KR0165749B1 - Reverse osmotic composite film having poly m-styreneamide or poly m-styreneamide/aromatic polyamide alloy layer - Google Patents
Reverse osmotic composite film having poly m-styreneamide or poly m-styreneamide/aromatic polyamide alloy layer Download PDFInfo
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- KR0165749B1 KR0165749B1 KR1019960000507A KR19960000507A KR0165749B1 KR 0165749 B1 KR0165749 B1 KR 0165749B1 KR 1019960000507 A KR1019960000507 A KR 1019960000507A KR 19960000507 A KR19960000507 A KR 19960000507A KR 0165749 B1 KR0165749 B1 KR 0165749B1
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- aminostyrene
- styreneamide
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 239000004760 aramid Substances 0.000 title claims abstract description 9
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 9
- 239000000956 alloy Substances 0.000 title claims description 6
- 229910045601 alloy Inorganic materials 0.000 title claims description 6
- 230000003204 osmotic effect Effects 0.000 title 1
- 239000012528 membrane Substances 0.000 claims abstract description 70
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- -1 aromatic acyl halide Chemical class 0.000 claims abstract description 17
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 14
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 claims description 28
- 125000003277 amino group Chemical group 0.000 claims description 9
- 150000001266 acyl halides Chemical class 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000007942 carboxylates Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 230000035699 permeability Effects 0.000 abstract description 16
- 150000003839 salts Chemical class 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 description 18
- 239000010410 layer Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229920002492 poly(sulfone) Polymers 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- SYZVQXIUVGKCBJ-UHFFFAOYSA-N 1-ethenyl-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(C=C)=C1 SYZVQXIUVGKCBJ-UHFFFAOYSA-N 0.000 description 7
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- VKVLTUQLNXVANB-UHFFFAOYSA-N 1-ethenyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C=C VKVLTUQLNXVANB-UHFFFAOYSA-N 0.000 description 5
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 5
- KURPPWHPIYBYBS-UHFFFAOYSA-N 2-ethenylaniline Chemical compound NC1=CC=CC=C1C=C KURPPWHPIYBYBS-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 5
- 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 5
- 230000029142 excretion Effects 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 3
- 229940067157 phenylhydrazine Drugs 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 2
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 2
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- 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
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
- B01D71/281—Polystyrene
-
- 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
- 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
-
- 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
- B01D2323/30—Cross-linking
Abstract
본 발명은 다공성 지지막 및 그 위에 폴리 m-아미노스티렌의 수용액과 방향족 아실 할라이드를 유기 용매에 용해시켜 제조한 용액을 계면 중합시켜 형성한 가교된 폴리 m-스티렌아미드 활성층으로 이루어지는 역삼투 복합막을 제공한다. 또한, 본 발명은 고분자 다공막 지지체 및 그 위에 폴리 m-아미노스티렌의 수용액과 방향족 아민의 수용액을 혼합하여 제조한 혼합 수용액과 방향족 아실 할라이드를 유기 용매에 용해시켜 제조한 용액을 계면 중합시켜 형성한 가교된 폴리 m-스티렌아미드/방향족 폴리아미드 활성층으로 이루어지는 역삼투 복합막을 제공한다. 본 발명에 의해 제공된 복합막은 수투과도 및 염배제율이 모두 우수하다.The present invention provides a reverse osmosis composite membrane comprising a crosslinked polym-styreneamide active layer formed by interfacial polymerization of a porous support membrane and a solution prepared by dissolving an aqueous solution of polym-aminostyrene and an aromatic acyl halide in an organic solvent thereon. do. In addition, the present invention is formed by interfacial polymerization of a polymer porous membrane support and a solution prepared by dissolving an aqueous solution of polym-aminostyrene and an aqueous solution of aromatic amine and an aromatic acyl halide in an organic solvent. It provides a reverse osmosis composite membrane composed of a crosslinked polym-styreneamide / aromatic polyamide active layer. The composite membrane provided by the present invention has excellent water permeability and salt rejection.
Description
본 발명은 우수한 수투과도와 염배제율을 갖는 역삼투 복합막에 관한 것이다. 더욱 구체적으로 말하자면, 본 발명은 다공성 지지막 및 그 위에 가교된 폴리 m-스티렌아미드 또는 폴리 m-스티렌아미드/방향족 폴리아미드 아로이(alloy)를 활성층으로 갖는 역삼투 복합막에 관한 것이다.The present invention relates to a reverse osmosis composite membrane having excellent water permeability and salt rejection rate. More specifically, the present invention relates to a reverse osmosis composite membrane having a porous support membrane and a poly m-styreneamide or a poly m-styreneamide / aromatic polyamide alloy crosslinked thereon as an active layer.
에너지 절약, 환경 보호 등의 측면에서, 역삼투막을 이용하여 해수, 염수, 폐수 등으로부터 염을 제거하는 공정은 오늘날까지 많은 주목을 받아오고 있다. 최초로 개발된 역삼투막은 레오브(Leob)와 수리라잔(Sourirajan)에 의해 1962년에 개발된 셀룰로오스 아세테이트 비대칭막이다. (미합중국 특허 제3,133,132호 및 동 제3,133,137호 참조). 셀룰로오스 아세테이트 비대칭막 이후 새로운 소재들에 대한 연구가 진행되어, 방향족 폴리아미드, 폴리아미드, 히드라지드(미합중국 특허 제3,567,632호 참조), 폴리아미드산(미합중국 특허 제3,878,109호 참조) 등을 이용한 비대칭막이 개발되었다.In terms of energy saving, environmental protection, etc., the process of removing salt from seawater, brine, wastewater, etc. using a reverse osmosis membrane has received much attention until today. The first reverse osmosis membrane developed was the cellulose acetate asymmetric membrane developed in 1962 by Leo and Sourirajan. (See US Pat. Nos. 3,133,132 and 3,133,137). After the cellulose acetate asymmetric membrane, new materials were studied to develop an asymmetric membrane using aromatic polyamide, polyamide, hydrazide (see US Pat. No. 3,567,632), polyamic acid (see US Pat. No. 3,878,109), and the like. It became.
그러나, 이들 비대칭막은 수처리 성능상의 문제점으로 인하여 거의 사용되지 않고 있으며, 최근에는 다공성 지지막 위에 분리 성능을 결정하는 초박막 형태의 활성층을 제막한 복합막이 개발되어 널리 사용되고 있다. 이 복합막은 활성층과 다공성 지지막의 소재를 상업적 응용 용도에 적합하게 선택함으로써 용도에 적합한 분리막을 제조할 수 있다는 잇점이 있다. 이들 복합막 중 최근에 가장 널리 사용되는 것은 가교된 폴리아미드를 활성층으로 이용하는 것들이다. (미합중국 특허 제4,277,344호, 동 제4,606,943호, 동 제4,643,829호, 동 제4,626,468호, 유럽 특허 출원 제863,059,440호 참조). 그러나, 가교된 폴리아미드를 활성층으로 이용한 복합막은 염배제율에서는 우수한 성능을 보였지만, 수투과도에서는 만족할만한 수준에 도달하지 못했다.However, these asymmetric membranes are rarely used due to problems in water treatment performance, and recently, a composite membrane in which an ultra-thin active layer is formed on the porous support membrane has been developed and widely used. This composite membrane has the advantage that a separator suitable for the application can be produced by selecting the active layer and the porous support membrane appropriately for commercial applications. The most widely used of these composite membranes in recent years are those using crosslinked polyamide as an active layer. (See, U.S. Patent Nos. 4,277,344, 4,606,943, 4,643,829, 4,626,468, and European Patent Application No.863,059,440). However, the composite membrane using the crosslinked polyamide as an active layer showed excellent performance in salt rejection, but did not reach a satisfactory level in water permeability.
이와 같이 폴리아미드를 활성층으로 하는 복합막의 불만족스러운 수투과도 문제를 해결하기 위해, 일본국 특허 공개 (소)55-97204호에서는 폴리 p-스티렌아미드 또는 폴리 o-스티렌아미드를 활성층으로 하는 복합막을 제안하고 있다. 이 문헌에 의하면, 스티렌 단량체로부터 폴리스티렌을 제조한 후, 이 폴리스티렌을 니트로화시켜 폴리 p-니트로스티렌 또는 폴리 o-니트로스티렌을 제조하고, 이어서 이를 환원시켜 폴리 p-아미노스티렌 또는 폴리 o-아미노스티렌을 제조한다. 이와 같이 하여 얻어진 폴리 p-아미노스티렌 또는 폴리 o-아미노스티렌의 수용액과 유기 용매에 용해시킨 방향족 아실 할라이드의 용액을 계면 중합시켜서 얻은 가교된 폴리 p-스티렌아미드 또는 폴리 o-스티렌아미드를 활성층으로 사용한다.In order to solve the problem of unsatisfactory water permeability of the composite membrane containing polyamide as an active layer, Japanese Patent Laid-Open No. 55-97204 proposes a composite membrane using poly p-styreneamide or poly o-styreneamide as an active layer. Doing. According to this document, polystyrene is prepared from styrene monomers, and then the polystyrene is nitrated to produce poly p-nitrostyrene or poly o-nitrostyrene, which is then reduced to poly p-aminostyrene or poly o-aminostyrene. To prepare. The crosslinked poly p-styreneamide or poly o-styreneamide obtained by interfacial polymerization of the aqueous solution of poly p-aminostyrene or polyo-aminostyrene thus obtained and the solution of aromatic acyl halide dissolved in an organic solvent is used as an active layer. do.
그러나, 상기 일본국 특허 공개 (소)55-97204호에서와 같이 스티렌 단량체로 부터 폴리스티렌을 제조한 후, 이 폴리스티렌을 니트로화하여 폴리 p-니트로스티렌 또는 폴리 o-니트로스티렌을 제조하는 경우에는 일부만이 니트로화되기 때문에 아미노기 치환율이 낮고, 또한 활성층을 제조하는 공정이 복잡할 뿐만 아니라, 제조된 역삼투 복합막은 상업적으로 응용되는 다른 복합막에 비해 수투과도의 향상은 기대할 수 있으나, 염배제율의 저하가 심각하여 상업적 응용이 불가능하였다.However, in the case of preparing polystyrene from styrene monomers as in Japanese Patent Laid-Open No. 55-97204, and then nitrifying the polystyrene to produce poly p-nitrostyrene or poly o-nitrostyrene, only a part thereof is used. Because of the nitration, the amino group substitution rate is low, and the process of preparing the active layer is not only complicated, but the prepared reverse osmosis composite membrane can be expected to have improved water permeability compared to other commercially available composite membranes. The degradation was so severe that commercial applications were not possible.
따라서, 본 발명의 목적은 수투과도가 우수할 뿐만 아니라 염배제율도 적절히 유지되어 상업적으로 응용이 가능한 역삼투 복합막을 제공하는 것이다.Accordingly, it is an object of the present invention to provide a reverse osmosis composite membrane which is not only excellent in water permeability but also properly maintained in salt excretion rate.
본 발명자들은 복합막 형태의 역삼투 분리막에 관한 연구를 거듭한 결과, m-니트로스티렌 또는 m-아미노스티렌 단량체로부터 폴리 m-아미노스티렌을 제조한 후, 이를 방향족 아실 할라이드와 계면 중합시켜서 얻은 가교된 폴리 m-스티렌아미드 또는 폴리 m-아미노스티렌과 방향족 아민의 혼합물과 방향족 아실 할라이드를 계면 중합시켜서 얻은 가교된 폴리 m-스티렌아미드/방향족 폴리아미드 아로이를 활성층으로 하는 역삼투 복합막이 기존의 다른 복합막에 비해 수투과도가 우수할 뿐만 아니라 염배제율도 적절히 유지되어 상업적 응용이 가능하다는 것을 발견하였다.The inventors of the present invention have repeatedly studied the reverse osmosis membrane in the form of a composite membrane, and thus, after the polym-aminostyrene is prepared from m-nitrostyrene or m-aminostyrene monomer, it is crosslinked obtained by interfacial polymerization with aromatic acyl halide. Reverse osmosis composite membranes having crosslinked polym-styreneamide / aromatic polyamide alloys obtained by interfacial polymerization of a mixture of polym-styreneamide or polym-aminostyrene with aromatic amines and aromatic acyl halides have been prepared. It was found that not only is the water permeability better than that, but also the salt excretion ratio is appropriately maintained for commercial applications.
본 발명의 한 특징에 따르면, 부직포 위에 다공성의 지지막을 제조한 후, 그 위에 폴리 m-아미노스티렌의 수용액과 유기 용매 중에 용해시킨 2개 이상의 반응성 아실기를 갖는 방향족 아실할라이드의 용액을 계면 중합시켜서 초박막 형태로 가교된 폴리 m-스티렌아미드 활성층을 제막함으로써 제조되는 역삼투 복합막이 제공된다.According to one aspect of the present invention, an ultrathin membrane is prepared by preparing a porous support membrane on a nonwoven fabric, and then performing interfacial polymerization of an aqueous solution of poly m-aminostyrene and an aromatic acyl halide having at least two reactive acyl groups dissolved in an organic solvent thereon. There is provided a reverse osmosis composite membrane prepared by forming a polym-styreneamide active layer crosslinked in the form.
또한, 본 발명의 다른 특징에 따르면, 부직포 위에 다공성의 지지막을 제조한 후, 그 위에 폴리 m-아미노스티렌의 수용액에 방향족 아민의 수용액을 적당량 혼합하여 만든 혼합 수용액과, 유기 용매 중에 용해시킨 2개 이상의 반응성 아실기를 갖는 방향족 아실 할라이드의 용액을 계면 중합시켜서 초박막 형태로 가교된 폴리 m-스티렌아미드/방향족 폴리아미드의 아로이 활성층을 제막함으로써 제조되는 역삼투 복합막이 제공된다.In addition, according to another feature of the present invention, after preparing a porous support membrane on a nonwoven fabric, a mixed aqueous solution made by mixing an appropriate amount of an aromatic amine with an aqueous solution of poly m-aminostyrene thereon, and two dissolved in an organic solvent There is provided a reverse osmosis composite membrane prepared by interfacially polymerizing a solution of the aromatic acyl halide having the reactive acyl group as described above to form an alloy active layer of polym-styreneamide / aromatic polyamide crosslinked in an ultra-thin film form.
이하, 본 발명을 더 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따른 역삼투 복합막의 제1 실시태양은 고분자 다공막 지지체, 및 그 위에 하기 일반식(I)의 폴리 m-아미노스티렌의 수용액과 하기 일반식(II) 또는 (III)의 방향족 아실 할라이드를 유기 용매에 용해시켜서 제조한 용액을 계면 중합시켜서 초박막 형태로 가교된 폴리 m-아미노스티렌 활성층을 제막함으로써 제조된다.A first embodiment of the reverse osmosis composite membrane according to the present invention is a polymer porous membrane support, and an aqueous solution of polym-aminostyrene of the following general formula (I) and an aromatic acyl halide of the following general formula (II) or (III) Is prepared by dissolving the solution prepared by dissolving in an organic solvent in an interfacial polymerization to form a polym-aminostyrene active layer crosslinked into an ultrathin film.
식 중, n은 3내지 100,000의 정수이고, a는 아실 할라이드의 개수를 나타내는 것으로서, 2이상, 바람직하게는 2 내지 4의 정수이며, Y는 가교된 폴리 m-스티렌아미드를 형성하는데 방해가 되지 않는 치환체로서, 브롬, 염소, 히드록실기, 알킬기, 알콕시기, 카르복실기 또는 카르복실레이트기로부터 선택되는 것이고, b는 0내지 4의 정수이며, c 및 d는 각각 아실 할라이드의 개수를 나타내는 것으로서, c+d는 2 이상의 정수, 바람직하게는 2 내지 4의 정수이다.Wherein n is an integer of 3 to 100,000, a is the number of acyl halides, and is an integer of 2 or more, preferably 2 to 4, and Y does not interfere with the formation of the crosslinked polym-styreneamide. Substituents which are not selected are bromine, chlorine, hydroxyl groups, alkyl groups, alkoxy groups, carboxyl groups or carboxylate groups, b is an integer of 0 to 4, c and d each represent the number of acyl halides, c + d is an integer of 2 or more, preferably an integer of 2 to 4.
이 반응에서 사용되는 폴리 m-아미노스티렌 수용액 중의 폴리 m-아미노스티렌의 농도는 약 0.01내지 10중량%이다. 또한, 유기 용매 중의 방향족 아실 할라이드 단량체의 농도는 약 0.01 내지 10중량%이다.The concentration of poly m-aminostyrene in the polym-aminostyrene aqueous solution used in this reaction is about 0.01 to 10% by weight. In addition, the concentration of the aromatic acyl halide monomer in the organic solvent is about 0.01 to 10% by weight.
본 발명에 따른 역삼투 복합막의 제2 실시태양은 고분자 다공막 지지체, 및 그 위에 상기 일반식(I)의 폴리 m-아미노스티렌의 수용액에 하기 일반식(IV)의 방향족 아민의 수용액을 혼합하여 제조한 혼합 수용액과 상기 일반식(II) 또는 (III)의 방향족 아실 할라이드를 유기 용매에 용해시켜서 제조한 용액을 계면 중합시켜서 가교된 폴리 m-아미노스티렌/방향족 폴리아미드의 아로이를 활성층으로서 제막함으로써 제조된다.According to a second embodiment of the reverse osmosis composite membrane according to the present invention, a polymer porous membrane support and an aqueous solution of the polym-aminostyrene of the general formula (I) are mixed with an aqueous solution of the aromatic amine of the general formula (IV) The resulting mixed aqueous solution and the solution prepared by dissolving the aromatic acyl halide of the general formula (II) or (III) in an organic solvent are subjected to interfacial polymerization to form a crosslinked polym-aminostyrene / aromatic polyamide alloy as an active layer. Are manufactured.
식 중, Ar'은 아민기를 제외하고는 아실 할라이드와 반응하지 않는 방향족 환이고, 이 방향족 환에서 아민기가 없는 위치의 수소는 알킬, 알콕시, 술폰산기, 술포네이트기, 카르복실산기, 카르복실레이트기, 아미노기, 아실, 히드록시기, 할로겐 또는 니트로기로 치환될 수 있고; e는 2 이상의 정수이다.In the formula, Ar 'is an aromatic ring which does not react with an acyl halide except for an amine group, and hydrogen in the position where no amine group is present in the aromatic ring is alkyl, alkoxy, sulfonic acid group, sulfonate group, carboxylic acid group, carboxylate May be substituted with a group, amino group, acyl, hydroxy group, halogen or nitro group; e is an integer of 2 or more.
이 반응에서 사용되는 폴리 m-아미노스티렌 수용액 중의 폴리 m-아미노스티렌의 농도는 0.01 내지 10중량%이고, 방향족 아민 단량체의 수용액 중의 방향족 아민 단량체의 농도는 약 0.01내지 10중량%이며, 다만, 혼합 수용액에서, 폴리 m-아미노스티렌과 방향족 아민 단량체의 합계량에 대한 폴리 m-아미노스티렌의 중량비는 0.05내지 1이어야 한다. 또한, 유기 용매 중의 방향족 아실 할라이드 단량체의 농도는 약 0.01 내지 10중량%이다.The concentration of the poly m-aminostyrene in the aqueous poly m-aminostyrene solution used in this reaction is 0.01 to 10% by weight, and the concentration of the aromatic amine monomer in the aqueous solution of the aromatic amine monomer is about 0.01 to 10% by weight, except that In aqueous solution, the weight ratio of poly m-aminostyrene to the total amount of poly m-aminostyrene and aromatic amine monomer should be 0.05 to 1. In addition, the concentration of the aromatic acyl halide monomer in the organic solvent is about 0.01 to 10% by weight.
상기 일반식(I)의 폴리 m-아미노스티렌은 m-니트로스티렌 단량체 또는 m-아미노스티렌 단량체로부터 제조된다. 구체적으로는, 상기 일반식(I)의 폴리 m-아미노스티렌은 적당한 개시제(예 : 아조비스이소부티로니트릴)을 사용하여 m-니트로스티렌 단량체를 라디칼 중합시켜 폴리 m-니트로스티렌을 제조한 후, 적당한 환원제(예 : 페닐 히드라진)을 사용하여 환원시켜 제조한다.The poly m-aminostyrene of the general formula (I) is prepared from an m-nitrostyrene monomer or an m-aminostyrene monomer. Specifically, the poly m-aminostyrene of the general formula (I) may be prepared by radically polymerizing m-nitrostyrene monomer using a suitable initiator (for example, azobisisobutyronitrile) to prepare poly m-nitrostyrene. Prepared by reducing with a suitable reducing agent (e.g., phenyl hydrazine).
다른 방법으로서, 상기 일반식(I)의 폴리 m-아미노스티렌은 m-아미노스티렌 단량체를 적당한 보호기(예 : 트리메틸실릴기 또는 t-부틸디메틸실리기)를 사용하여 아미노기를 보호시킨 후, 보호된 m-아미노스티렌 단량체를 적당한 개시제(예 : 아조비스이소부티로니트릴)를 사용하여 라디칼 중합시키고, 이어서 적당한 시약(예 : 순수)을 사용하여 보호기를 제거함으로써 제조한다.Alternatively, the poly m-aminostyrene of formula (I) may be prepared by protecting the amino group with an appropriate protecting group (e.g. trimethylsilyl or t-butyldimethylsilyl group) of the m-aminostyrene monomer, Aminostyrene monomers are prepared by radical polymerization with a suitable initiator (eg azobisisobutyronitrile) followed by removal of the protecting group with a suitable reagent (eg pure water).
본 발명에 사용되는 방향족 아실 할라이드는 반응성 아실기를 2개 이상 갖는 것, 예를 들면 트리메조일클로라이드, 테레프탈로일클로라이드 또는 트리멜리트산 무수물 클로라이드 등으로부터 선택된다.The aromatic acyl halides used in the present invention are selected from those having two or more reactive acyl groups, for example trimesoyl chloride, terephthaloyl chloride or trimellitic anhydride chloride.
본 발명에서 사용되는 방향족 아민은 예를 들면 m- 또는 p- 페닐렌 디아민을 들 수 있다.Aromatic amines used in the present invention include, for example, m- or p-phenylene diamine.
본 발명에 따른 역삼투 복합막은 그 사용 용도에 따라서 활성층의 두께를 조절할 수 있지만, 활성층의 두께는 10 내지 1,000nm인 것이 바람직하다.The reverse osmosis composite membrane according to the present invention can adjust the thickness of the active layer according to its use, but the thickness of the active layer is preferably 10 to 1,000 nm.
본 발명에 따르면, 상기 일본국 특허 (소)55-97204호에 따른 폴리 p-아미노스티렌 또는 폴리 o-아미노스티렌의 제조방법보다 간단한 방법으로 폴리 m-아미노스티렌을 제조할 수 있다. 또한, 스티렌 단량체 당 아미노기가 각각 하나씩 있기 때문에, 폴리 m-니트로스티렌의 경우 100%의 치환을 기대할 수 있어, 방향족 아실 할라이드와의 계면 중합시에 가교도 및 물에 대한 용해도를 증가시킬 수 있다.According to the present invention, poly m-amino styrene can be produced by a simpler method than the method for producing poly p-amino styrene or poly o-amino styrene according to Japanese Patent No. 55-97204. In addition, since there is one amino group per styrene monomer, 100% substitution can be expected in the case of polym-nitrostyrene, thereby increasing the degree of crosslinking and solubility in water during interfacial polymerization with aromatic acyl halides.
본 발명에 따른 역삼투 복합막은 기존의 다른 복합막에 비해 수투과도가 우수할 뿐만 아니라 염배제율도 적절히 유지되어 상업적 응용이 가능하다.Reverse osmosis composite membrane according to the present invention is excellent in water permeability compared to other conventional composite membranes, and the salt excretion ratio is properly maintained, allowing commercial applications.
이하, 본 발명을 실시예를 들어 상세히 설명한다. 이 실시예는 본 발명을 예시하기 위한 것이며, 본 발명을 한정하지는 않는다.Hereinafter, the present invention will be described in detail with reference to Examples. This example is intended to illustrate the invention and does not limit the invention.
[실시예 1]Example 1
3구 플라스크에 m-니트로스티렌 단량체와 에틸벤젠을 1:10 중량비로 넣고, 반응 개시제로서 아조비스이소부티로니트릴을 m-니트로스티렌 단량체의 0.05중량%가 되는 양으로 첨가한 후, 80℃에서 3시간 동안 질소 하에서 교반하면서 중합시켜 폴리 m-니트로스티렌(중량 평균 부자량 : 50,000)을 제조하였다.Into a three-necked flask, m-nitrostyrene monomer and ethylbenzene were added at a 1:10 weight ratio, and azobisisobutyronitrile was added as an reaction initiator in an amount of 0.05% by weight of m-nitrostyrene monomer, followed by 80 ° C. Polymerization was carried out with stirring under nitrogen for 3 hours to prepare poly m-nitrostyrene (weight average rich weight: 50,000).
이와같이 하여 얻어진 섬유상의 폴리 m-니트로스티렌을 충분히 세척한 후 분쇄하여, 새로운 3구 플라스크에 폴리 m-니트로스티렌 5중량%를 넣고, 교반하면서 질소 하에서 페닐히드라진을 95중량% 넣어 180℃에서 8시간 반응시킨 후, 이 반응 용액을 과량의 에틸이스에 미량씩 주입하면서 침전시켜 폴리 m-아미노스티렌을 제조하였다.The fibrous polym-nitrostyrene thus obtained was sufficiently washed and pulverized, and 5 weight% of polym-nitrostyrene was added to a new three-necked flask, and 95% by weight of phenylhydrazine was added under nitrogen while stirring for 8 hours at 180 ° C. After the reaction, the reaction solution was precipitated while injecting a small amount of excess ethyl acetate to prepare poly m-aminostyrene.
한편, 디메틸 포름 아미드에 폴리술폰 18중량%를 용해시킨 용액을 폴리에스테르 부직포 위에 제막한 후, 즉시 물에 침지시켜 겔화된 부직포 보강 다공성 폴리술폰 지지막을 제조하였다. 이 지지막은 부직포와 접촉하는 부분은 다소 큰 기공을 가지고 있으나 물과 직접 접촉하여 겔화된 반대쪽 표면층은 기공의 크기가 15nm이하이었다.On the other hand, a solution in which 18% by weight of polysulfone was dissolved in dimethyl formamide was formed on a polyester nonwoven fabric, and then immediately immersed in water to prepare a gelled nonwoven fabric-reinforced porous polysulfone support membrane. The support membrane had a rather large pores in contact with the nonwoven fabric, but the opposite surface layer gelled by direct contact with water had a pore size of 15 nm or less.
이렇게 하여 제조된 부직포 보강 폴리술폰 지지막을, 건조 과정없이, 상기 폴리 m-아미노스티렌 0.5중량%를 물에 용해시켜 제조한 용액에 5분 동안 침지시켰다. 폴리술폰 지지막 표면에 과량으로 존재하는 폴리 m-아미노스티렌 수용액을 고무 롤러로 압착하여 제거한 후, 트리메조일클로라이드 0.5중량%를 n-헥산에 용해시킨 용액을 즉시 도포하였다. 계면 중합을 위해 30초간 방치한 후, 얻어진 폴리 술폰/가교된 폴리 m-스티렌아미드 복합막을 60℃오븐에서 건조시켰다.The nonwoven reinforced polysulfone support membrane thus prepared was immersed in a solution prepared by dissolving 0.5% by weight of the poly m-aminostyrene in water without drying for 5 minutes. After removing the polym-aminostyrene aqueous solution present in excess on the surface of the polysulfone support membrane by pressing with a rubber roller, a solution in which 0.5% by weight of trimezoyl chloride was dissolved in n-hexane was immediately applied. After left for 30 seconds for interfacial polymerization, the resulting poly sulfone / crosslinked poly m-styreneamide composite membrane was dried in a 60 ° C. oven.
이와 같이 하여 제조된 복합막에 대한 역삼투 시험은 5,000ppm의 인조 염수를 사용하여 20℃, 50기압에서 수행하였다. 시험결과, 염배제율은 90.2%이었으며, 수투과도는 120gfd(4,890 L/m2, 1일 기준) 이었다.The reverse osmosis test for the composite membrane thus prepared was performed at 20 ° C. and 50 atm using 5,000 ppm of artificial saline. As a result, the salt rejection rate was 90.2% and the water permeability was 120gfd (4,890 L / m 2 , based on 1 day).
[실시예 2-6]Example 2-6
수용액 중의 폴리 m-아미노스티렌의 농도 및 트리메조일클로라이드의 농도를 표1과 같이 변화시킨 것을 제외하고는, 실시예 1과 동일하게 행하여 폴리술폰/폴리 m-스티렌아미드 복합막을 제조하였다.A polysulfone / poly m-styreneamide composite membrane was prepared in the same manner as in Example 1 except that the concentration of poly m-aminostyrene and the concentration of trimesoyl chloride in the aqueous solution were changed as shown in Table 1.
제조된 복합막의 염배제율 및 수투과도를 실시예 1에서와 동일한 방법으로 측정하였다. 그 결과를 표 1에 나타내었다.The salt excretion rate and water permeability of the prepared composite membrane were measured in the same manner as in Example 1. The results are shown in Table 1.
[실시예 7]Example 7
트리메조일클로라이드를 n-헥산에 용해시킨 용액 대신, 테레프탈로일클로라이드 0.5중량%를 n-헥산에 용해시킨 용액을 사용한 것을 제외하고는, 실시예 1과 동일하게 행하여 폴리술폰/폴리 m-스티렌아미드 복합막을 제조하였다.Polysulfone / poly m-styrene was carried out in the same manner as in Example 1, except that 0.5% by weight of terephthaloyl chloride was dissolved in n-hexane, instead of a solution of trimesoyl chloride in n-hexane. An amide composite membrane was prepared.
제조된 복합막의 염배제율 및 수투과도를 실시예 1과 동일한 방법으로 측정한 결과, 각각 80% 및 173gfd(7,040 L/m , 1일 기준)이었다.The salt rejection rate and water permeability of the prepared composite membrane were measured in the same manner as in Example 1, and 80% and 173 gfd (7,040 L / m, respectively) were measured. , Per day).
[실시예 8]Example 8
트리메조일클로라이드를 n-헥산에 용해시킨 용액을 사용하는 대신, 트리멜리트산 무수물 클로라이드 0.25중량% 및 트리메조일클로라이드 0.25 중량%를 n-헥산에 용해시킨 용액을 사용한 것을 제외하고는, 실시예 1과 동일하게 행하여 폴리술폰/폴리 m-스티렌아미드 복합막을 제조하였다.Instead of using a solution in which trimesoyl chloride was dissolved in n-hexane, except that a solution in which 0.25% by weight of trimellitic anhydride chloride and 0.25% by weight of trimesoyl chloride was used in n-hexane was used. In the same manner as in 1, a polysulfone / poly m-styreneamide composite membrane was prepared.
제조된 복합막에 대해 실시예 1과 동일한 방법으로 염배제율 및 수투과도를 측정한 결과, 각각 82% 및 168gfd(6,840 L/m , 1일 기준)이었다.As a result of measuring the excretion rate and water permeability of the prepared composite membrane in the same manner as in Example 1, 82% and 168 gfd (6,840 L / m, respectively) , Per day).
[실시예 9]Example 9
실시예 1에서 제조한 부직포 보강 폴리술폰 지지막을, 폴리 m-아미노스티렌 0.5 중량%를 용해시킨 수용액 및 m-페닐렌 디아민 0.5 중량%를 용해시킨 수용액을 1:1의 비율로 혼합한 수용액에 건조 단계를 거치지 않고 5분 동안 침지시켰다. 실시예 1에서 제조한 트리메조일클로라이드 용액을 사용하여 실시예 1과 동일한 계면 중합시켜 복합막을 제조하였다.The nonwoven fabric-reinforced polysulfone support membrane prepared in Example 1 was dried in an aqueous solution in which an aqueous solution in which 0.5% by weight of poly m-aminostyrene was dissolved and an aqueous solution in which 0.5% by weight of m-phenylene diamine were mixed in a ratio of 1: 1. Soak for 5 minutes without going through the steps. The composite membrane was prepared by interfacial polymerization in the same manner as in Example 1 using the trimezoyl chloride solution prepared in Example 1.
제조된 복합막에 대해 실시예 1과 동일한 방법으로 염배제율 및 수투과도를 측정한 결과, 각각 97% 및 86gfd(3,500 L/m , 1일 기준)이었다.The salt rejection rate and water permeability were measured in the same manner as in Example 1 for the prepared composite membrane, 97% and 86gfd (3,500 L / m, respectively) , Per day).
[실시예 10]Example 10
m-페닐렌 디아민 대신 p-페닐렌 디아민을 사용한 것을 제외하고는, 실시예 9와 동일하게 행하여 복합막을 제조하였다.A composite membrane was prepared in the same manner as in Example 9 except that p-phenylene diamine was used instead of m-phenylene diamine.
복합막의 염배제율 및 수투과도는 각각 93% 및 96gfd(3,910 L/m , 1일 기준)이었다.Salt rejection and water permeability of the composite membrane were 93% and 96gfd (3,910 L / m, respectively) , Per day).
[실시예 11]Example 11
3구 플라스크에 m-아미노스티렌 단량체와 t-부틸디메틸실릴을 1:1 몰비로 넣고, 상온에서 3시간 동안 질소 하에서 교반하면서 반응시킨 후, 에틸벤젠을 m-아미노스티렌 단량체와 10:1 중량비가 되게 넣은 다음, 반응 개시제인 아조비스이소부티로니트릴을 m-아미노스티렌 단량체의 0.05%가 되는 양으로 첨가하여, 80℃에서 3시간 동안 질소 하에서 교반하면서 중합시켰다.In a three-necked flask, m-aminostyrene monomer and t-butyldimethylsilyl were added in a 1: 1 molar ratio, and reacted with stirring under nitrogen for 3 hours at room temperature. Then, ethylbenzene was reacted with m-aminostyrene monomer and 10: 1 weight ratio. Then, azobisisobutyronitrile, a reaction initiator, was added in an amount of 0.05% of the m-aminostyrene monomer and polymerized with stirring under nitrogen at 80 ° C. for 3 hours.
이렇게 얻어진 섬유상의 고분자를 충분히 세척한 후 분쇄하여 새로운 3구 플라스크에 넣고 교반하면서 순수 95 중량%를 넣어 60℃에서 5시간 반응시킨 후 이 반응 용액을 과량의 에틸이스에 미량씩 주입하면서 침전시켜 폴리 m-아미노스티렌을 제조한다.The fibrous polymer thus obtained was sufficiently washed, pulverized, and placed in a new three-necked flask, followed by stirring with 95% by weight of pure water for 5 hours at 60 ° C. The reaction solution was precipitated by injecting a small amount of excess into ethyl acetate. Prepare m-aminostyrene.
이렇게 제조된 폴리 m-아미노스티렌을 이용하는 것을 제외하고는, 실시예 1과 동일하게 행하여 복합막을 제조하였다. 이렇게 제조된 복합막의 염배제율 및 수투과도는 각각 88% 및 130gfd(5,280 L/m , 1일 기준)이었다.A composite membrane was produced in the same manner as in Example 1, except that poly m-aminostyrene thus prepared was used. The salt rejection and water permeability of the composite membrane thus prepared were 88% and 130 gfd (5,280 L / m, respectively). , Per day).
[비교실시예 1]Comparative Example 1
3구 플라스크에 스티렌 단량체로부터 제조한 폴리스티렌(중량 평균 분자량 ; 240,000) 10중량% 및 질산 90 중량%를 넣은 후, 5℃에서 6시간 동안 질소 하에서 교반하여 폴리 p-니트로스티렌 또는 폴리 o-니트로스티렌을 제조하였다.10 weight percent polystyrene (weight average molecular weight; 240,000) prepared from styrene monomer and 90 weight percent nitric acid were added to a three-necked flask, followed by stirring under nitrogen at 5 ° C. for 6 hours to give poly p-nitrostyrene or poly o-nitrostyrene. Was prepared.
이와같이 하여 얻어진 섬유상의 폴리 p-니트로스티렌 또는 폴리 o-니트로스티렌을 충분히 세척한 후 분쇄하여, 새로운 3구 플라스크에 폴리 p-니트로스티렌 또는 폴리 o-니트로스티렌 5중량 %를 넣고, 교반하면서 질소 하에서 페닐히드라진을 95 중량% 넣어 180℃에서 8시간 반응시킨 후, 이 반응 용액을 과량의 에틸이스에 미량씩 주입하면서 침전시켜 폴리 p-아미노스티렌 또는 폴리 o-아미노스티렌을 제조하였다.The fibrous poly p-nitrostyrene or poly o-nitrostyrene thus obtained was sufficiently washed and pulverized, and 5 weight% of poly p-nitrostyrene or poly o-nitrostyrene was added to a new three-necked flask, and stirred under nitrogen. After adding 95% by weight of phenylhydrazine and reacting at 180 ° C. for 8 hours, the reaction solution was precipitated by injecting an excessive amount of ethyl acetate in a small amount to prepare poly p-aminostyrene or poly o-aminostyrene.
상기 실시예 1에서 제조한 부직포 보강 다공성 폴리술폰 지지막을, 건조과정없이, 상기 폴리 p-아미노스티렌 또는 폴리 o-아미노스티렌 0.5 중량%를 물에 용해시켜 제조한 용액에 5분동안 침지시켰다. 폴리술폰 지지막 표면에 과량으로 존재하는 폴리 p-아미노스티렌 또는 폴리 o-아미노스티렌 수용액을 고무 롤러로 압착하여 제거한 후, 트리메조일클로라이드 0.5 중량%를 n-헥산에 용해시킨 용액을 즉시 도포하였다. 계면 중합을 위해 30초간 방치한 후, 얻어진 폴리술폰/가교된 폴리 p-스티렌아미드 또는 폴리 o-스티렌아미드 복합막을 60℃ 오븐에서 건조시켰다.The nonwoven reinforced porous polysulfone support membrane prepared in Example 1 was immersed in a solution prepared by dissolving 0.5 wt% of poly p-aminostyrene or poly o-aminostyrene in water for 5 minutes without drying. After removing poly p-aminostyrene or poly o-aminostyrene aqueous solution present in excess on the surface of the polysulfone support membrane by pressing with a rubber roller, a solution in which 0.5% by weight of trimezoyl chloride was dissolved in n-hexane was immediately applied. . After left for 30 seconds for interfacial polymerization, the resulting polysulfone / crosslinked poly p-styreneamide or poly o-styreneamide composite membrane was dried in a 60 ° C. oven.
이와 같이 하여 제조된 복합막에 대한 역삼투 시험은 상기 실시예 1에서와 같은 방법으로 수행하였다. 시험 결과, 염배제율은 32.5%이었으며, 수투과도는 123gfd(5,010 L/m , 1일 기준)이었다.The reverse osmosis test for the composite membrane thus prepared was performed in the same manner as in Example 1. As a result, salt rejection was 32.5% and water permeability was 123gfd (5,010 L / m , Per day).
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| KR970059224A (en) | 1997-08-12 |
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