KR102067861B1 - Composition for preparing reverse osmosis membrane, method for preparing reverse osmosis membrane using the same, and reverse osmosis membrane and water treatment module - Google Patents
Composition for preparing reverse osmosis membrane, method for preparing reverse osmosis membrane using the same, and reverse osmosis membrane and water treatment module Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 65
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 52
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- 239000011241 protective layer Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
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- 150000003839 salts Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 7
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
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- 239000012267 brine Substances 0.000 description 2
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- 125000001424 substituent group Chemical group 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
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- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 1
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- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 244000005700 microbiome Species 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 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
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- 229920000131 polyvinylidene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
-
- 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
-
- 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
- B01D69/1216—Three or more 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
- B01D71/56—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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- 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
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
본 명세서는 역삼투막 제조용 조성물 및 이를 이용한 역삼투막 제조방법을 제공한다.The present specification provides a composition for preparing a reverse osmosis membrane and a reverse osmosis membrane manufacturing method using the same.
Description
본 명세서는 역삼투막 제조용 조성물 및 이를 이용한 역삼투막 제조방법에 관한 것이다.The present specification relates to a composition for preparing a reverse osmosis membrane and a method for preparing a reverse osmosis membrane using the same.
최근 수질환경의 심각한 오염과 물부족으로 인해 새로운 수자원 공급원을 개발하는 것이 시급한 당면 과제로 대두되고 있다. 수질환경 오염에 대한 연구는 양질의 생활 및 공업용수, 각종 생활하수 및 산업폐수 처리를 목표로 하고 있으며, 에너지 절약의 장점을 지닌 분리막을 이용한 수 처리 공정에 대한 관심이 고조되고 있다. 또한, 가속화되고 있는 환경 규제의 강화는 분리막 기술의 활성화를 앞당길 것으로 예상된다. 전통적인 수처리 공정으로는 강화되는 규제에 부합하기 힘드나, 분리막 기술의 경우 우수한 처리효율과 안정적인 처리를 보증하기 때문에 향후 수처리 분야의 주도적인 기술로 자리매김할 것으로 예상된다.Due to the recent severe pollution and lack of water in the water environment, the development of new water resources is an urgent challenge. Water pollution research aims to treat high quality living and industrial water, various kinds of domestic sewage and industrial wastewater, and interest in water treatment processes using membranes has advantages of energy saving. In addition, accelerating environmental regulations are expected to accelerate membrane technology. Conventional water treatment processes are difficult to meet the tightening regulations, but the membrane technology is expected to become a leading technology in the future because of the excellent treatment efficiency and stable treatment.
액체분리는 막의 기공에 따라 정밀여과(Micro Filtration), 한외여과(Ultra Filtration), 나노여과(Nano Filtration), 역삼투(Reverse Osmosis), 침석, 능동수 송 및 전기투석 등으로 분류된다. 그 중에서 역삼투 방법은 물은 투과하지만, 염에 대해서는 불투과성을 보이는 반투막을 사용하여 탈염작업을 하는 공정을 말하는 것으로 염이 녹아 있는 고압수가 반투막의 한쪽 면에 유입될 때, 염이 제거된 순수가 낮은 압력으로 다른 쪽 면으로 나오게 된다.Liquid separation is classified into micro filtration, ultra filtration, nano filtration, reverse osmosis, sedimentation, active transport, and electrodialysis depending on the pore of the membrane. The reverse osmosis method refers to a process of desalting using a semipermeable membrane that transmits water but is impermeable to salt. When the high pressure water in which the salt is dissolved flows into one side of the semipermeable membrane, the pure water is removed. Will come out on the other side at low pressure.
근래에 들어 전 세계적으로 대략 10억 gal/day 규모의 물이 역삼투법을 통해 탈염화 공정을 거치고 있으며, 1930년대 최초의 역삼투를 이용한 탈염화 공정이 발표된 이후, 이 분야의 반투막 물질에 대한 많은 연구가 수행되었다. 그 중에서도 상업적 성공으로 주류를 이루게 된 것은 셀룰로오스계 비대칭막(Asymmetric membrane)과 폴리아미드계 복합막(Composite membrane)이다. 역삼투막 초기에 개발된 셀룰로오스계막은 운전 가능한 pH 범위가 좁다는 점, 고온에서 변형된다는 점, 높은 압력을 사용하여 운전에 필요한 비용이 많이 든다는 점, 그리고 미생물에 취약하다는 점 등 여러 가지 단점으로 인해 근래에 들어서는 거의 사용되지 않는 추세이다.In recent years, about 1 billion gal / day of water worldwide has undergone desalination through reverse osmosis, and since the first desalination using reverse osmosis was introduced in the 1930s, many of the The study was conducted. Among them, the main successes of commercial success are cellulose-based asymmetric membranes and polyamide-based composite membranes. Cellulose membranes developed in the early stages of reverse osmosis membranes have suffered from several shortcomings due to their narrow operating pH range, their deformation at high temperatures, the high cost of operation using high pressure, and their vulnerability to microorganisms. This is a rarely used trend.
한편, 폴리아미드계 복합막은, 부직포 위에 폴리설폰층을 형성하여 미세 다공성 지지체를 형성하고, 이 미세 다공성 지지체를 m-페닐렌디아민(m-Phenylene Diamine, 이하, mPD) 수용액에 침지시켜 mPD층을 형성하고, 이를 다시 트리메조일클로라이드(TriMesoyl Chloride, 이하, TMC) 유기용액에 침지 혹은 코팅시켜 mPD층을 TMC와 접촉시켜 계면 중합시킴으로써 폴리 아미드 활성층을 형성하는 방법으로 제조되고 있다. 비극성 용액과 극성 용액을 접촉시킴으로써 상기 중합은 그 계면에서만 일어나 매우 두께가 얇은 폴리아미드층을 형성한다. 상기 폴리아미드계 복합 막은 기존 셀룰로오스 계열의 비대칭 막에 비하여, pH 변화에 대해 안정성이 높고, 낮은 압력에서 운전 가능하며, 염 제거율이 우수하여, 현재 수처리 분리막의 주종을 이루고 있다.On the other hand, in the polyamide composite membrane, a polysulfone layer is formed on a nonwoven fabric to form a microporous support, and the microporous support is immersed in an aqueous solution of m-phenylenediamine (mPD) to form an mPD layer. After forming, it is immersed or coated in a trimesoyl chloride (TMC) organic solution, and the mPD layer is contacted with TMC to prepare a polyamide active layer by interfacial polymerization. By contacting the nonpolar and polar solutions, the polymerization takes place only at the interface to form a very thin polyamide layer. The polyamide-based composite membrane has high stability against pH change, can be operated at low pressure, and excellent salt removal rate, compared to existing cellulose-based asymmetric membranes.
이와 같은 폴리아미드계 복합막의 성능을 높이는 것에 대한 연구가 지속적으로 이루어지고 있다.Research on improving the performance of such a polyamide composite membrane has been continuously made.
본 명세서에는 역삼투막 제조용 조성물 및 이를 이용한 역삼투막의 제조방법이 기재된다.Herein, a composition for preparing a reverse osmosis membrane and a method for preparing a reverse osmosis membrane using the same are described.
본 명세서의 일 실시상태는 하기 화학식 1로 표시되는 화합물을 포함하는 역삼투막 제조용 조성물으로서, 상기 화합물의 함량은 전체 조성물 중량을 기준으로 0.01 중량% 이상 0.1 중량% 미만인 역삼투막 제조용 조성물을 제공한다.An exemplary embodiment of the present specification provides a composition for preparing a reverse osmosis membrane including a compound represented by the following Formula 1, wherein the content of the compound is 0.01 wt% or more and less than 0.1 wt% based on the total weight of the composition.
[화학식 1] [Formula 1]
상기 화학식 1에 있어서, R1 내지 R4은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 또는 치환 또는 비치환된 알킬기이고, a는 0 내지 4의 정수이며, a가 2 이상인 경우, R4는 서로 같거나 상이하다.In Formula 1, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group, a is an integer from 0 to 4, and when a is 2 or more, R 4 is the same as or different from each other.
본 명세서의 또 하나의 실시상태는 다공성 지지체를 준비하는 단계; 및 상기 다공성 지지체 상에 아민 화합물을 포함하는 수용액 및 전술한 조성물의 계면중합을 이용하여, 폴리아미드 활성층을 형성하는 단계를 포함하는 역삼투막 제조 방법을 제공한다.Another embodiment of the present specification comprises the steps of preparing a porous support; And it provides a reverse osmosis membrane manufacturing method comprising the step of forming a polyamide active layer by using an interfacial polymerization of the above-described composition and an aqueous solution containing an amine compound on the porous support.
본 명세서의 또 하나의 실시상태는 다공성 지지체; 및 상기 다공성 지지체 상에 구비된 폴리아미드 활성층을 포함하고, 상기 폴리아미드 활성층은 아민 화합물을 포함하는 수용액 및 전술한 조성물의 계면중합으로 형성된 것인 역삼투막을 제공한다.Another embodiment of the present specification is a porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer is formed by interfacial polymerization of an aqueous solution containing an amine compound and the above-described composition.
본 명세서의 또 하나의 실시상태는 다공성 지지체; 및 상기 다공성 지지체 상에 구비된 폴리아미드 활성층을 포함하고, 상기 폴리아미드 활성층은 상기 화학식 1로 표시되는 화합물을 포함하는 것인 역삼투막을 제공한다.Another embodiment of the present specification is a porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer includes a compound represented by Chemical Formula 1.
본 명세서의 또 하나의 실시상태는 전술한 역삼투막을 1 이상 포함하는 수처리 모듈을 제공한다.Another embodiment of the present specification provides a water treatment module including at least one reverse osmosis membrane.
본 명세서에 일 실시상태에 따른 조성물에 의하여 제조된 역삼투막은 우수한 투과유량을 나타낸다.The reverse osmosis membrane prepared by the composition according to the exemplary embodiment herein shows an excellent permeate flow rate.
나아가, 본 명세서의 일 실시상태에 조성물에 의하여 제조된 역삼투막은 역삼투막 제조시 조성물 내에 침전을 발생시키지 않아, 투과유량 향상과 함께 우수한 염제거율을 나타낼 수 있다. Furthermore, the reverse osmosis membrane prepared by the composition in one embodiment of the present specification does not cause precipitation in the composition during the preparation of the reverse osmosis membrane, and may exhibit excellent salt removal rate along with an improved permeate flow rate.
도 1은 본 명세서의 일 실시상태에 따른 역삼투막을 도시한 것이다.1 illustrates a reverse osmosis membrane according to one embodiment of the present specification.
본 명세서에서 어떤 부재가 다른 부재 "상에" 위치하고 있다고 할 때, 이는 어떤 부재가 다른 부재에 접해 있는 경우뿐 아니라 두 부재 사이에 또 다른 부재가 존재하는 경우도 포함한다.In this specification, when a member is located "on" another member, this includes not only when a member is in contact with another member but also when another member exists between the two members.
본 명세서에서 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 포함할 수 있다는 것을 의미한다.In the present specification, when a part "includes" a certain component, this means that the component may further include other components, except for the case where there is no description to the contrary.
이하 본 명세서에 대하여 더욱 상세하게 설명한다.Hereinafter, the present specification will be described in more detail.
기존 역삼투막에 적용되고 있는 투과유량 향상제는 유량 면에서는 유리하지만, 염제거율을 과도하게 감소시키는 문제가 있었다. 또한, 일부 투과유량 향상제의 경우에 일정 수준 이상으로 농도가 증가하면 역삼투막 제조 용액 조성물 내에 침전을 발생시키기도 하며, 이는 역삼투막 성능에 부정적인 영향을 미치게 된다. 본 명세서에 기재된 실시 상태들에 따른 역삼투막은 하기 화학식 1로 표시되는 화합물이 유기 용액 내의 반응 가능한 단량체의 말단 작용기를 가수분해(hydrolize)시켜 폴리아미드 고분자의 자유 부피(free volume)을 증가시키므로 기존 역삼투막에 비하여 우수한 투과유량을 나타낼 수 있다.Permeate flow rate improvers applied to the existing reverse osmosis membrane, but advantageous in terms of flow rate, there was a problem of excessively reducing the salt removal rate. In addition, in the case of some permeation flux improver concentration increases above a certain level may cause precipitation in the reverse osmosis membrane production solution composition, which negatively affects the reverse osmosis membrane performance. The reverse osmosis membrane according to the embodiments described in the present specification increases the free volume of the polyamide polymer by hydrolizing the terminal functional groups of the reactive monomers in the organic solution by the compound represented by Formula 1 below. As compared with the present invention, an excellent permeate flow rate can be exhibited.
본 명세서의 일 실시상태는 하기 화학식 1로 표시되는 화합물을 포함하는 역삼투막 제조용 조성물으로서, 상기 화합물의 함량은 전체 조성물 중량을 기준으로 0.01 중량% 이상 0.1 중량% 미만인 역삼투막 제조용 조성물을 제공한다.An exemplary embodiment of the present specification provides a composition for preparing a reverse osmosis membrane including a compound represented by the following Formula 1, wherein the content of the compound is 0.01 wt% or more and less than 0.1 wt% based on the total weight of the composition.
[화학식 1] [Formula 1]
상기 화학식 1에 있어서, R1 내지 R4은 서로 같거나 상이하고, 각각 독립적으로 수소; 중수소; 또는 치환 또는 비치환된 알킬기이고, a는 0 내지 4의 정수이며, a가 2 이상인 경우, R4는 서로 같거나 상이하다.In Formula 1, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group, a is an integer from 0 to 4, and when a is 2 or more, R 4 is the same as or different from each other.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R3는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기이며, R4는 수소일 수 있다. According to an exemplary embodiment of the present specification, R1 to R3 are the same as or different from each other, each independently represent a substituted or unsubstituted alkyl group, R4 may be hydrogen.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R3는 서로 같거나 상이하고, 각각 독립적으로 탄소수 1 내지 30의 치환 또는 비치환된 알킬기일 수 있다.According to an exemplary embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently may be a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 R1 내지 R3는 서로 같거나 상이하고, 각각 독립적으로 탄소수 1 내지 15의 치환 또는 비치환된 알킬기일 수 있다.According to an exemplary embodiment of the present specification, R1 to R3 are the same as or different from each other, and each independently may be a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms.
본 명세서의 일 실시상태에 따르면, 상기 알킬기는 직쇄, 분지쇄 또는 고리쇄일 수 있다. 또한, 본 명세서의 일 실시상태에 따르면, 상기 알킬기는 메틸기, 에틸기, n-프로필기, iso-프로필기, n-부틸기, sec-부틸기, t-부틸기, n-펜틸기, iso-펜틸기, neo-펜틸기, n-헥실기, 시클로프로필기, 시클로부틸기, 시클로펜틸기 또는 시클로헥실기일 수 있다. 다만, 이에 한정되는 것은 아니다.According to an exemplary embodiment of the present specification, the alkyl group may be linear, branched or cyclic. In addition, according to an exemplary embodiment of the present specification, the alkyl group is a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, iso- Pentyl group, neo-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group or cyclohexyl group. However, the present invention is not limited thereto.
상기 "치환 또는 비치환"은 할로겐기, 히드록시기, 알킬기, 시클로알킬기, 알케닐기, 알콕시기, 및 아릴옥시기로 이루어진 군에서 선택된 1개 이상의 치환기로 치환되었거나, 어떠한 치환기도 갖지 않는 것을 의미한다.The "substituted or unsubstituted" means substituted with one or more substituents selected from the group consisting of a halogen group, a hydroxy group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, and an aryloxy group, or has no substituent.
본 명세서의 일 실시상태에 따르면, 상기 화학식 1로 표시되는 화합물의 함량은 전체 조성물 중량을 기준으로 0.01 중량% 이상 0.1 중량% 미만일 수 있고, 바람직하게는 0.02 중량% 이상 0.05 중량% 이하일 수 있다. 상기 화합물의 함량이 0.01 중량% 미만인 경우 소량 첨가로 투과 유량 효과가 미미할 수 있고, 상기 화합물의 함량이 0.1 중량% 이상인 경우 유기 용액 내 반응 가능한 단량체 농도를 과도하게 감소시키므로 폴리아마이드 고분자 형성을 방해하여 염제거율 및 투과유량이 감소할 수 있다.According to an exemplary embodiment of the present specification, the content of the compound represented by Formula 1 may be 0.01% by weight or more and less than 0.1% by weight based on the total weight of the composition, preferably 0.02% by weight or more and 0.05% by weight or less. When the content of the compound is less than 0.01% by weight, a small amount of permeation flux effect may be insignificant, and when the content of the compound is 0.1% by weight or more, the concentration of the reactive monomer in the organic solution is excessively reduced, thereby preventing the formation of the polyamide polymer. Salt removal rate and permeate flow rate can be reduced.
본 명세서의 또 하나의 실시상태에 따르면, 상기 조성물은 아실 할라이드 화합물 및 유기 용매를 더 포함할 수 있다. 상기 아실 할라이드 화합물은, 이로써 제한되는 것은 아니나, 예를 들면, 2 내지 3개의 카르복실산 할라이드를 갖는 방향족 화합물로서, 트리메조일클로라이드, 이소프탈로일클로라이 및 테레프탈로일클로라이드로 이루어진 화합물군으로부터 선택되는 1종 이상의 혼합물일 수 있다. According to another exemplary embodiment of the present specification, the composition may further include an acyl halide compound and an organic solvent. The acyl halide compound is, but is not limited to, for example, an aromatic compound having 2 to 3 carboxylic acid halides, from a group of compounds consisting of trimezoyl chloride, isophthaloyl chlorlai and terephthaloyl chloride. It may be one or more mixtures selected.
본 명세서의 일 실시상태에 따르면, 상기 유기용매로는 지방족 탄화수소 용매, 예를 들면, 프레온류와 탄소수가 5 내지 12인 헥산, 사이클로헥산, 헵탄, 알칸과 같은 물과 섞이지 않는 소수성 액체, 예를 들면, 탄소수가 5 내지 12인 알칸과 그 혼합물인 IsoPar(Exxon), IsoPar G(Exxon), ISOL-C(SK Chem), ISOL-G(Exxon)등이 사용될 수 있으나, 이로써 제한되는 것은 아니다.According to an exemplary embodiment of the present specification, the organic solvent is an aliphatic hydrocarbon solvent, for example, a hydrophobic liquid which is not mixed with freons and water such as hexane, cyclohexane, heptane, and alkanes having 5 to 12 carbon atoms, for example. For example, alkanes having 5 to 12 carbon atoms and mixtures thereof, such as IsoPar (Exxon), IsoPar G (Exxon), ISOL-C (SK Chem), ISOL-G (Exxon), and the like may be used, but are not limited thereto.
본 명세서의 또 하나의 실시상태는 다공성 지지체를 준비하는 단계; 및 상기 다공성 지지체 상에 아민 화합물을 포함하는 수용액 및 전술한 조성물의 계면중합을 이용하여, 폴리아미드 활성층을 형성하는 단계를 포함하는 역삼투막 제조 방법을 제공한다.Another embodiment of the present specification comprises the steps of preparing a porous support; And it provides a reverse osmosis membrane manufacturing method comprising the step of forming a polyamide active layer by using an interfacial polymerization of the above-described composition and an aqueous solution containing an amine compound on the porous support.
본 명세서의 일 실시상태에 따르면, 상기 다공성 지지체로는, 부직포 상에 고분자 재료의 코팅층이 형성된 것을 사용할 수 있다. 상기 고분자 재료로는, 예를 들면, 폴리설폰, 폴리에테르설폰, 폴리카보네이트, 폴리에틸렌옥사이드, 폴리이미드, 폴리에테르이미드, 폴리에테르에테르케톤, 폴리프로필렌, 폴리메틸펜텐, 폴리메틸클로라이드 및 폴리비닐리덴플루오라이드 등이 사용될 수 있으나, 반드시 이들로 제한되는 것은 아니다. 구체적으로, 상기 고분자 재료로서 폴리설폰을 사용할 수 있다.According to one embodiment of the present specification, as the porous support, a coating layer of a polymer material may be used on a nonwoven fabric. Examples of the polymer material include polysulfone, polyethersulfone, polycarbonate, polyethylene oxide, polyimide, polyetherimide, polyether ether ketone, polypropylene, polymethylpentene, polymethyl chloride and polyvinylidene fluorine. Ride or the like may be used, but is not necessarily limited thereto. Specifically, polysulfone may be used as the polymer material.
본 명세서의 일 실시상태에 따르면, 상기 폴리아미드 활성층은 다공성 지지체 상에 아민 화합물을 포함하는 수용액층을 형성하는 단계; 상기 아민 화합물을 포함하는 수용액층 상에 전술한 조성물을 접촉시켜 폴리아미드 활성층을 형성하는 단계를 통하여 형성될 수 있다.According to one embodiment of the present specification, the polyamide active layer may include forming an aqueous solution layer including an amine compound on a porous support; It can be formed through the step of forming the polyamide active layer by contacting the above-described composition on the aqueous solution layer containing the amine compound.
상기 아민 화합물을 포함하는 수용액층과 전술한 조성물의 접촉시, 상기 다공성 지지체의 표면에 코팅된 아민 화합물과 아실 할라이드 화합물이 반응하면서 계면 중합에 의해 폴리아미드를 생성하고, 미세 다공성 지지체에 흡착되어 박막이 형성된다. 상기 접촉 방법에 있어서, 침지, 스프레이 또는 코팅 등의 방법을 통해 폴리아미드 활성층을 형성할 수도 있다.Upon contact of the aqueous solution layer containing the amine compound with the above-described composition, the amine compound and acyl halide compound coated on the surface of the porous support react with each other to generate polyamide by interfacial polymerization, and are adsorbed onto the microporous support to form a thin film. Is formed. In the contact method, the polyamide active layer may be formed through a method such as dipping, spraying or coating.
본 명세서의 일 실시상태에 따르면, 상기 다공성 지지체 상에 아민 화합물을 포함하는 수용액층을 형성하는 방법은 특별히 한정하지 않으며, 지지체 위에 수용액층을 형성할 수 있는 방법이라면 제한하지 않고 사용할 수 있다. 구체적으로, 상기 다공성 지지체 상에 아민 화합물을 포함하는 수용액층을 형성하는 방법은 분무, 도포, 침지, 적하 등을 들 수 있다.According to one embodiment of the present specification, a method of forming an aqueous solution layer including an amine compound on the porous support is not particularly limited, and any method capable of forming an aqueous solution layer on the support may be used without limitation. Specifically, the method of forming the aqueous solution layer containing an amine compound on the porous support may be sprayed, applied, immersed, dripping and the like.
이때, 상기 수용액층은 필요에 따라 과잉의 아민 화합물을 포함하는 수용액을 제거하는 단계를 추가적으로 거칠 수 있다. 상기 다공성 지지체 상에 형성된 수용액층은 지지체 상에 존재하는 수용액이 지나치게 많은 경우에는 불균일하게 분포할 수 있는데, 수용액이 불균일하게 분포하는 경우에는 이후의 계면 중합에 의해 불균일한 폴리아미드 활성층이 형성될 수 있다. 따라서, 상기 지지체 상에 수용액층을 형성한 후에 과잉의 수용액을 제거하는 것이 바람직하다. 상기 과잉의 수용액 제거는 특별히 제한되지는 않으나, 예를 들면, 스펀지, 에어나이프, 질소 가스 블로잉, 자연건조, 또는 압축 롤 등을 이용하여 행할 수 있다.At this time, the aqueous solution layer may be further subjected to the step of removing the aqueous solution containing the excess amine compound as necessary. The aqueous solution layer formed on the porous support may be unevenly distributed when there are too many aqueous solutions present on the support. When the aqueous solution is unevenly distributed, a non-uniform polyamide active layer may be formed by subsequent interfacial polymerization. have. Therefore, it is preferable to remove excess aqueous solution after forming an aqueous solution layer on the said support body. The removal of the excess aqueous solution is not particularly limited, but may be performed using, for example, a sponge, air knife, nitrogen gas blowing, natural drying, or a compression roll.
본 명세서의 일 실시상태에 따르면, 상기 아민 화합물을 포함하는 수용액에서 상기 아민 화합물은 역삼투막 제조에 사용되는 아민 화합물이라면 그 종류를 제한하지 않으나, 구체적인 예를 든다면, m-페닐렌디아민, p-페닐렌디아민, 1,3,6-벤젠트리아민, 4-클로로-1,3-페닐렌디아민, 6-클로로-1,3-페닐렌디아민, 3-클로로-1,4-페닐렌 디아민 또는 이들의 혼합물인 것이 바람직하다.According to an exemplary embodiment of the present specification, the amine compound in the aqueous solution containing the amine compound is not limited if the amine compound used in the preparation of reverse osmosis membrane, but specific examples, m-phenylenediamine, p- Phenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3-chloro-1,4-phenylene diamine or It is preferable that it is a mixture of these.
본 명세서의 일 실시상태에 따르면, 상기 폴리아미드 활성층 상에 보호층을 형성하는 단계를 더 포함할 수 있다.According to one embodiment of the present specification, the method may further include forming a protective layer on the polyamide active layer.
상기 보호층을 형성하는 단계는, 예를 들면, 폴리아미드 활성층이 형성된 지지체를 보호층을 형성하는 수용액에 침지시키는 방법을 통해 수행될 수 있다.The forming of the protective layer may be performed by, for example, immersing the support on which the polyamide active layer is formed in an aqueous solution forming the protective layer.
본 명세서의 또 하나의 실시상태는 다공성 지지체; 및 상기 다공성 지지체 상에 구비된 폴리아미드 활성층을 포함하고, 상기 폴리아미드 활성층은 아민 화합물을 포함하는 수용액 및 전술한 조성물의 계면중합으로 형성된 것인 역삼투막을 제공한다.Another embodiment of the present specification is a porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer is formed by interfacial polymerization of an aqueous solution containing an amine compound and the above-described composition.
본 명세서의 일 실시상태에 따르면, 상기 역삼투막은 상기 폴리아미드 활성층 상에 구비된 보호층을 더 포함할 수 있다. 더욱 구체적으로는 폴리아미드막 표면에 폴리비닐알코올과 같은 친수성 고분자를 코팅하거나, 폴리알킬렌 옥사이드를 함유하는 코팅층을 형성할 수 있으며, 플루오르를 포함하는 소수성 코팅층을 형성할 수 있다. 상기 보호층을 더 포함함으로써, 투과유량 저하를 최소화하면서도 내오염성 및 내구성을 향상시킬 수 있다.According to an exemplary embodiment of the present specification, the reverse osmosis membrane may further include a protective layer provided on the polyamide active layer. More specifically, a hydrophilic polymer such as polyvinyl alcohol may be coated on the surface of the polyamide film, or a coating layer containing polyalkylene oxide may be formed, and a hydrophobic coating layer containing fluorine may be formed. By further including the protective layer, it is possible to improve pollution resistance and durability while minimizing a decrease in permeation flow rate.
본 명세서의 또 하나의 실시상태는 다공성 지지체; 및 상기 다공성 지지체 상에 구비된 폴리아미드 활성층을 포함하고, 상기 폴리아미드 활성층은 상기 화학식 1로 표시되는 화합물을 포함하는 것인 역삼투막을 제공한다.Another embodiment of the present specification is a porous support; And a polyamide active layer provided on the porous support, wherein the polyamide active layer includes a compound represented by Chemical Formula 1.
본 명세서의 또 하나의 실시상태는 전술한 역삼투막을 1 이상 포함하는 수처리 모듈을 제공한다.Another embodiment of the present specification provides a water treatment module including at least one reverse osmosis membrane.
본 명세서의 일 실시상태에 따르면, 상기 역삼투막은 정밀 여과막(Micro Filtration), 한외 여과막(Ultra Filtration), 나노 여과막(Nano Filtration) 또는 역삼투막(Reverse Osmosis) 등으로 이용될 수 있으며, 구체적으로 역삼투막으로 이용될 수 있다.According to one embodiment of the present specification, the reverse osmosis membrane may be used as a micro filtration membrane, an ultra filtration membrane, an ultra filtration membrane, a nano filtration membrane, or a reverse osmosis membrane, and specifically used as a reverse osmosis membrane. Can be.
또한, 본 명세서의 일 실시상태는, 상기 역삼투막을 1 이상 포함하는 수처리 모듈을 제공한다.In addition, an exemplary embodiment of the present specification provides a water treatment module including at least one reverse osmosis membrane.
상기 수처리 모듈의 구체적인 종류는 특별히 제한되지 않으며, 그 예에는 판형(plate & frame) 모듈, 관형(tubular) 모듈, 중공사형(Hollow & Fiber) 모듈 또는 나권형(spiral wound) 모듈 등이 포함된다. 또한, 상기 수처리 모듈은 전술한 역삼투막을 포함하는 한, 그 외의 기타 구성및 제조 방법 등은 특별히 한정되지 않고, 이 분야에서 공지된 일반적인 수단을 제한 없이 채용할 수 있다.A specific kind of the water treatment module is not particularly limited, and examples thereof include a plate & frame module, a tubular module, a hollow & fiber module or a spiral wound module. In addition, as long as the water treatment module includes the reverse osmosis membrane described above, other configurations and manufacturing methods are not particularly limited, and general means known in the art may be employed without limitation.
한편, 본 명세서의 일 실시상태에 따른 수처리 모듈은 염제거율 및 투과유량이 우수하며, 화학적 안정성이 우수하여 가정용/산업용 정수 장치, 하수 처리 장치, 해담수 처리 장치 등과 같은 수처리 장치에 유용하게 사용될 수 있다.Meanwhile, the water treatment module according to one embodiment of the present specification has excellent salt removal rate and permeation flow rate, and has excellent chemical stability, and thus may be usefully used for water treatment devices such as household / industrial water purification devices, sewage treatment devices, seawater treatment devices, and the like. have.
이하, 본 명세서를 구체적으로 설명하기 위해 실시예를 들어 상세하게 설명하기로 한다. 그러나, 본 명세서에 따른 실시예들은 여러 가지 다른 형태로 변형될수 있으며, 본 명세서의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되지 않는다. 본 명세서의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 명세서를 보다 완전하게 설명하기 위해 제공되는 것이다.Hereinafter, the present invention will be described in detail with reference to Examples. However, the embodiments according to the present disclosure may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.
실시예Example 1 One
DMF(N,N-디메틸포름아미드) 용액에 18중량%의 폴리술폰 고형분을 넣고 80℃ 내지 85℃에서 12시간 이상 녹여 균일한 액상을 얻었다. 이 용액을 폴리에스테르 재질의 95 ㎛ 내지 100 ㎛ 두께의 부직포 위에 150 ㎛ 두께로 캐스팅하였다. 그런 다음, 캐스팅된 부직포를 물에 넣어 다공성 폴리술폰 지지체를 제조하였다.18% by weight of polysulfone solids were added to a DMF (N, N-dimethylformamide) solution and dissolved at 80 ° C. to 85 ° C. for at least 12 hours to obtain a uniform liquid phase. This solution was cast 150 μm thick on a 95 μm to 100 μm thick nonwoven fabric made of polyester. Then, the cast nonwoven fabric was put in water to prepare a porous polysulfone support.
메타페닐렌디아민(mPD)을 포함하는 수용액을 슬롯 코팅 방법으로 상기 다공성 폴리술폰 지지체 상에 도포하여 수용액층을 형성하였다. 나아가, 도포시 발생한 여분의 수용액을 에어 나이프를 이용하여 제거하였다. An aqueous solution containing metaphenylenediamine (mPD) was applied onto the porous polysulfone support by a slot coating method to form an aqueous solution layer. Furthermore, the excess aqueous solution generated at the time of application was removed using an air knife.
2-(4-메틸페닐)프로판-2-올(2-(4-Methylphenyl)propan-2-ol)을 0.05 중량% 포함하고, 아실 할라이드 화합물(1, 3, 5-benzenetricarbonyl trichloride, TMC), IsoPar G(Exxon) 및 메시틸렌을 포함하는 조성물을 제조하고, 상기 조성물을 수용액층 상에 도포하였다. 그리고, 95℃ 에서 액상 성분이 모두 증발할 때까지 건조한 후, 초순수 증류수(DIW)로 세척하여 역삼투막을 제조하였다.2- (4-methylphenyl) propan-2-ol (2- (4-Methylphenyl) propan-2-ol) containing 0.05% by weight of acyl halide compound (1, 3, 5-benzenetricarbonyl trichloride, TMC), IsoPar A composition comprising G (Exxon) and mesitylene was prepared and the composition was applied onto an aqueous layer. And, after drying until all the liquid components evaporated at 95 ℃, washed with ultrapure distilled water (DIW) to prepare a reverse osmosis membrane.
실시예Example 2 2
상기 조성물 내의 2-(4-메틸페닐)프로판-2-올(2-(4-Methylphenyl)propan-2-ol)의 함량을 0.02 중량%로 한 것을 제외하고, 실시예 1과 동일한 방법으로 역삼투막을 제조하였다.Reverse osmosis membranes were prepared in the same manner as in Example 1, except that the content of 2- (4-methylphenyl) propan-2-ol (2- (4-Methylphenyl) propan-2-ol) in the composition was 0.02% by weight. Prepared.
비교예Comparative example 1 One
상기 조성물 내의 2-(4-메틸페닐)프로판-2-올(2-(4-Methylphenyl)propan-2-ol)을 포함하지 않은 것을 제외하고, 실시예 1과 동일한 방법으로 역삼투막을 제조하였다.Reverse osmosis membranes were prepared in the same manner as in Example 1, except that 2- (4-methylphenyl) propan-2-ol (2- (4-Methylphenyl) propan-2-ol) was not included in the composition.
비교예Comparative example 2 2
상기 조성물 내의 2-(4-메틸페닐)프로판-2-올(2-(4-Methylphenyl)propan-2-ol)의 함량을 0.1 중량%로 한 것을 제외하고, 실시예 1과 동일한 방법으로 역삼투막을 제조하였다.Reverse osmosis membranes were prepared in the same manner as in Example 1, except that the content of 2- (4-methylphenyl) propan-2-ol (2- (4-Methylphenyl) propan-2-ol) in the composition was 0.1% by weight. Prepared.
비교예Comparative example 3 3
상기 조성물 내의 2-(4-메틸페닐)프로판-2-올(2-(4-Methylphenyl)propan-2-ol)의 함량을 0.5 중량%로 한 것을 제외하고, 실시예 1과 동일한 방법으로 역삼투막을 제조하였다.Reverse osmosis membranes were prepared in the same manner as in Example 1, except that the content of 2- (4-methylphenyl) propan-2-ol (2- (4-Methylphenyl) propan-2-ol) was 0.5% by weight. Prepared.
실험예Experimental Example
250 ppm NaCl을 함유하는 염수를 이용하여 60 psi 하에서 상기 실시예 및 비교예에 따라 제조된 역삼투막의 성능을 평가하였다. 생산수와 원수의 전도도 차이를 측정하여 염제거율을 측정하였으며, 단위 시간(5분)당 확보된 생산수의 부피를 측정하여 투과유량(Flux)을 산출하였다.The performance of the reverse osmosis membrane prepared according to the examples and comparative examples under 60 psi using brine containing 250 ppm NaCl was evaluated. The salt removal rate was measured by measuring the conductivity difference between the produced water and the raw water, and the permeate flux (Flux) was calculated by measuring the volume of the produced water obtained per unit time (5 minutes).
이와 같이 측정된 실시예 및 비교예에 따른 역삼투막의 성능은 하기 표 1과 같다.The performance of the reverse osmosis membrane according to the measured examples and the comparative examples is as shown in Table 1 below.
상기 투과유량의 GFD는 gallon/ft2day를 의미한다. The permeation flux of GFD means gallon / ft 2 day.
상기 표 1에 따르면, 실시예에 따른 역삼투막은 염제거율 및 투과유량이 모두 우수한 반면, 비교예에 따른 역삼투막은 투과유량이 현저히 감소되었다는 사실을 알 수 있다.According to Table 1, the reverse osmosis membrane according to the embodiment is excellent in both the salt removal rate and the permeate flow rate, the reverse osmosis membrane according to the comparative example it can be seen that the permeate flow rate is significantly reduced.
100: 부직포
200: 다공성 지지체
300: 폴리아미드 활성층
400: 염수
500: 정제수
600: 농축수100: non-woven
200: porous support
300: polyamide active layer
400: brine
500: purified water
600: concentrated water
Claims (9)
[화학식 1]
상기 화학식 1에 있어서,
R1 내지 R3는 서로 같거나 상이하고, 각각 독립적으로 치환 또는 비치환된 알킬기이고,
R4는 수소이며,
a는 4이다.A composition for preparing a reverse osmosis membrane comprising a compound represented by Formula 1, wherein the content of the compound is 0.01 wt% or more and less than 0.1 wt% based on the total weight of the composition:
[Formula 1]
In Chemical Formula 1,
R1 to R3 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group,
R4 is hydrogen,
a is 4
상기 조성물은 아실 할라이드 화합물 및 유기 용매를 더 포함하는 것인 역삼투막 제조용 조성물.The method according to claim 1,
The composition is a composition for producing a reverse osmosis membrane further comprising an acyl halide compound and an organic solvent.
상기 다공성 지지체 상에 아민 화합물을 포함하는 수용액 및 청구항 1 또는 3에 따른 조성물의 계면중합을 이용하여, 폴리아미드 활성층을 형성하는 단계를 포함하는 역삼투막 제조 방법.Preparing a porous support; And
Method for producing a reverse osmosis membrane comprising the step of forming a polyamide active layer by using an interfacial polymerization of the aqueous solution containing the amine compound and the composition according to claim 1 or 3 on the porous support.
상기 폴리아미드 활성층 상에 보호층을 형성하는 단계를 더 포함하는 역삼투막의 제조 방법.The method according to claim 4,
The method of manufacturing a reverse osmosis membrane further comprising the step of forming a protective layer on the polyamide active layer.
상기 다공성 지지체 상에 구비된 폴리아미드 활성층을 포함하고,
상기 폴리아미드 활성층은 아민 화합물을 포함하는 수용액 및 청구항 1 또는 3에 따른 조성물의 계면중합으로 형성된 것인 역삼투막.Porous support; And
It comprises a polyamide active layer provided on the porous support,
The polyamide active layer is a reverse osmosis membrane formed by interfacial polymerization of an aqueous solution containing an amine compound and the composition according to claim 1 or 3.
상기 폴리아미드 활성층 상에 구비된 보호층을 더 포함하는 역삼투막.The method according to claim 6,
Reverse osmosis membrane further comprising a protective layer provided on the polyamide active layer.
상기 폴리아미드 활성층은 상기 화학식 1로 표시되는 화합물을 포함하는 것인 역삼투막.The method according to claim 6,
The polyamide active layer is a reverse osmosis membrane comprising a compound represented by the formula (1).
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