially or fully excluded, and where necessary cooling of the radiation curable composition is foreseen to prevent build up of heat as much as possible.
- the radiation curable composition is prepared in two steps. First, the polymer is dissolved in a suitable solvent at elevated temperature, usually in the range 50-150° C., preferably in the range 70-90° C.
- the homogeneous polymer solution is cooled down and the hydrophobic monomer or oligomer and optionally a photoinitiator and a co-solvent are added.
- Preferred radiation curable compositions have a polymer concentration ranging from 12 wt % to 30 wt %, preferable from 15 wt % to 25 wt %; the most preferable from 17 wt % to 22 wt % based on the total weight of the radiation curable composition.
- slot and extrusion coating techniques are particularly preferred. Slot and extrusion coating techniques belong to a class of coating methods known as premetered coating in which the thickness of the coated liquid is in principle set by the flow rate of the feed to the die, the width of the web and the speed of the substrate moving past and is independent of other process variables.
- the dope at the impregnation temperature preferably has a viscosity at a shear rate of 1 s ⁇ 1 in the range of 1 to 500 mPa ⁇ s at 20° C.
- the dope at the impregnation temperature preferably has a viscosity at a shear rate of 1 s 1 of greater than 10 3 mPa ⁇ s at 20° C.
- polymeric membranes are prepared by a phase inversion process which allows a controlled transformation of a polymer from solution to the solid state.
- the polymeric solution may be inverted to a solid polymeric membrane by various phase inversion methods which include Liquid Induced Phase Separation (LIPS), where phase inversion is induced by immersion of the cast membrane in a non-solvent (or mixture of solvent and non-solvent), Vapour Induced Phase Separation (VIPS), where the initiating phase inversion medium is a vapour, Evaporation Induced Phase Separation (EIPS), where phase inversion is carried out by controlled evaporation of the solvent, as well as Thermal Induced Phase Separation (TIPS), where the membrane is prepared by thermal precipitation.
- LIPS Liquid Induced Phase Separation
- VIPS Vapour Induced Phase Separation
- EIPS Evaporation Induced Phase Separation
- TIPS Thermal Induced Phase Separation
- Liquid Induced Phase Separation is particularly preferred.
- the polymeric membrane according to a preferred embodiment of the present invention is cured by exposure to actinic radiation, such as ⁇ -rays, electron beam radiation, UV- and visible light.
- actinic radiation is preferably electron beam radiation and/or UV-light, more preferably UV-light.
- Any ultraviolet light source as long as part of the emitted light can be absorbed by the photoinitiator or photoinitiator system, may be applied as a radiation source, such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser and a flash light.
- a radiation source such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser and a flash light.
- UV-light sources dominantly emitting in the UV-A region of the spectrum are particularly preferred.
- the UV-curing dose is preferably in the range from 1 to 20 J/cm 2 ; more preferably from 3-15 J/cm 2 and most preferably from 7 up to 13 J/cm 2 .
- the method for manufacturing a polymeric membrane includes a step e) of conditioning the polymeric membrane by immersion of the cured polymeric membrane in a solution comprising a conditioning agent and a solvent.
- Conditioning of the radiation cured polymeric membrane improves mechanical properties of the membrane, e.g. elasticity, as well as filtration properties, e.g. improved permeability by avoiding pore collapsing in the membrane.
- the conditioning agent is preferably a low volatile organic liquid selected from the group consisting of glycols (polyalkylene glycols more preferably polyethylene glycol or polypropylene glycol), glycerols, mineral oils, synthetic oils, vegetable fats and oils are used.
- the solvent for dissolving the one or more conditioning agents preferably includes one or more alcohols, ketones, hydrocarbons or mixtures thereof.
- the radiation cured membrane is conditioned in a glycerol/isopropanol bath with a glycerol concentration of at least 30% (v/v). In the most preferred embodiment, the radiation cured membrane is conditioned for at least 24 h.
- the polymeric membranes obtained from the methods according to preferred embodiments of the present invention can be used as filtration elements for microfiltration, ultrafiltration, nanofiltration, reverse osmosis, membrane distillation, pervaporation, gas separation, immobilizing biologically active species (e.g. enzyme and biofilm reactors); in membrane contactors e.g. supported liquid membranes, pertraction, water degassing, aeration, humidification (vapour permeation), controlled release; in membrane bioreactors (for permeate withdrawal) and in air conditioning for gas/air cleaning, and other membrane applications, especially those employing (aggressive) organic solvents.
- biologically active species e.g. enzyme and biofilm reactors
- membrane contactors e.g. supported liquid membranes, pertraction, water degassing, aeration, humidification (vapour permeation), controlled release
- membrane bioreactors for permeate withdrawal
- air conditioning for gas/air cleaning, and other membrane applications, especially those employing (aggressive) organic solvents.
- the radiation cured polymeric membranes of the invention especially the polysulfone membranes can be advantageously used in applications requiring solvent resistance, more particularly in separation processes which are performed in aprotic solvents, such as NMP, THF, and DMF.
- aprotic solvents such as NMP, THF, and DMF.
- TPO is 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, a photoinitiator available as DarocurTM TPO from BASF.
- BAPO is bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, a photoinitiator available as IrgacureTM 819 from BASF.
- PSf is polysulfone P-1700 supplied by Solvay and having the following structure:
- PI is a polyimide polymer available as MatrimidTM 9725 from HUNTSMAN.
- SR285 is tetrahydrofurfuryl acrylate available as SartomerTM SR285 from SARTOMER.
- DEGDA is ethylene glycol diacrylate.
- NovatexxTM 2413 N is a porous PET polyester support having a weight of 100 g/m 2 and an air permeability of 300 l/m 2 s at 200 Pa, available from FREUDENBERG FILTER TECHNOLOGIES.
- NovatexxTM 2481 is a porous PET/PBT polyester support having a weight of 100 g/m 2 and an air permeability of 125 l/m 2 s at 200 Pa, available from FREUDENBERG FILTER TECHNOLOGIES.
- Rose Bengal is 4,5,6,7-tetrachloro-2′,4′,5′,7′-tetraiodofluorescein (CASRN 11121-48-5, C.I. 45440), available from PFALZ & BAUER INC.
- the solvent resistance is tested by immersion of a membrane in an organic solvent at 20° C. for 24 hours and evaluated according to a criterion as disclosed in Table 3.
- the average solvent resistance is defined as the summation of all individual scores of solvent resistance divided by the number of organic solvents tested. The smaller this number, the higher the solvent resistance.
- An average solvent resistance over a wide range of different types of organic solvents should preferably not be more than 2.0, more preferably less than 1.0.
- a filtration test was performed using a laboratory-made high-throughput (HT) filtration module.
- HT high-throughput
- the separation was carried out under various pressures such as 10, 15, 20 or 27 bars depending on the membrane.
- the retention R is calculated as a percentage from the measured concentration of Rose Bengal divided by the original concentration of Rose Bengal in the solution.
- the permeability P is the volume of isopropanol collected after filtration for the same surface area of membrane and duration of filtration, taking into account the pressure applied.
- This example illustrates the effect of a polymeric membrane prepared using a radiation curable composition in accordance to a preferred embodiment of the present invention in comparison to a polymeric membrane prepared in the traditional manner without radiation curing.
- the coating compositions COMP-1 and INV-1 to INV-4 were prepared using the components according to Table 4.
- the coating compositions were prepared by adding the membrane polymer polysulfone PSf to DMF and stirring the solution at 80° C. for 3 hours before cooling to 20° C.
- the non-radiation curable coating composition COMP-1 was completed by addition of THF to the polysulfone solution and degassing the homogeneous solution for 2 hours in order to remove air bubbles.
- the radiation curable coating compositions INV-1 to INV-4 were completed by adding to the polysulfone solution in DMF, in order, the multifunctional monomer, the photoinitiator and THF and stirring the homogeneous composition for 2 hours.
- non-woven polyethylene terephthalate porous supports were wetted by DMF.
- the comparative coating composition COMP-1 was cast at a speed of 0.65 m/min and the inventive coating compositions INV-1 and INV-4 were cast at speed of 1.81 m/min, both using an automated casting knife (Braine Instruments) with a gap of 200 ⁇ m, on the wetted porous supports according to Table 5.
- the membranes were exposed to air for 30 s to evaporate THF.
- the membranes prepared using the radiation curable compositions INV-1 to INV-4 were then transported through a Fusion Systems with a UV exposure unit having a D-bulb above the conveyor belt at a speed of 10 m/min.
- the main irradiation light was UV-A (320-390 nm).
- the energy dose to cure a membrane was 11.87 J/cm 2 .
- the comparative membrane MEM-1 and the inventive membranes MEM-2 to MEM-5 were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- IPA iso-propanol
- This example illustrates the effect on solvent resistance of the number of free radical polymerizable groups of the hydrophobic monomer or oligomer in a radiation curable composition for manufacturing a polymeric membrane.
- the comparative radiation curable composition COMP-2 and the inventive radiation curable compositions INV-5 to INV-9 were prepared in the same manner as in Example 1 but using the components in the weight percentages according to Table 8.
- the radiation curable compositions COMP-2 and INV-5 and INV-9 were cast at speed of 1.81 m/min using an automated casting knife (Braine Instruments) with a gap of 200 ⁇ m on the NovatexxTM 2413 N porous support. Before immersion for 15 minutes into a coagulation bath containing distilled water, the membranes were exposed to air for 30 s to evaporate THF.
- the membranes were stored in distilled water before the curing step, where they were transported through a Fusion Systems with a UV exposure unit having a D-bulb above the conveyor belt at a speed of 10 m/min.
- the main irradiation light was UV-A (320-390 nm).
- the energy dose to cure a membrane was 11.87 J/cm 2 .
- the membranes were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- IPA iso-propanol
- the membrane MEM-6 made from a radiation curable composition with a hydrophobic monomer having a single free radical polymerizable group is not solvent resistant.
- the solvent resistance improves with the number of free radical polymerizable groups. No further improvement of solvent resistance was observed when the hydrophobic monomer or oligomer included at least four free radical polymerizable groups.
- PI polyimide
- DMF dimethylformamide
- the NovatexxTM 2481 porous support was wetted by DMF. Then membranes with a wet thickness of 200 ⁇ m were cast at a speed of 1.81 m/min on the NovatexxTM 2481 porous support. The membranes were kept in air for 30 s to evaporate THF before the coagulation step by immersion for 15 minutes in distilled water.
- the membranes were transported through a Fusion Systems with a UV exposure unit having a D-bulb above the conveyor belt at a speed of 10 m/min.
- the main irradiation light was UV-A (320-390 nm).
- the energy dose to cure a membrane was 11.87 J/cm 2 .
- the membranes were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- IPA iso-propanol
- the radiation cured polyimide membranes were tested in the organic solvents of Example 1. After immersion in the different solvents, the membrane only delaminated from the polyester support and became gel-like without dissolving when immersing it in NMP. All other organic solvents had minor or no deteriorating effect on the solvent resistance of the radiation cured polyimide membrane.
- the radiation cured polyimide membrane exhibited good filtration performance with a permeability of 1.45 l m ⁇ 2 h ⁇ 2 bar ⁇ 2 and retention of 96% for Rose Bengal.
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Abstract
A radiation curable composition for preparing a polymeric membrane includes a) a membrane polymer selected from the group consisting of a polysulfone (PSU), a polyether sulfone (PES), a polyether etherketone (PEEK), a polyvinylchloride (PVC), a polyacrylonitrile (PAN), a polyvinylidene fluoride (PVDF), a polyimide (PI), a polyamide (PA) and copolymers thereof; b) a hydrophobic monomer or oligomer having at least two free radical polymerizable groups independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group, a maleate group, a fumarate group, an itaconate group, and a maleimide group; and c) an organic solvent for the membrane polymer and the hydrophobic monomer. A polymeric membrane and a method for manufacturing the membrane are also disclosed.
Description
- This application is a 371 National Stage Application of PCT/EP2013/055723, filed Mar. 19, 2013. This application claims the benefit of U.S. Provisional Application No. 61/615,905, filed Mar. 27, 2012, which is incorporated by reference herein in its entirety. In addition, this application claims the benefit of European Application No. 12161017.4, filed Mar. 23, 2012, which is also incorporated by reference herein in its entirety.
- 1. Field of the Invention
- The present invention relates to solvent resistant polymeric membranes and to methods for manufacturing these membranes.
- 2. Description of the Related Art
- Polymeric membranes are widely used in separation technologies and the field of application is continuously expanding towards ever more demanding applications. The use of harsh solvents in different applications requires highly solvent resistant polymeric membranes. Conventional polymeric membranes using polymers such as polyimides and polyaryl sulfones are not sufficiently resistant towards heat and harsh solvents.
- The general approach in polymer technology to enhance chemical resistance is to cross-link the polymers. Cross-linking is a process during which two or more polymer chains are connected to each other by joints, called cross-links. Cross-linking can be physical with the cross-links being part of an intrinsic physical property of a crystalline, a semi-crystalline polymer or block copolymer, where crystallites or domains of the dispersed phase act as physical cross-links. Generally, polymeric membranes having physical cross-links exhibit poor solvent resistance.
- Chemical cross-links are formed by a chemical reaction initiated by e.g. thermal treatment. WO2007/125367 A1 (IMP INNOVATIONS) discloses membranes formed from polyimides by phase inversion which are then crosslinked by addition of amine crosslinking agents that react with the imide groups of the polyimide creating amide bonds. The authors claim the membrane to be stable in DMF, NMP, DCM and 1,4-dioxane. A similar approach is disclosed by WO2008/138078 A1 (KU Leuven).
- WO2010/111755 A2 (KU Leuven) discloses a simplified method for the preparation of crosslinked polyimide nanofiltration membranes, by adding the cross-linking agent to the polyimide polymer cast solution or to the phase inversion coagulation medium.
- Often a post heat treatment is required to complete the thermal cross-linking of polymeric membranes, making manufacturing of these membranes less compatible with roll to roll production technology. In addition, cross-linking is only possible with certain specific polymers, such as polyimide. The modification of a non-cross-linkable polymer used in polymeric membranes to a cross-linkable copolymer represents not only an economic penalization, but often also leads to undesired changes in other properties of the membrane.
- UV irradiation has been used in membrane technology for modifying the surface of a membrane in order to enhance the performance of the membrane such as permeability and selectivity. U.S. Pat. No. 5,468,390 (RENSSELAER POLYTECH) discloses a process for modifying the surface of aryl polysulfone membranes by placing an aryl polysulfone membrane into the presence of a hydrophilic vinyl monomer dissolved in a solvent and exposing it then to ultraviolet light. The resulting ultrafiltration and microfiltration membranes exhibit low fouling characteristics. Membrane fouling is a process where particles deposit onto a membrane surface or into membrane pores in a way that degrades the membrane's performance.
- US2003209487 A1 (RENSSELAER POLYTECH) discloses a method for modifying a polyethersulfone membrane by immersing the membrane in a monomer solution and exposing it to UV irradiation having a wavelength of 280 nm to 300 nm. A similar method is disclosed by US2005139545 A1 (RENSSELAER POLYTECH) for photografting polyethersulfone or polysulfone membranes with various monomers, such as acrylic acid, N-vinyl-2-pyrrolidinone, and 2-hydroxyethyl-methacrylate; and also by US2002161066 A1 (University of Toulouse) for preparing a hollow fibre polysulfone membrane by immersion in a solution comprising acrylic acid and exposing it to UV light.
- In another approach, blends of (co)polymers are used to prepare polymeric membranes. U.S. Pat. No. 5,885,456 (MILLIPORE) discloses a method for the preparation of a UF or MF membrane comprising a blend of a polysulfone polymer and a graft copolymer of the polysulfone polymer and a polymerized monomer. The graft copolymer membrane is obtained by casting a solution comprising polyethersulfone and the polymerizable monomer, and subsequently exposing the cast membrane to UV irradiation. The membrane obtained after coagulation exhibits a highly hydrophilic surface.
- U.S. Pat. No. 5,079,272 (MILLIPORE) discloses a method for the preparation of a porous membrane formed from an interpenetrating polymer network of a hydrophobic polymer and a polymerized and crosslinked hydrophilic monomeric composition. A solution of the polymer and monomeric composition is cast, exposed to ultraviolet radiation, coagulated and dried. The resulting dried membrane is annealed in order to render its surface hydrophilic.
- UV irradiation has been used in the above described membrane technology to synthesize an interpenetrating polymer network with a hydrophilic surface, as well as to synthesize copolymer membranes. In these approaches a hydrophilic monomer is added to the dope solution. The dope solution is cast, UV irradiated and finally coagulated to obtain a membrane. There is however little or no information on their resistance to organic solvents. Other methods to prepare fully solvent resistant membranes, e.g. by thermal crosslinking, require specially designed (co)polymers or post heat treatment steps, making the approaches expensive and less interesting from an economical point of view.
- Therefore, there is still a need for fully inert membrane designs, accessible from industrially available compounds and compatible with a roll to roll production method.
- It was surprisingly found that the above cited problems could be solved through a single step approach by coating a radiation curable composition containing a polymer for a membrane and a multifunctional hydrophobic monomer or oligomer having at least two free radical polymerizable groups on a porous substrate, followed, in order, by phase inversion and radiation curing.
- Preferred embodiments of the present invention provide a method for manufacturing polymeric membranes exhibiting improved solvent resistance, more particularly with a preparation method compatible with roll to roll coating. In the latter, a continuous production of membranes integrated in a coating line becomes possible.
- Preferred embodiments of the present invention provide highly solvent resistant polymeric membranes without affecting the filtration performance.
- These and other objects and advantages of the present invention will become apparent from the detailed description below.
- The term “actinic radiation” as used in disclosing the present invention, means electromagnetic radiation capable of initiating photochemical reactions.
- The term “alkyl” means all variants possible for each number of carbon atoms in the alkyl group i.e. for three carbon atoms: n-propyl and isopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl; for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyl and 2-methyl-butyl etc.
- The radiation curable composition according to a preferred embodiment of the present invention for manufacturing a polymeric membrane including: a) a membrane polymer selected from the group consisting of a polysulfone (PSU), a polyether sulfone (PES), a polyether etherketone (PEEK), a polyvinylchloride (PVC), a polyacrylonitrile (PAN), a polyvinylidene fluoride (PVDF), a polyimide (PI), a polyamide (PA) and copolymers thereof; b) a hydrophobic monomer or oligomer having at least two free radical polymerizable groups, preferably at least three free radical polymerizable groups, and most preferably at least four free radical polymerizable groups which are independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group, a maleate group, a fumarate group, an itaconate group, and a maleimide group; and c) an organic solvent for the membrane polymer and the hydrophobic monomer or oligomer.
- In a preferred embodiment of the radiation curable composition, the membrane polymer is selected from the group consisting of a polysulfone, a polyether sulfone, a polyimide and a polyetheretherketone.
- The radiation curable composition according to a preferred embodiment of the present invention is used to manufacture a polymeric membrane with an improved solvent resistance.
- In a preferred embodiment of the radiation curable composition, the weight ratio between the polymer and the hydrophobic monomer or oligomer is between 10 to 1 and 1 to 1.
- In a preferred embodiment of the radiation curable composition, the weight ratio between the polymer and the at least one photoinitiator is between 12 to 1 and 1 to 1.
- The membrane polymer is selected from the group consisting of a polysulfone (PSU), a polyether sulfone (PES), a polyether etherketone (PEEK), a polyvinylchloride (PVC), a polyacrylonitrile (PAN), a polyvinylidene fluoride (PVDF), a polyimide (PI), a polyamide (PA) and copolymers thereof.
- The membrane polymer is preferably selected from the group consisting of a polysulfone, a polyether sulfone, a polyimide and a polyether etherketone; and even more preferably selected from the group consisting of a polysulfone and a polyether sulfone.
- In a preferred embodiment, the membrane polymer is a polysulfone or a copolymer thereof having repeating units according to Formula (I):
-
—Ar1-SO2—Ar2-X—(R1-Y)n— Formula (I), - with:
- Ar1 and Ar2 represent an aryl group;
- Ar1 and Ar2 may represent the same aryl group or a different aryl group;
- X and Y are independently selected from the group consisting of an oxygen, a sulfur, an amine group and a substituted or unsubstituted methylene group;
- n is an integer representing 0 or 1;
- R1 is selected from the group consisting of an aryl group and a group according to Formula (II):
-
—Ar3-Z—Ar4- Formula (II), - with:
- Ar3 and Ar4 represent an aryl group;
- Ar3 and Ar4 may represent the same aryl group or a different aryl group;
- Z represents a group selected from the group consisting of O, S(O)m, and a substituted or unsubstituted methylene group; and m is an integer representing 0 or 1.
- In a particularly preferred embodiment X and Y represent an oxygen. In a even more preferred embodiment Ar1 to Ar4 represent a substituted or unsubstituted 1,4-phenylene group, an unsubstituted 1,4-phenylene group being particularly preferred.
- Particularly preferred groups representing R1 are given in Table 1, without being limited thereto.
- Preferred polysulfones and polyethersulfones are disclosed in EP0997182 A (ASAHI MEDICAL), EP1634610 A (TOYO BOSEKI), U.S. Pat. No. 6,045,899 (USF), US2006228483 A (AQUASOURCE), EP1733784 A (TOYO BOSEKI), EP1007195 A (USF), US2006076288 A (3M) and EP1609522 A (MILLIPORE).
- Preferred commercially available polysulfones and polyethersulfones are the Udel™ types supplied by Solvay, more specifically the P-1835, P-3500 LCD, P-3500 LCD MB3, P-3500 LCD MB7 and P-3500 LCD MB8 grades, polysulfone P-1700 LCD being most preferred.
- The organic solvent of the radiation curable composition is capable of dissolving the polymer and the hydrophobic monomer or oligomer. If present, the photoinitiator and the co-initiator is preferably also dissolved by the organic solvent.
- The organic solvent may also be a mixture of solvents as long as they are capable of dissolving the polymer and the hydrophobic monomer or oligomer.
- Preferred organic solvents are on or more organic solvents selected from the group selected of dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), tetrahydrofuran (THF), 1,4-dioxane, alcohols and ketones.
- The organic solvent is most preferably a water-miscible organic solvent.
- The coagulation bath includes one or a mixture of organic solvents and preferably also a surfactant, e.g. Triton™ X-100 (octylphenoxy-polyethoxyethanol). The conditions for effecting coagulation are well known to those skilled in the art.
- The hydrophobic monomer or oligomer of the radiation curable composition has at least two, preferably at least three and most preferably at least four free radical polymerizable groups independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group, a maleate group, a fumarate group, an itaconate group, and a maleimide group.
- In a preferred embodiment, the free radical polymerizable groups of the hydrophobic monomer or oligomer are selected from the group consisting of an acrylate group and a methacrylate group, an acrylate group being the most preferred.
- The hydrophobic monomer or oligomer of the radiation curable composition needs to be hydrophobic because hydrophilic monomers, such as acrylic acid and 2-hydroxyethyl-methacrylate, have a too high solubility in water whereby they are largely removed by the phase inversion step during the manufacturing of polymeric membranes and no longer available in the subsequent radiation curing step for improving the solvent resistance of the polymeric membrane.
- In a preferred embodiment, the hydrophobic monomer or oligomer has a solubility in water at 20° C. of less than 20 mg/l, preferably less than 10 mg/l.
- Particularly preferred hydrophobic monomers and oligomers are pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexacrylate, ethoxylated dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol pentaacrylate, ethoxylated dipentaerythritol hexaacrylate, propoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol pentaacrylate, propoxylated dipentaerythritol hexaacrylate, tetra-, penta- or hexafunctional urethane acrylate oligomers, tetra-, penta- or hexafunctional polyester acrylate oligomers and tetra-, penta- or hexafunctional polyether acrylate oligomers.
- The hydrophobic monomers and oligomers preferably have a molecular weight of less than 5000 Da, more preferably less than 3000 Da.
- The majority of the photoinitiators can be classified as Norrish type I or Norrish type II initiators. Norrish type I initiators generate initiating radicals by α-cleavage upon exposure to UV radiation. Norrish type II initiators abstract a hydrogen from a second molecule, a so called coinitiator, upon exposure to UV light. The initiating radicals are formed on the coinitiator. The radiation curable composition according to the present invention preferably includes at least one photoinitiator. For fast curing, the at least one photoinitiator preferably has an absorption maximum at a wavelength above 320 nm, more preferably above 340 nm.
- Particularly preferred bathochromic photoinitiators are thioxanthone photoinitiators, carbazole based photoinitiators and acyl phosphineoxide based photoinitiators, acyl phosphine based initiators being particularly preferred. In a preferred embodiment, the at least one photoinitiator is selected from the group consisting of a thioxanthone photoinitiator and an acyl phosphineoxide photoinitiator.
- Typical preferred photoinitiators according to the present invention are given below in Table 2 without being limited thereto.
- Coinitiators are preferably selected from aliphatic tertiary amines and dialkylamino substituted aromatic compounds, dialkylamino substituted aromatic compounds being more preferred, 4-dialkylamino benzoic acid esters being the most preferred.
- The radiation curable composition according to a preferred embodiment of the present invention preferably includes a 4-dialkylaminobenzoic acid derivative as coinitiator.
- In a preferred embodiment the polymer to initiator ratio is between 12 to 1 and 1 to 1, more preferably between 10 to 1 and 2 to 1, and most preferably between 8 to 1 and 3 to 1.
- In another preferred embodiment the polymer to coinitiator ratio is between 12 to 1 and 1 to 1, more preferably between 10 to 1 and 2 to 1, and most preferably between 8 to 1 and 3 to 1.
- The radiation curable composition according to a preferred embodiment of the present invention is cast on a porous support. The porous support preferably has also a high resistance against organic solvents and other chemicals.
- Preferred porous supports include woven or non-woven materials such as polyester/nylon fabrics, polyphenylene sulphide fabrics, cellulose/polyester fabrics, polytetrafluoroethylene, polyvinyl chloride, Teflon, sintered glass, glass fibres, ceramic supports, and a metal mesh.
- Preferably, the supporting material is a non-woven fabric, such as polyethylene, polypropylene, a polyethylene/polypropylene blend or a polyester material.
- Preferred porous supports are disclosed in EP0012557 A (ABCOR), U.S. Pat. No. 6,045,899 (USF), WO2007125367 A (IMP INNOVATIONS), US2010181253 A (EVONIK FIBRES), and WO2010111755 A (KU Leuven).
- In view of its high solvent resistance, the supporting material is preferably a polyester support, more preferably a polyethylene terephthalate porous support, such as the Novatexx™ grades available from Freudenberg Filter Technologies.
- There is no real limitation on the thickness of the porous support, but preferably the porous support has a thickness of at least 0.10 mm.
- A method for manufacturing a polymeric membrane according to a preferred embodiment of the present invention includes, in order, the steps of:
- a) preparing a radiation curable composition according to the present invention;
- b) coating a layer of the radiation curable composition on a porous support;
- c) phase inverting the coated layer; and
- d) curing the phase inverted coated layer by actinic radiation.
- The method is preferably performed by roll to roll coating.
- Once the hydrophobic monomer or oligomer is added to the coating composition, the manufacturing steps are performed under light conditions in which actinic radiation has been substantially or fully excluded, and where necessary cooling of the radiation curable composition is foreseen to prevent build up of heat as much as possible.
- The manufacturing steps will now be explained in more detail.
- In a preferred embodiment, the radiation curable composition is prepared in two steps. First, the polymer is dissolved in a suitable solvent at elevated temperature, usually in the range 50-150° C., preferably in the range 70-90° C.
- Subsequently, the homogeneous polymer solution is cooled down and the hydrophobic monomer or oligomer and optionally a photoinitiator and a co-solvent are added.
- Preferred radiation curable compositions have a polymer concentration ranging from 12 wt % to 30 wt %, preferable from 15 wt % to 25 wt %; the most preferable from 17 wt % to 22 wt % based on the total weight of the radiation curable composition.
- Any industrial coating technique, suitable for the coating of highly concentrated polymer solutions can be used. Slot and extrusion coating techniques are particularly preferred. Slot and extrusion coating techniques belong to a class of coating methods known as premetered coating in which the thickness of the coated liquid is in principle set by the flow rate of the feed to the die, the width of the web and the speed of the substrate moving past and is independent of other process variables. When slot coating techniques are used, the dope at the impregnation temperature preferably has a viscosity at a shear rate of 1 s−1 in the range of 1 to 500 mPa·s at 20° C. When slot coating techniques are used, the dope at the impregnation temperature preferably has a viscosity at a shear rate of 1 s1 of greater than 103 mPa·s at 20° C.
- In a preferred embodiment of the present invention, polymeric membranes are prepared by a phase inversion process which allows a controlled transformation of a polymer from solution to the solid state.
- The polymeric solution may be inverted to a solid polymeric membrane by various phase inversion methods which include Liquid Induced Phase Separation (LIPS), where phase inversion is induced by immersion of the cast membrane in a non-solvent (or mixture of solvent and non-solvent), Vapour Induced Phase Separation (VIPS), where the initiating phase inversion medium is a vapour, Evaporation Induced Phase Separation (EIPS), where phase inversion is carried out by controlled evaporation of the solvent, as well as Thermal Induced Phase Separation (TIPS), where the membrane is prepared by thermal precipitation. Liquid Induced Phase Separation is particularly preferred.
- The polymeric membrane according to a preferred embodiment of the present invention is cured by exposure to actinic radiation, such as γ-rays, electron beam radiation, UV- and visible light. The actinic radiation is preferably electron beam radiation and/or UV-light, more preferably UV-light.
- Any ultraviolet light source, as long as part of the emitted light can be absorbed by the photoinitiator or photoinitiator system, may be applied as a radiation source, such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser and a flash light.
- UV-light sources dominantly emitting in the UV-A region of the spectrum, defined as 320 to 400 nm, are particularly preferred. The UV-curing dose is preferably in the range from 1 to 20 J/cm2; more preferably from 3-15 J/cm2 and most preferably from 7 up to 13 J/cm2.
- In a preferred embodiment, the method for manufacturing a polymeric membrane includes a step e) of conditioning the polymeric membrane by immersion of the cured polymeric membrane in a solution comprising a conditioning agent and a solvent.
- Conditioning of the radiation cured polymeric membrane improves mechanical properties of the membrane, e.g. elasticity, as well as filtration properties, e.g. improved permeability by avoiding pore collapsing in the membrane.
- The conditioning agent is preferably a low volatile organic liquid selected from the group consisting of glycols (polyalkylene glycols more preferably polyethylene glycol or polypropylene glycol), glycerols, mineral oils, synthetic oils, vegetable fats and oils are used.
- The solvent for dissolving the one or more conditioning agents preferably includes one or more alcohols, ketones, hydrocarbons or mixtures thereof.
- In a preferred embodiment, the radiation cured membrane is conditioned in a glycerol/isopropanol bath with a glycerol concentration of at least 30% (v/v). In the most preferred embodiment, the radiation cured membrane is conditioned for at least 24 h.
- The polymeric membranes obtained from the methods according to preferred embodiments of the present invention can be used as filtration elements for microfiltration, ultrafiltration, nanofiltration, reverse osmosis, membrane distillation, pervaporation, gas separation, immobilizing biologically active species (e.g. enzyme and biofilm reactors); in membrane contactors e.g. supported liquid membranes, pertraction, water degassing, aeration, humidification (vapour permeation), controlled release; in membrane bioreactors (for permeate withdrawal) and in air conditioning for gas/air cleaning, and other membrane applications, especially those employing (aggressive) organic solvents.
- The radiation cured polymeric membranes of the invention, especially the polysulfone membranes can be advantageously used in applications requiring solvent resistance, more particularly in separation processes which are performed in aprotic solvents, such as NMP, THF, and DMF.
- All materials used in the following examples were readily available from standard sources such as ALDRICH CHEMICAL Co. (Belgium) and ACROS (Belgium) unless otherwise specified. The water used was deionized water.
- TPO is 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, a photoinitiator available as Darocur™ TPO from BASF. BAPO is bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, a photoinitiator available as Irgacure™ 819 from BASF. PSf is polysulfone P-1700 supplied by Solvay and having the following structure:
- PI is a polyimide polymer available as Matrimid™ 9725 from HUNTSMAN.
- SR285 is tetrahydrofurfuryl acrylate available as Sartomer™ SR285 from SARTOMER.
- SR295 is pentaerythritol tetraacrylate available as Sartomer™ SR295 from SARTOMER.
- SR351 is trimethylolpropane triacrylate available as Sartomer™ SR351 from SARTOMER.
- SR399LV is dipentaerythritol pentaacrylate available as Sartomer™ SR399LV from SARTOMER.
- M600 is dipentaerythritol hexaacrylate available as Miramer™ M600 from RAHN.
- DEGDA is ethylene glycol diacrylate.
- DMF is dimethylformamide.
- THF is tetrahydrofuran.
- Novatexx™ 2413 N is a porous PET polyester support having a weight of 100 g/m2 and an air permeability of 300 l/m2 s at 200 Pa, available from FREUDENBERG FILTER TECHNOLOGIES. Novatexx™ 2481 is a porous PET/PBT polyester support having a weight of 100 g/m2 and an air permeability of 125 l/m2 s at 200 Pa, available from FREUDENBERG FILTER TECHNOLOGIES.
- Rose Bengal is 4,5,6,7-tetrachloro-2′,4′,5′,7′-tetraiodofluorescein (CASRN 11121-48-5, C.I. 45440), available from PFALZ & BAUER INC.
- The solvent resistance is tested by immersion of a membrane in an organic solvent at 20° C. for 24 hours and evaluated according to a criterion as disclosed in Table 3. The average solvent resistance is defined as the summation of all individual scores of solvent resistance divided by the number of organic solvents tested. The smaller this number, the higher the solvent resistance. An average solvent resistance over a wide range of different types of organic solvents should preferably not be more than 2.0, more preferably less than 1.0.
-
TABLE 3 Score Criterion 0 Stable membrane 1 Some swelling or shrinkage 2 Swelling or shrinkage 3 Pronounced swelling or shrinkage 4 Partially dissolved membrane 5 Dissolved membrane - A filtration test was performed using a laboratory-made high-throughput (HT) filtration module. A solution of 17.5 μM of Rose Bengal (Mw=1017 Da) in IPA was used as feed. The separation was carried out under various pressures such as 10, 15, 20 or 27 bars depending on the membrane. The concentration of Rose Bengal in IPA was determined by means of UV/Vis spectrophotometry at λmax=555 nm.
- The retention R is calculated as a percentage from the measured concentration of Rose Bengal divided by the original concentration of Rose Bengal in the solution.
- The permeability P is the volume of isopropanol collected after filtration for the same surface area of membrane and duration of filtration, taking into account the pressure applied.
- This example illustrates the effect of a polymeric membrane prepared using a radiation curable composition in accordance to a preferred embodiment of the present invention in comparison to a polymeric membrane prepared in the traditional manner without radiation curing.
- The coating compositions COMP-1 and INV-1 to INV-4 were prepared using the components according to Table 4.
-
TABLE 4 wt % of component: COMP-1 INV-1 INV-2 INV-3 INV-4 PSf 21 21 21 21 21 DMF 67 61 61 54 54 THF 12 10 10 9 9 SR399LV — 5 5 10 10 TPO — 3 — 6 — BAPO — — 3 — 6 - The coating compositions were prepared by adding the membrane polymer polysulfone PSf to DMF and stirring the solution at 80° C. for 3 hours before cooling to 20° C.
- The non-radiation curable coating composition COMP-1 was completed by addition of THF to the polysulfone solution and degassing the homogeneous solution for 2 hours in order to remove air bubbles.
- The radiation curable coating compositions INV-1 to INV-4 were completed by adding to the polysulfone solution in DMF, in order, the multifunctional monomer, the photoinitiator and THF and stirring the homogeneous composition for 2 hours.
- First, non-woven polyethylene terephthalate porous supports were wetted by DMF. Then, the comparative coating composition COMP-1 was cast at a speed of 0.65 m/min and the inventive coating compositions INV-1 and INV-4 were cast at speed of 1.81 m/min, both using an automated casting knife (Braine Instruments) with a gap of 200 μm, on the wetted porous supports according to Table 5. Before immersion for 15 minutes into a coagulation bath containing distilled water for phase inversion, the membranes were exposed to air for 30 s to evaporate THF.
- The membranes prepared using the radiation curable compositions INV-1 to INV-4 were then transported through a Fusion Systems with a UV exposure unit having a D-bulb above the conveyor belt at a speed of 10 m/min. The main irradiation light was UV-A (320-390 nm). The energy dose to cure a membrane was 11.87 J/cm2.
-
TABLE 5 Polymeric Coating Membrane solution Porous support MEM-1 COMP-1 Novatexx ™ 2413 N MEM-2 INV-1 Novatexx ™ 2481 MEM-3 INV-2 Novatexx ™ 2481 MEM-4 INV-3 Novatexx ™ 2413 N MEM-5 INV-4 Novatexx ™ 2413 N - Before testing the solvent stability and filtration performance, the comparative membrane MEM-1 and the inventive membranes MEM-2 to MEM-5 were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- The solvent resistance of the air-dried membranes MEM-1 to MEM-5 were tested by means of immersion for 24 hours in 17 different organic solvents. The results are summarized in Table 6.
-
TABLE 6 Organic Solvent MEM-1 MEM-2 MEM-3 MEM-4 MEM-5 Acetone 4 0 0 0 0 Acetonitrile 0 0 0 0 0 Butyl acetate 4 0 0 0 0 Chlorobenzene 5 3 3 3 3 Cyclohexane 0 0 0 0 0 Cyclohexanone 5 1 1 1 1 Ethyl acetate 4 0 0 0 0 Iso-propanol 0 0 0 0 0 n-Heptane 0 0 0 0 0 n-Hexane 0 0 0 0 0 Methanol 0 0 0 0 0 NMP 5 1 1 1 1 Propylene 0 0 0 0 0 carbonate THF 5 1 1 1 1 Toluene 5 0 0 0 0 Triethylphosphate 5 1 1 1 1 Xylene mixture 5 0 0 0 0 Average solvent 2.8 0.4 0.4 0.4 0.4 resistance - From Table 6, it becomes immediately apparent that the inventive membranes MEM-2 to MEM-5 are highly solvent resistant.
- The filtration performance of the comparative membrane MEM-1 and the inventive membranes MEM-2 to MEM-5 were tested after the membranes were rinsed in distilled water for 48 hours to remove glycerol. The results of the filtration tests are summarized in Table 7.
-
TABLE 7 Polymeric Permeability P Retention Membrane (l m−2 h−1 bar−1) R (%) MEM-1 0.32 95 MEM-2 0.19 94 MEM-3 0.13 95 MEM-4 0.22 94 MEM-5 0.14 97 - From Table 7, is should be clear that filtration performance of all membranes are comparable.
- This example illustrates the effect on solvent resistance of the number of free radical polymerizable groups of the hydrophobic monomer or oligomer in a radiation curable composition for manufacturing a polymeric membrane.
- The comparative radiation curable composition COMP-2 and the inventive radiation curable compositions INV-5 to INV-9 were prepared in the same manner as in Example 1 but using the components in the weight percentages according to Table 8.
-
TABLE 8 wt % of component: COMP-2 INV-5 INV-6 INV-7 INV-8 INV-9 PSf 21 21 21 21 21 21 DMF 60 60 60 60 60 60 THF 11 11 11 11 11 11 TPO 3 3 3 3 3 3 SR285 5 — — — — — DEGDA — 5 — — — — SR351 — — 5 — — — SR295 — — — 5 — — SR399LV — — — — 5 — M600 — — — — — 5 - After the Novatexx™ 2413 N porous support was wetted by DMF, the radiation curable compositions COMP-2 and INV-5 and INV-9 were cast at speed of 1.81 m/min using an automated casting knife (Braine Instruments) with a gap of 200 μm on the Novatexx™ 2413 N porous support. Before immersion for 15 minutes into a coagulation bath containing distilled water, the membranes were exposed to air for 30 s to evaporate THF.
- The membranes were stored in distilled water before the curing step, where they were transported through a Fusion Systems with a UV exposure unit having a D-bulb above the conveyor belt at a speed of 10 m/min. The main irradiation light was UV-A (320-390 nm). The energy dose to cure a membrane was 11.87 J/cm2.
- Before testing the solvent stability and filtration performance, the membranes were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- The solvent resistance of the air-dried membranes MEM-6 to MEM-11 were tested by means of immersion for 24 hours in 7 of the most aggressive organic solvents used in Example 1. The results are summarized in Table 9.
-
TABLE 9 Organic Solvent MEM-6 MEM-7 MEM-8 MEM-9 MEM-10 MEM-11 THF 5 5 5 2 2 2 Acetone 3 2 0 0 0 0 Butyl acetate 0 0 0 0 0 0 Cyclo- 5 5 5 2 2 2 hexanone Ethyl acetate 4 2 0 0 0 0 Toluene 3 0 0 0 0 0 Mixture of 0 0 0 0 0 0 xylenes - The filtration performance of the membranes MEM-6 to MEM-11 was tested after the membranes were rinsed in distilled water for 48 hours to remove glycerol. The results of the filtration tests together with the average solvent resistance are summarized in Table 10.
-
TABLE 10 Radiation Number Permeability Curable of Average P Retention Polymeric Composi- Acrylate Solvent (l m−2 h−1 R Membrane tion Groups Resistance bar−1) (%) MEM-6 COMP-2 1 2.9 1.80 82 MEM-7 INV-5 2 2.0 2.55 70 MEM-8 INV-6 3 1.4 0.24 90 MEM-9 INV-7 4 0.6 0.27 89 MEM-10 INV-8 5 0.6 0.26 93 MEM-11 INV-9 6 0.6 0.14 93 - From Table 10, it should be clear that the membrane MEM-6 made from a radiation curable composition with a hydrophobic monomer having a single free radical polymerizable group is not solvent resistant. The solvent resistance improves with the number of free radical polymerizable groups. No further improvement of solvent resistance was observed when the hydrophobic monomer or oligomer included at least four free radical polymerizable groups.
- This example illustrates that the improvement of solvent resistance is also obtained with a different type of membrane polymer than in Examples 1 and 2.
- A viscous solution containing 20.96 parts of polyimide (PI, Matrimid 9725) (Huntsman) and 53.50 parts of dimethylformamide (DMF) was stirred at 80° C. for 3 hours. Subsequently, the solution was cooled down to 20° C. and 9.47 parts of tetrahydrofuran (THF), 9.97 parts of the multifunctional monomer SR399LV, and 6.10 parts of the photoinitiator TPO were added under stirring. After obtaining a homogeneous solution, the casting solution was degassed for 24 hours in order to remove air bubbles.
- First, the Novatexx™ 2481 porous support was wetted by DMF. Then membranes with a wet thickness of 200 μm were cast at a speed of 1.81 m/min on the Novatexx™ 2481 porous support. The membranes were kept in air for 30 s to evaporate THF before the coagulation step by immersion for 15 minutes in distilled water.
- The membranes were transported through a Fusion Systems with a UV exposure unit having a D-bulb above the conveyor belt at a speed of 10 m/min. The main irradiation light was UV-A (320-390 nm). The energy dose to cure a membrane was 11.87 J/cm2.
- Before testing the solvent stability and filtration performance, the membranes were impregnated for 48 h at room temperature in a bath containing 40% (v/v) of glycerol and 60% (v/v) of iso-propanol (IPA) and subsequently air-dried.
- The radiation cured polyimide membranes were tested in the organic solvents of Example 1. After immersion in the different solvents, the membrane only delaminated from the polyester support and became gel-like without dissolving when immersing it in NMP. All other organic solvents had minor or no deteriorating effect on the solvent resistance of the radiation cured polyimide membrane.
- The radiation cured polyimide membrane exhibited good filtration performance with a permeability of 1.45 l m−2 h−2 bar−2 and retention of 96% for Rose Bengal.
- While preferred embodiments of the present invention have been described above, it is to be understood that variations and modifications will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. The scope of the present invention, therefore, is to be determined solely by the following claims.
Claims (12)
1-15. (canceled)
16. A radiation curable composition for manufacturing a polymeric membrane, the radiation curable composition comprising:
a membrane polymer selected from the group consisting of a polysulfone (PSU), a polyether sulfone, a polyether etherketone, a polyvinylchloride, a polyacrylonitrile, a polyvinylidene fluoride, a polyimide, a polyamide, and copolymers thereof;
a hydrophobic monomer or oligomer including at least two free radical polymerizable groups independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group, a maleate group, a fumarate group, an itaconate group, and a maleimide group;
an organic solvent for the membrane polymer and the hydrophobic monomer or oligomer; and
an acyl phosphineoxide photoinitiator having a maximum absorption at a wavelength above 320 nm.
17. The radiation curable composition according to claim 16 , wherein the hydrophobic monomer or oligomer includes at least three free radical polymerizable groups independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group, a maleate group, a fumarate group, an itaconate group, and a maleimide group.
18. The radiation curable composition according to claim 16 , wherein the hydrophobic monomer or oligomer includes at least four free radical polymerizable groups independently selected from the group consisting of an acrylate group, a methacrylate group, an acrylamide group, a methacrylamide group, a styrene group, a vinyl ether group, a vinyl ester group, a maleate group, a fumarate group, an itaconate group, and a maleimide group.
19. The radiation curable composition according to claim 16 , wherein the membrane polymer is selected from the group consisting of a polysulfone, a polyether sulfone, a polyimide, and a polyether etherketone.
20. The radiation curable composition according to claim 16 , wherein the hydrophobic monomer or oligomer is selected from the group consisting of an acrylate group and a methacrylate group.
21. The radiation curable composition according to claim 16 , wherein the membrane polymer is a polysulfone having repeating units according to Formula (I)
—Ar1-SO2—Ar2-X—(R1-Y)n— Formula (I)
—Ar1-SO2—Ar2-X—(R1-Y)n— Formula (I)
wherein:
Ar1 and Ar2 represent an aryl group;
Ar1 and Ar2 may represent the same aryl group or a different aryl group;
X and Y are independently selected from the group consisting of an oxygen, a sulfur, an amine group, and a substituted or unsubstituted methylene group;
n is an integer representing 0 or 1;
R1 is selected from the group consisting of an aryl group and a group according to Formula (II):
—Ar3-Z—Ar4- Formula (II)
—Ar3-Z—Ar4- Formula (II)
wherein:
Ar3 and Ar4 represent an aryl group;
Ar3 and Ar4 may represent the same aryl group or a different aryl group;
Z represents a group selected from the group consisting of O, S(O)m, and a substituted or unsubstituted methylene group; and
m is an integer representing 0 or 1.
22. The radiation curable composition according to claim 16 , wherein a weight ratio between the membrane polymer and the hydrophobic monomer or oligomer is between 10 to 1 and 1 to 1.
23. The radiation curable composition according to claim 16 , wherein a weight ratio between the membrane polymer and the photoinitiator is between 12 to 1 and 1 to 1.
24. A method for manufacturing a polymeric membrane, the method comprising, in order, the steps of:
a) preparing a radiation curable composition according to claim 16 ;
b) coating a layer of the radiation curable composition onto a porous support;
c) phase inverting the coated layer; and
d) curing the phase inverted coated layer by actinic radiation.
25. The method according to claim 24 , wherein the step b) is performed by roll to roll coating.
26. The method according to claim 24 , further comprising the step of:
e) conditioning the polymeric membrane by immersing the polymeric membrane in a solution including a conditioning agent and a solvent.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105854653A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing fibroin grafted polyacrylonitrile nanofiltration membrane |
JP2021522990A (en) * | 2018-04-30 | 2021-09-02 | インテグリス・インコーポレーテッド | Polyamide coated filter membranes, filters and methods |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9724649B2 (en) | 2015-06-25 | 2017-08-08 | Pall Corporation | Self-wetting porous membranes (I) |
EP3586948A1 (en) * | 2018-06-29 | 2020-01-01 | 3M Innovative Properties Company | Low protein binding polyethersulfone microfiltration membranes |
CN109550405B (en) * | 2018-11-26 | 2020-08-04 | 江南大学 | Preparation method and application of ion selective polymer containing membrane |
CN110052172B (en) * | 2019-03-17 | 2021-08-24 | 浙江工业大学 | Preparation method of cross-linked heat-resistant solvent-resistant homogeneous pore membrane and related block copolymer |
CN110548423B (en) * | 2019-08-28 | 2022-04-01 | 陈泉学 | Modified ultrafiltration membrane and modification method thereof |
CN114672049B (en) * | 2020-05-29 | 2023-04-28 | 深圳硅基传感科技有限公司 | Method for producing polymer film for biosensor |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2964867D1 (en) | 1978-12-06 | 1983-03-24 | Abcor Inc | Hydrophilic polymeric membranes, process for their preparation, their use as ultrafiltration membranes, and precursor membranes adapted to be converted thereto |
US4931182A (en) * | 1989-11-08 | 1990-06-05 | Air Products And Chemicals, Inc. | Membranes formed from unsaturated polyimides |
US5079272A (en) | 1989-11-30 | 1992-01-07 | Millipore Corporation | Porous membrane formed from interpenetrating polymer network having hydrophilic surface |
US5788862A (en) * | 1992-05-13 | 1998-08-04 | Pall Corporation | Filtration medium |
US5468390A (en) | 1992-11-23 | 1995-11-21 | Rensselaer Polytechnic Institute | Low fouling ultrafiltration and microfiltration aryl polysulfone |
US5264166A (en) * | 1993-04-23 | 1993-11-23 | W. R. Grace & Co.-Conn. | Polyimide membrane for separation of solvents from lube oil |
JP4080565B2 (en) * | 1996-04-26 | 2008-04-23 | 大日本インキ化学工業株式会社 | Method for producing porous body and porous body |
US5885456A (en) | 1996-08-09 | 1999-03-23 | Millipore Corporation | Polysulfone copolymer membranes and process |
US6045899A (en) | 1996-12-12 | 2000-04-04 | Usf Filtration & Separations Group, Inc. | Highly assymetric, hydrophilic, microfiltration membranes having large pore diameters |
US6432309B1 (en) | 1997-05-19 | 2002-08-13 | Asahi Medical Co, Ltd | Polysulfone-base hollow-fiber hemocathartic membrane and processes for the production thereof |
US5886059A (en) | 1997-07-08 | 1999-03-23 | Memtec America Corporation | Highly asymmetric polyethersulfone filtration membranes |
CA2371060A1 (en) * | 1999-05-14 | 2000-11-23 | Pall Corporation | Charged membrane |
FR2810259B1 (en) | 2000-06-14 | 2002-08-30 | Univ Toulouse | METHOD FOR MANUFACTURING A NANOFILTRATION MEMBRANE, AND MEMBRANE OBTAINED |
JP3734085B2 (en) | 2000-10-05 | 2006-01-11 | レンセレアー ポリテクニック インスティテュート | Method for UV-assisted grafting of PES and PSF films |
US20050139545A1 (en) | 2002-03-12 | 2005-06-30 | Rensselaer Polytechnic , A New York Corporation, | Photo-processing and cleaning of pes and psf membranes |
FR2850297B1 (en) | 2003-01-29 | 2005-04-15 | Aquasource | METHOD FOR MANUFACTURING MEMBRANES FOR FILTRATION MODULES, IN PARTICULAR FOR THE TREATMENT OF WATER |
JP3551971B1 (en) | 2003-11-26 | 2004-08-11 | 東洋紡績株式会社 | Polysulfone permselective hollow fiber membrane |
JP3636199B1 (en) | 2004-03-23 | 2005-04-06 | 東洋紡績株式会社 | Polysulfone-based permselective hollow fiber membrane bundle, method for producing the same and blood purifier |
JP4748655B2 (en) | 2004-06-25 | 2011-08-17 | ミリポア・コーポレイション | Ultrafiltration membrane and manufacturing method |
WO2006044463A1 (en) | 2004-10-13 | 2006-04-27 | 3M Innovative Properties Company | Method for preparing hydrophilic polyethersulfone membrane |
US7339009B2 (en) * | 2004-12-16 | 2008-03-04 | General Electric Company | Cross-linked polyimide and method of making them |
US20070056901A1 (en) * | 2005-09-14 | 2007-03-15 | General Electric Company | Solvent-resistant membranes from solvent-inert polyimides and polyketones |
GB2437519B (en) | 2006-04-28 | 2010-04-21 | Imp Innovations Ltd | Method for separation |
CN101274227B (en) * | 2007-03-28 | 2010-09-15 | 宁波大学 | Method for preparing polymer micro-filter membrane |
GB0709228D0 (en) | 2007-05-14 | 2007-06-20 | Katholieke Universltelt Leuven | Cross-linked polyimide membranes |
US8177892B2 (en) * | 2007-05-24 | 2012-05-15 | Fujifilm Manufacturing Europe B.V. | Membrane comprising oxyethylene groups |
CA2694273A1 (en) * | 2007-07-25 | 2009-01-29 | Lydall Solutech B.V. | Hydrophilic membrane |
WO2010111755A2 (en) | 2009-04-01 | 2010-10-07 | Katholieke Universiteit Leuven - K.U.Leuven R & D | Improved method for making cross-linked polyimide membranes |
US8353410B2 (en) * | 2009-11-24 | 2013-01-15 | International Business Machines Corporation | Polymeric films made from polyhedral oligomeric silsesquioxane (POSS) and a hydrophilic comonomer |
CN102019149B (en) * | 2010-12-01 | 2012-08-15 | 杭州水处理技术研究开发中心有限公司 | Method for preparing solvent-resistant modified polyamide nanofiltration membrane |
-
2012
- 2012-03-23 EP EP12161017.4A patent/EP2641653B1/en active Active
-
2013
- 2013-03-19 WO PCT/EP2013/055723 patent/WO2013139805A1/en active Application Filing
- 2013-03-19 CN CN201380015482.1A patent/CN104364005B/en active Active
- 2013-03-19 US US14/386,909 patent/US20150291843A1/en not_active Abandoned
-
2017
- 2017-01-11 US US15/403,530 patent/US10626276B2/en active Active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105854653A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing fibroin grafted polyacrylonitrile nanofiltration membrane |
JP2021522990A (en) * | 2018-04-30 | 2021-09-02 | インテグリス・インコーポレーテッド | Polyamide coated filter membranes, filters and methods |
JP7455761B2 (en) | 2018-04-30 | 2024-03-26 | インテグリス・インコーポレーテッド | Polyamide coated filter membrane, filter and method |
Also Published As
Publication number | Publication date |
---|---|
CN104364005B (en) | 2017-08-22 |
WO2013139805A1 (en) | 2013-09-26 |
CN104364005A (en) | 2015-02-18 |
US20170121529A1 (en) | 2017-05-04 |
US10626276B2 (en) | 2020-04-21 |
EP2641653B1 (en) | 2021-05-12 |
EP2641653A1 (en) | 2013-09-25 |
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