WO2014204220A1 - 염제거율 및 투과유량 특성이 우수한 폴리아미드계 역삼투 분리막 제조방법 및 상기 제조방법으로 제조된 역삼투 분리막 - Google Patents
염제거율 및 투과유량 특성이 우수한 폴리아미드계 역삼투 분리막 제조방법 및 상기 제조방법으로 제조된 역삼투 분리막 Download PDFInfo
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- WO2014204220A1 WO2014204220A1 PCT/KR2014/005383 KR2014005383W WO2014204220A1 WO 2014204220 A1 WO2014204220 A1 WO 2014204220A1 KR 2014005383 W KR2014005383 W KR 2014005383W WO 2014204220 A1 WO2014204220 A1 WO 2014204220A1
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- WIPO (PCT)
- Prior art keywords
- reverse osmosis
- osmosis membrane
- amine compound
- aromatic amine
- active layer
- Prior art date
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- 229920002647 polyamide Polymers 0.000 title claims abstract description 93
- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract 2
- 150000003839 salts Chemical class 0.000 title description 24
- 230000004907 flux Effects 0.000 title description 3
- -1 aromatic amine compound Chemical class 0.000 claims abstract description 108
- 239000004952 Polyamide Substances 0.000 claims abstract description 92
- 239000000243 solution Substances 0.000 claims abstract description 74
- 239000007864 aqueous solution Substances 0.000 claims abstract description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 99
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000012695 Interfacial polymerization Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 claims description 3
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- 229940044174 4-phenylenediamine Drugs 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 84
- 230000000052 comparative effect Effects 0.000 description 21
- 239000012466 permeate Substances 0.000 description 19
- 230000008569 process Effects 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 229920002492 poly(sulfone) Polymers 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 230000003204 osmotic effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000000576 supplementary effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- 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
- B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/1213—Laminated layers
-
- 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
- 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
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/06—Surface irregularities
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Definitions
- the present invention relates to a polyamide reverse osmosis membrane production method and a reverse osmosis membrane prepared by the above production method, and more specifically, to increase the surface area and roughness of the polyamide active layer to improve the salt removal rate and permeate flow rate characteristics It relates to a method for preparing an amide reverse osmosis membrane and a reverse osmosis membrane prepared by the above method.
- Osmotic phenomenon in which a solvent moves from a solution having a low solute concentration toward a high solution between two solutions separated by a semipermeable membrane is called an osmotic phenomenon.
- applying an external pressure higher than osmotic pressure causes the solvent to move toward a solution with a low concentration of solute.
- This phenomenon is called reverse osmosis.
- a pressure gradient can be used as a driving force to separate various salts or organic substances through the semipermeable membrane.
- Reverse osmosis membrane using the reverse osmosis phenomenon is used to separate the material of the molecular level, remove the salt from the brine or sea water to supply the domestic, construction, industrial water.
- the most important function of the reverse osmosis membrane is to have a high salt removal rate at the boundary of the membrane and to maintain a high flux of solvent even at a relatively low pressure.
- a reverse osmosis membrane has been proposed that has a high salt removal rate while maintaining a high permeate flow rate by forming a thin active layer on the porous support for maintaining the mechanical strength of the separator.
- the reverse osmosis membrane disclosed in U.S. Patent No. 4,277,344 include a polyamide reverse osmosis membrane, and the polyamide reverse osmosis membrane is prepared by a method of forming a polyamide active layer on a microporous support.
- a polysulfone layer is formed on the nonwoven fabric to form a microporous support, and the microporous support is immersed in an m-phenylenediamine (mPD) aqueous solution to form an mPD layer.
- mPD m-phenylenediamine
- TMC TriMesoyl Chloride
- the reverse osmosis membrane presented above has a problem that the replacement cycle of the membrane is short due to a rapid decrease in chlorine resistance with time. Therefore, a method for increasing the specific surface area of the active layer has been proposed to slow down the decrease in chlorine resistance of the reverse osmosis membrane.
- Japanese Patent Application Laid-open No. Hei 10-337454 discloses that the surface of the skin layer is uneven or wrinkled by immersing it in an acidic solution after forming an active layer to increase the specific surface area of the skin layer of the reverse osmosis membrane.
- the method discloses a method of increasing the surface roughness by post-treatment with a strong acid after the reverse osmosis membrane production.
- the present invention is to solve the above problems, after the polyamide active layer is polymerized to form a membrane by increasing the surface area and roughness of the polyamide active layer through the process of further contacting the organic solution containing the polyfunctional aromatic amine compound
- An object of the present invention is to provide a polyamide reverse osmosis membrane having excellent salt removal rate and permeate flow rate.
- the present invention comprises the steps of forming an aqueous solution layer comprising a multifunctional aromatic amine compound on the porous support; Contacting an organic solution containing an acyl halide compound on the aqueous solution layer to form a polyamide active layer; And it provides a method for producing a reverse osmosis membrane comprising the step of contacting the organic solution containing a polyfunctional aromatic amine compound on the polyamide active layer.
- the polyfunctional aromatic amine compound is preferably a compound represented by the following formula (1).
- R 1 to R 6 are NX 1 X 2 , the remainder are each independently H or halogen, wherein X 1 and X 2 are each independently hydrogen, C 1-8 alkoxy, C 1 -15 alkyl, C 2-12 alkenyl, C 3-8 cycloalkyl, C 3-8 cycloalkenyl, C 4-12 alkylcycloalkyl, C 4-12 alkylcycloalkenyl, C 6-10 aryl, and C 6-10 aryl-C 1-8 alkyl.
- the polyfunctional aromatic amine compound is m-phenylenediamine, p-phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3 It may be selected from the group consisting of -phenylenediamine, 3-chloro-1,4-phenylenediamine and mixtures thereof, preferably m-phenylenediamine.
- the acyl halide compound may be at least one selected from the group consisting of trimezoyl chloride, isophthaloyl chloride and terephthaloyl chloride.
- the step of contacting the organic solution containing the polyfunctional aromatic amine compound on the polyamide active layer to form a polyamide through an additional interfacial polymerization reaction of the unreacted acyl halide compound and the polyfunctional aromatic amine compound on the polyamide active layer may include the step.
- the organic solution containing the polyfunctional aromatic amine compound may be an alcohol solvent.
- the organic solution containing the polyfunctional aromatic amine compound may include one or more solvents selected from the group consisting of isopropyl alcohol (IPA), methanol, ethanol, n-propanol.
- IPA isopropyl alcohol
- methanol ethanol
- n-propanol n-propanol
- the organic solution containing the polyfunctional aromatic amine compound contains 1 to 30% by weight of the polyfunctional aromatic amine compound.
- the polyfunctional aromatic amine compound used in the aqueous solution layer containing the said polyfunctional aromatic amine compound and the organic solution containing a polyfunctional aromatic amine compound use the same kind of compound.
- the present invention includes a polyamide active layer formed on the porous support prepared by the method of the present invention, wherein the polyamide active layer is further polymerized with an unreacted acyl halide compound and a polyfunctional aromatic amine compound. It provides a reverse osmosis membrane comprising a three-dimensional network structure region formed by.
- the thickness of the polyamide active layer in the reverse osmosis membrane is 200 to 1000nm
- the three-dimensional network structure region formed in the polyamide active layer provides a reverse osmosis membrane of 50 to 90% of the total area of the polyamide active layer.
- the present invention provides a water treatment module including at least one or more reverse osmosis membranes and a water treatment apparatus including at least one water treatment module.
- the reverse osmosis membrane formed by the method of the present invention which further contacts the organic solution containing the high concentration polyfunctional aromatic amine compound, increases the surface area and roughness of the polyamide active layer, thereby increasing high permeate flow rate and It has the effect of showing excellent salt removal rate.
- Example 1 is a SEM photograph taken at 10000 magnification of the surface of the polyamide active layer prepared in Example 4.
- FIG. 2 is a SEM photograph taken at 20000 magnification of the surface of the polyamide active layer prepared in Example 4.
- FIG. 2 is a SEM photograph taken at 20000 magnification of the surface of the polyamide active layer prepared in Example 4.
- Example 3 is a SEM photograph taken at 50000 magnification of the surface of the polyamide active layer prepared in Example 4.
- the present inventors conducted a study to develop a reverse osmosis membrane having excellent salt removal rate and permeate flow rate characteristics, forming a polyfunctional aromatic amine compound aqueous solution layer on a support, and using the organic solution containing an acyl halide compound on the aqueous solution layer. If the polyamide active layer is further formed by contacting an organic solution containing a polyfunctional aromatic amine compound after forming a polyamide active layer, a reverse osmosis membrane having excellent salt removal rate and permeate flow rate can be obtained. It has been found that the present invention has been completed.
- the reverse osmosis membrane of the present invention comprises the steps of forming an aqueous solution layer containing a polyfunctional aromatic amine compound on the porous support (hereinafter 'step 1'); After contacting the organic solution containing an acyl halide compound on the aqueous solution layer to form a polyamide active layer (hereinafter referred to as "step 2"), the polyamide active layer includes a polyfunctional aromatic amine compound After the step of contacting the organic solution (hereinafter referred to as '3 steps'), the unreacted acyl halide compound and the polyfunctional aromatic amine compound form a polyamide through an additional interfacial polymerization reaction to increase the surface area or roughness reverse osmosis membrane To prepare.
- a coating layer of a polymer material is formed on the nonwoven fabric
- the polymer material For example, polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyetheretherketone, polypropylene, polymethylpentene, polymethyl chloride and polyvinylidene fluoride may be used. However, it is not necessarily limited thereto. Among these, polysulfone is particularly preferable.
- the polyfunctional aromatic amine compound in the aqueous solution containing the amine compound is not limited if the polyfunctional aromatic amine compound used for the reverse osmosis membrane production, but is preferably a compound represented by the formula (1).
- R 1 to R 6 are NX 1 X 2 , the remainder are each independently H or halogen, wherein X 1 and X 2 are each independently hydrogen, C 1-8 alkoxy, C 1 -15 alkyl, C 2-12 alkenyl, C 3-8 cycloalkyl, C 3-8 cycloalkenyl, C 4-12 alkylcycloalkyl, C 4-12 alkylcycloalkenyl, C 6-10 aryl, and C 6-10 aryl-C 1-8 alkyl.
- the polyfunctional aromatic amine compound is not limited thereto, for example, m-phenylenediamine (mPD), p-phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1, More preferred is 3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylene diamine or mixtures thereof.
- mPD m-phenylenediamine
- p-phenylenediamine 1,3,6-benzenetriamine
- 4-chloro-1 More preferred is 3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylene diamine or mixtures thereof.
- the content of the polyfunctional aromatic amine compound in the aqueous amine solution is preferably about 0.5 to 5% by weight.
- the membrane is sufficiently formed to exhibit high salt removal rate and at the same time have proper water permeability.
- the method of forming the aqueous amine layer on the porous support is not excluded any method as long as it can form an aqueous solution on the support.
- any method such as spraying, coating, dipping and dropping can be used.
- the step of removing the aqueous solution comprising the excess polyfunctional aromatic amine compound can be further subjected to the step, if the excess aqueous solution is not removed, the polyamide active layer is not formed safely on the support layer and forms a non-uniform layer after interfacial polymerization. Problems will arise. Removal of the excess aqueous solution may be performed using a sponge, air knife, nitrogen gas blowing, natural drying, or a compression roll, but is not particularly limited thereto.
- an organic solution containing an acyl halide compound is contacted on the aqueous solution layer to form a polyamide active layer.
- the polyfunctional aromatic amine compound coated on the surface and the acyl halide compound react with each other to produce polyamide by interfacial polymerization, and adsorbed onto the microporous support to form a thin film.
- the polyamide active layer may be formed through a method such as dipping, spraying or coating.
- the acyl halide compound is not limited thereto, but is, for example, an aromatic compound having 2-3 carboxylic acid halides, and is selected from the group consisting of trimezoyl chloride, isophthaloyl chloride and terephthaloyl chloride. It may be one or more mixtures selected.
- the organic solvent of the solution containing the acyl halide compound it is preferable to use a solvent which does not participate in the interfacial polymerization reaction as a hydrocarbon compound, does not cause chemical bonding with the acyl halide compound, and does not damage the porous support layer.
- a solvent which does not participate in the interfacial polymerization reaction as a hydrocarbon compound, does not cause chemical bonding with the acyl halide compound, and does not damage the porous support layer.
- a solvent which does not participate in the interfacial polymerization reaction as a hydrocarbon compound, does not cause chemical bonding with the acyl halide compound, and does not damage the porous support layer.
- a solvent which does not participate in the interfacial polymerization reaction as a hydrocarbon compound, does not cause chemical bonding with the acyl halide compound, and does not damage the porous support layer.
- the contact or immersion time may be about 1 minute to 5 hours, more preferably about 1 minute to 3 hours. If the immersion time is less than 1 minute, the coating layer is not formed sufficiently, if the immersion time exceeds 5 hours, the coating layer thickness is too thick has a negative effect of reducing the permeate flow rate of the reverse osmosis membrane.
- the drying is preferably performed for 1 to 10 minutes in the oven at 45 °C to 80 °C.
- the washing is not particularly limited, but may be, for example, washed in a basic aqueous solution.
- the basic aqueous solution that can be used is not particularly limited, but for example, an aqueous sodium carbonate solution can be used, and specifically, it is preferably carried out in an aqueous sodium carbonate solution at 20 ° C. to 30 ° C. for 1 hour to 24 hours.
- a polyamide active layer is formed on the porous support, and then contacting the organic solution containing the polyfunctional aromatic amine compound on the polyamide active layer (step 3).
- the three step process may be carried out after drying in an oven and before washing in a basic aqueous solution.
- the three-step process is characterized in that the polyamide is produced through an additional interfacial polymerization of the polyfunctional aromatic amine compound newly contacted with the remaining acyl halide compound of the polyamide active layer.
- the polyamide active layer by further polymerizing the polyamide active layer, a polyamide having a three-dimensional network structure is produced.
- an additional interfacial polymerization reaction may be used to remove some regions in which the degree of polymerization of the polyamide is poor.
- the salt removal rate is greatly improved.
- the organic solvent of the organic solution containing the polyfunctional aromatic amine compound is not limited thereto, but preferably includes an alcohol solvent, and is selected from the group consisting of isopropyl alcohol (IPA), methanol, ethanol and n-propanol. It is more preferred to include at least one solvent.
- IPA isopropyl alcohol
- methanol methanol
- ethanol ethanol
- n-propanol n-propanol
- the concentration of the alcohol is preferably 50% or more, more preferably 70% or more.
- the type of the polyfunctional aromatic amine compound used in the three-step process is the same as the polyfunctional aromatic amine compound used in the one-step process, it is preferable that the compound represented by the formula (1).
- the multifunctional amine compound to be post-treated is a cyclic amine compound such as piperazine, which is not an aromatic amine compound, the reactivity with the acyl halide compound is small, and in the case of the chain amine compound, the pore of the polyamide is formed by further interfacial polymerization. The size becomes large. As a result, there is a problem that the salt removal rate is greatly lowered and it is impossible to use the reverse osmosis membrane.
- the polyfunctional aromatic amine compound used in the aqueous solution layer containing the said polyfunctional aromatic amine compound and the organic solution containing a polyfunctional aromatic amine compound use the same kind mutually. This is because it is advantageous in view of the adhesion between the polyamide active layer and the polyamide to be further produced and the uniformity of the pore size of the polyamide active layer.
- the multifunctional aromatic amine compound in the organic solution including the multifunctional aromatic amine compound may be included in an amount of 1 to 30% by weight, preferably 5 to 30% by weight, and more preferably 10 to 30% by weight. . If the content of the polyfunctional aromatic amine compound is less than 1% by weight, it is difficult to increase the surface area of the polyamide active layer through sufficient reaction with the unreacted acyl halide compound present on top of the polyamide active layer due to the low amine compound concentration. If it exceeds, the reaction with the unreacted acyl halide compound is too excessive and proceeds rapidly to decrease the permeate flow rate, and as the concentration of the solution increases, the solution progresses rapidly, making it difficult to use continuously under uniform conditions. Because.
- the three-step process performs interfacial polymerization with an unreacted acyl halide compound on the polyamide active layer. As such, by introducing an excess of polyfunctional aromatic amine compounds, an additional interfacial polymerization reaction is caused.
- the contact time is preferably about 1 second to 60 seconds, more preferably about 5 seconds to 20 seconds. If the contact time is less than 1 second, no further interfacial polymerization reaction occurs, and if the contact time is longer than 60 seconds, the polymerization proceeds excessively, and the unreacted remaining polyfunctional aromatic amine compound due to volatilization of the solvent There is a problem that browning occurs on the surface.
- the present invention is a reverse osmosis membrane prepared by the above method, comprising a porous support and a polyamide active layer formed on the porous support, the polyamide active layer is an unreacted acyl halide compound and a polyfunctional aromatic It provides a reverse osmosis membrane comprising a three-dimensional network structure region formed by the polymerization of the amine compound.
- the polyamide active layer of the reverse osmosis membrane prepared by the production method of the present invention is polymerized by the organic solution containing the polyfunctional aromatic amine compound to be contacted additionally to form a three-dimensional network structure region ( 1 to 3).
- the concentration of the unreacted acyl halide is locally different and thus the degree of polymerization of the polyamide is significantly different, the polymerization proceeds in some regions to form different polyamides having different heights depending on positions. Comparing FIGS. 1 to 3 with FIGS. 4 to 6, the polyamide active layer of FIG. 1 has a large roughness difference and a three-dimensional network structure having numerous large and small pores.
- the area of the three-dimensional network structure region may be about 50% to 90%, preferably 60% to 80% of the total area of the polyamide active layer.
- the area of the three-dimensional network structure region is obtained by, for example, using a microscope to obtain a two-dimensional image of the surface of the separator in a state of maximizing contrast due to the difference in roughness, and then formed by additional polymerization to the total separator area. It can obtain by calculating the ratio of polyamide.
- the thickness of the polyamide active layer is 200 to 1000 nm, preferably 300 to 500 nm, more preferably 350 to 400 nm.
- the polyamide active layer has a thickness of 100 to 200 nm, and when the polyamide active layer is thicker, the salt removal rate is maintained, but the permeate flow rate is significantly reduced.
- the polyamide active layer produced by the present invention has a very large roughness due to the three-dimensional network structure, the transmission flow rate does not decrease even if the polymerization thickness is increased to 200 nm or more due to the polyamide of the three-dimensional network structure.
- the thickness of the polyamide active layer exceeds 1000 nm, the permeate flow rate is likely to decrease as in the conventional polyamide reverse osmosis membrane.
- porous polysulfone support prepared by the above method was soaked for 2 minutes in an aqueous solution containing 2% by weight of m-phenylenediamine (mPD), and then the excess aqueous solution on the support was removed by using a 25 psi roller, and at room temperature. It dried for 1 minute.
- mPD m-phenylenediamine
- the support was immersed for 1 minute in an organic solution containing 0.1% by weight of trimezoyl chloride (TMC) using an ISOL-G (EXXONMOBIL CHEMICAL) solvent, and then dried for 10 minutes in an oven at 60 °C.
- TMC trimezoyl chloride
- the reverse osmosis membrane obtained by the above method was washed with 0.2 wt% sodium carbonate aqueous solution at room temperature for 2 minutes, and then washed again with distilled water for 1 minute to prepare a reverse osmosis membrane having a polyamide active layer.
- the initial salt removal rate and initial permeation flux of the reverse osmosis membranes prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated in the following manner.
- the initial salt removal rate and initial permeate flow rate were measured while supplying a 32,000 ppm aqueous sodium chloride solution at 25 ° C. at a flow rate of 4500 mL / min.
- the reverse osmosis membrane cell device used for the membrane evaluation was equipped with a flat permeation cell, a high pressure pump, a storage tank, and a cooling device.
- the flat permeation cell has a cross-flow type, and its effective permeation area is 140 cm 2 . .
- Example 1 Table 1 division Solvent Composition (wt%) MPD addition amount (% by weight) Salt removal rate (%) Permeate Flow Rate (GFD)
- Example 1 IPA 75% One 99.18 31.01
- Example 2 5 99.25 31.58
- Example 3 10 99.45 34.89
- Example 4 20 99.71 36.91
- Example 5 30 99.60 35.34
- Example 6 Ethanol 75% 20 99.65 35.76
- Example 7 Methanol 75% 20 99.61 35.24 Comparative Example 1 - - 99.12 30.37 Comparative Example 2 DI Water 100% 20 99.09 30.04 Comparative Example 3 IPA 75% 20 98.85 35.73
- Comparative Example 4 IPA 75% 0.05 98.87 30.26 Comparative
- Example 5 IPA 75% 50 99.35 28.52
- the surface of the polyamide active layer prepared according to Example 4 and Example 1 was photographed by SEM photograph by adjusting the magnification.
- 4 to 6 show photographs photographing the surface of the polyamide active layer of Example 4, and photographs photographing the surface of the polyamide active layer prepared according to Comparative Example 1, respectively. 1 to 3, it can be seen that the polyamide active layer prepared in Example 4 has a three-dimensional network structure.
- the range of the polymerization region further formed through the three-dimensional network structure on the surface of the reverse osmosis membrane prepared in Examples 4, 6 and 7 and Comparative Examples 1, 2, 4 and 5 is summarized in [Table 2].
- the image analysis program was used to calculate the ratio of the total image area-by-list (ie, 3D network structure area formed on the surface due to further polymerization) to the total area of the polyamide active layer.
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Abstract
Description
구분 | 용매 조성(중량%) | MPD 첨가량(중량%) | 염제거율(%) | 투과유량(GFD) |
실시예 1 | IPA 75% | 1 | 99.18 | 31.01 |
실시예 2 | 5 | 99.25 | 31.58 | |
실시예 3 | 10 | 99.45 | 34.89 | |
실시예 4 | 20 | 99.71 | 36.91 | |
실시예 5 | 30 | 99.60 | 35.34 | |
실시예 6 | Ethanol 75% | 20 | 99.65 | 35.76 |
실시예 7 | Methanol 75% | 20 | 99.61 | 35.24 |
비교예 1 | - | - | 99.12 | 30.37 |
비교예 2 | D.I Water 100% | 20 | 99.09 | 30.04 |
비교예 3 | IPA 75% | 20 | 98.85 | 35.73 |
비교예 4 | IPA 75% | 0.05 | 98.87 | 30.26 |
비교예 5 | IPA 75% | 50 | 99.35 | 28.52 |
구분 | 용매 조성(중량%) | MPD 첨가량(중량%) | 추가 중합 영역(%) |
실시예 4 | IPA 75% | 20 | 80 |
실시예 6 | ETHANOL 75% | 20 | 65 |
실시예 7 | Methanol 75% | 20 | 60 |
비교예 1 | - | - | 15 |
비교예 2 | D.I WATER 100% | 20 | 20 |
비교예 4 | IPA 75% | 0.05 | 25 |
비교예 5 | IPA 75% | 50 | 45 |
Claims (14)
- 다공성 지지체 상에 다관능성 방향족 아민 화합물을 포함하는 수용액층을 형성하는 단계;상기 수용액층 상에 아실 할라이드 화합물을 포함하는 유기용액을 접촉시켜 폴리아미드 활성층을 형성하는 단계; 및상기 폴리아미드 활성층 상에 다관능성 방향족 아민 화합물을 포함하는 유기용액을 접촉시키는 단계를 포함하는 역삼투 분리막 제조방법.
- 제1항에 있어서,상기 다관능성 방향족 아민 화합물은 m-페닐렌디아민, p-페닐렌디아민, 1,3,6-벤젠트리아민, 4-클로로-1,3-페닐렌디아민, 6-클로로-1,3-페닐렌디아민, 3-클로로-1,4-페닐렌 디아민 및 이들의 혼합물로 이루어진 군으로부터 선택되는 역삼투 분리막 제조방법.
- 제1항에 있어서,상기 아실 할라이드 화합물은 트리메조일클로라이드, 이소프탈로일클로라이드 및 테레프탈로일클로라이드로 이루어진 군으로부터 선택되는 1종 이상인 역삼투 분리막 제조방법.
- 제1항에 있어서,상기 폴리아미드 활성층 상에 다관능성 방향족 아민 화합물을 포함하는 유기용액을 접촉시키는 단계는 상기 폴리아미드 활성층 상의 미반응 아실 할라이드 화합물과 다관능성 방향족 아민 화합물의 추가적인 계면 중합 반응을 통해 폴리아미드를 형성하는 단계를 포함하는 역삼투 분리막 제조방법.
- 제1항에 있어서,상기 다관능성 방향족 아민 화합물을 포함하는 유기용액은 알코올 용매를 포함하는 것인 역삼투 분리막 제조방법.
- 제1항에 있어서,상기 다관능성 방향족 아민 화합물을 포함하는 유기용액은 이소프로필알코올(IPA), 메탄올, 에탄올 및 n-프로판올로 이루어진 군으로부터 선택되는 1종 이상의 용매를 포함하는 것인 역삼투 분리막 제조방법.
- 제1항에 있어서,상기 다관능성 방향족 아민 화합물을 포함하는 유기용액은 1 내지 30 중량%의 다관능성 방향족 아민 화합물을 포함하는 역삼투 분리막 제조방법.
- 제1항에 있어서,상기 다관능성 방향족 아민 화합물을 포함하는 수용액층 및 다관능성 방향족 아민 화합물을 포함하는 유기용액에서 이용되는 다관능성 방향족 아민 화합물은 서로 동일한 종류의 화합물인 역삼투 분리막 제조방법.
- 다공성 지지체; 및상기 다공성 지지체 상에 형성되는 폴리아미드 활성층을 포함하고,상기 폴리아미드 활성층은 미반응된 아실 할라이드 화합물과 다관능성 방향족 아민 화합물이 추가적으로 중합하여 형성된 3차원 망상 구조 영역을 포함하는 역삼투 분리막.
- 제10항에 있어서,상기 폴리아미드 활성층에 형성된 3차원 망상 구조 영역은 폴리아미드 활성층 전체 면적에 대하여 50 내지 90%인 역삼투 분리막.
- 제10항에 있어서,상기 폴리아미드 활성층의 두께는 200 내지 1000nm인 역삼투 분리막.
- 제10항 내지 제12항 중 어느 한 항의 역삼투 분리막을 적어도 하나 이상 포함하는 수처리 모듈.
- 제13항에 따른 수처리 모듈을 적어도 하나 이상 포함하는 수처리 장치.
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US14/387,486 US20150375179A1 (en) | 2013-06-18 | 2014-06-18 | Method of manufacturing polyamide-based reverse omosis membrane having excellent salt rejection and high permeable flux properties, and reverse osmosis membrane manufactured using the same |
JP2016516463A JP6212205B2 (ja) | 2013-06-18 | 2014-06-18 | 塩除去率及び透過流量特性に優れたポリアミド系逆浸透分離膜の製造方法、及び上記製造方法で製造された逆浸透分離膜 |
CN201480000953.6A CN104507556B (zh) | 2013-06-18 | 2014-06-18 | 具有优异脱盐率和高渗透通量性质的聚酰胺类反渗透膜的制备方法,以及使用该方法制备的反渗透膜 |
EP14766383.5A EP2842621B1 (en) | 2013-06-18 | 2014-06-18 | Method for preparing polyamide-based reverse osmosis membrane |
US16/044,356 US20180326366A1 (en) | 2013-06-18 | 2018-07-24 | Method of manufacturing polyamide-based reverse osmosis membrane having excellent salt rejection and high permeable flux properties, and reverse osmosis membrane manufactured using the same |
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US16/044,356 Continuation US20180326366A1 (en) | 2013-06-18 | 2018-07-24 | Method of manufacturing polyamide-based reverse osmosis membrane having excellent salt rejection and high permeable flux properties, and reverse osmosis membrane manufactured using the same |
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- 2014-06-18 WO PCT/KR2014/005383 patent/WO2014204220A1/ko active Application Filing
- 2014-06-18 US US14/387,486 patent/US20150375179A1/en not_active Abandoned
- 2014-06-18 KR KR1020140074430A patent/KR101682759B1/ko active IP Right Grant
- 2014-06-18 JP JP2016516463A patent/JP6212205B2/ja active Active
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Title |
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See also references of EP2842621A4 |
Also Published As
Publication number | Publication date |
---|---|
JP6212205B2 (ja) | 2017-10-11 |
CN104507556A (zh) | 2015-04-08 |
CN104507556B (zh) | 2017-02-22 |
US20180326366A1 (en) | 2018-11-15 |
KR101682759B1 (ko) | 2016-12-12 |
KR20140147053A (ko) | 2014-12-29 |
EP2842621B1 (en) | 2020-02-19 |
JP2016524530A (ja) | 2016-08-18 |
EP2842621A4 (en) | 2015-11-04 |
EP2842621A1 (en) | 2015-03-04 |
US20150375179A1 (en) | 2015-12-31 |
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