KR100817450B1 - Molecualr imprinted separation membrane for preparing optically pure compounds and method of preparing the same - Google Patents
Molecualr imprinted separation membrane for preparing optically pure compounds and method of preparing the same Download PDFInfo
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- KR100817450B1 KR100817450B1 KR1020060027664A KR20060027664A KR100817450B1 KR 100817450 B1 KR100817450 B1 KR 100817450B1 KR 1020060027664 A KR1020060027664 A KR 1020060027664A KR 20060027664 A KR20060027664 A KR 20060027664A KR 100817450 B1 KR100817450 B1 KR 100817450B1
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- 238000000926 separation method Methods 0.000 title claims abstract description 45
- 239000012528 membrane Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 title description 7
- 230000003287 optical effect Effects 0.000 claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000004952 Polyamide Substances 0.000 claims abstract description 15
- 229920002647 polyamide Polymers 0.000 claims abstract description 15
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 12
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000012695 Interfacial polymerization Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 150000001266 acyl halides Chemical class 0.000 claims description 3
- 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 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920006037 cross link polymer Polymers 0.000 claims 1
- MTCFGRXMJLQNBG-UWTATZPHSA-N D-Serine Chemical compound OC[C@@H](N)C(O)=O MTCFGRXMJLQNBG-UWTATZPHSA-N 0.000 abstract description 19
- 229930195711 D-Serine Natural products 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229940024606 amino acid Drugs 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229960001153 serine Drugs 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction 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
- 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
- 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
- B01D69/105—Support pretreatment
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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 광학이성질체 분리효율의 극대화를 위한 분리막의 제조방법에 관한 것으로, 더욱 상세하게는 폴리설폰 용액을 이용하여 다공성 지지체를 제조하고 피페라진(PIP)과 트리메소일클로라이드(TMC)를 계면중합하여 분리막 표면에 폴리 아마이드 활성층을 갖는 복합막 제조과정에서 (D)-세린과 같은 분리하고자 하는 특정 광학 이성질체를 복합막의 활성층에 분자각인(Molecular Imprinting) 시킴으로써 특정물질의 선택적 분리효율을 극대화시킬 수 있으며 장시간 높은 분리효율을 유지시킬 수 있는 분리막 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a separator for maximizing optical isomer separation efficiency, and more particularly, to prepare a porous support using a polysulfone solution and to pipepiazine (PIP) and trimethoyl chloride (TMC) in the interface. In addition, in the process of manufacturing a composite membrane having a polyamide active layer on the surface of the separator, specific optical isomers such as (D) -serine may be molecularly imprinted on the active layer of the composite membrane to maximize the selective separation efficiency of a specific material. It relates to a membrane production method that can maintain a high separation efficiency for a long time.
분자각인, 광학이성질체, 분리막 Molecular imprint, optical isomer, separator
Description
도 1은 본 발명에 따른 분자 각인된 분리막의 구조를 도식화한 것이다.1 is a schematic of the structure of a molecular-engraved separator according to the present invention.
본 발명은 광학이성질체 분리효율의 극대화를 위한 분리막의 제조방법에 관한 것으로, 더욱 상세하게는 폴리설폰 용액을 이용하여 다공성 지지체를 제조하고 피페라진(PIP)과 트리메소일클로라이드(TMC)를 계면중합하여 표면에 폴리아마이드 활성층을 갖는 복합막 제조과정에서 (D)-세린과 같은 분리하고자 하는 특정 광학 이성질체를 복합막의 활성층에 분자각인(Molecular Imprinting) 시킴으로써 특정물질의 선택적 분리효율을 극대화시킬 수 있으며 장시간 높은 분리효율을 유지시킬 수 있는 분리막 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a separator for maximizing optical isomer separation efficiency, and more particularly, to prepare a porous support using a polysulfone solution and to pipepiazine (PIP) and trimethoyl chloride (TMC) in the interface. In addition, in the process of manufacturing a composite membrane having a polyamide active layer on its surface, specific optical isomers such as (D) -serine can be imprinted on the active layer of the composite membrane by molecular imprinting to maximize the selective separation efficiency of a specific material. It relates to a membrane production method that can maintain a high separation efficiency.
키랄 화합물은 항상 서로에 대해 거울상인 구조로 된 이성질체를 지니고 있 으며 이들을 광학이성질체라고 하며, 키랄리티는 생합성과 신진대사를 조절하는 주요 인자이다. 이를 지니고 있는 키랄화합물은 여러 산업에 걸쳐 매우 중요한 역할을 담당하고 있으며 관련산업으로 의약, 농약, 식음료산업 그리고 석유화학산업 등이 있다. 키랄화합물은 단일 이성질체로 있을 때만 키랄화합물 고유의 성질을 나타낼 수 있으므로 키랄화합물 산업에서 가장 중요한 공정 중의 하나는 단일 이성질체 제조라고 할 수 있다. 광학이성질체는 화학구조상의 차이가 없음에도 불구하고 각 이성질체가 가지는 특이성은 매우 크며 이성질체 간의 서로 다른 활성 때문에 이들을 제대로 활용하기 위해서는 이성체들이 단일 이성체 상태로 제조되어야만 한다. 일반적인 유기합성법으로 키랄화합물을 제조할 시 단일 이성질체만 형성되는 것이 아니고 이성질체의 혼합물인 라세메이트(Racemate)가 제조되며 이들의 분리는 일반적인 분리방법으로는 한계가 있다.Chiral compounds always have isomers in a structure that are mirror images of each other and are called optical isomers, and chirality is a major factor controlling biosynthesis and metabolism. Its chiral compounds play a very important role in many industries and are related to medicine, pesticides, food and beverage industry, and petrochemical industry. Since chiral compounds can exhibit inherent properties only when they exist as single isomers, one of the most important processes in the chiral compound industry is the production of single isomers. Although optical isomers have no difference in chemical structure, the specificity of each isomer is very large, and due to the different activity between the isomers, the isomers must be prepared in a single isomeric state in order to utilize them properly. When a chiral compound is prepared by a general organic synthesis method, not only a single isomer is formed, but racemate, which is a mixture of isomers, is prepared, and their separation has a limitation as a general separation method.
키랄화합물의 단일 이성질체를 제조하기 위한 방법으로는 촉매 등을 이용한 비대칭 합성방법과 제조된 광학이성질체 혼합물을 분리하는 방법을 이용하고 있으며 키랄 화합물 분리를 위해서 지금까지 널리 사용된 방법으로는 1)재결정법 과 2)HPLC법 등이 있다. 재결정법은 적용에 많은 한계를 지니고 있으며 재결정법으로 분리할 수 없는 광학이성질체 혼합물이 많이 존재하며 이러한 재결정법의 단점을 극복하기 위해서 HPLC법이 발달되어 왔으나 이 또한 여러 가지 산업화에 어려운 점을 지니고 있다. 즉, HPLC를 이용한 분리는 높은 분리성능을 나타내는 반면, 한번에 처리할 수 있는 처리용량이 적은 단점을 지니고 있으며 한번에 처리할 수 있는 양의 제한은 곧바로 고비용 공정으로 연결되므로 관련 산업으로의 적용에 제한이 따르게 된다.As a method for preparing a single isomer of a chiral compound, asymmetric synthesis using a catalyst or the like and a method for separating the prepared optical isomeric mixture are used. And 2) HPLC method. The recrystallization method has many limitations in application and there are many optical isomeric mixtures that cannot be separated by the recrystallization method. Although the HPLC method has been developed to overcome the disadvantages of the recrystallization method, this also has difficulties in various industrializations. . In other words, the separation using HPLC shows a high separation performance, but has a disadvantage in that the processing capacity can be processed at one time, and the limitation of the amount that can be processed at one time is directly linked to a high-cost process. Will follow.
본 발명은 상기의 문제를 해결하기 위한 방법으로 한번에 처리할 수 있는 용량이 크고 고효율 저비용의 특징을 지니고 있는 분리막법을 이용하였으며, 물리화학적으로 안정하고 투과특성이 우수한 나노 복합막의 제조과정에서 (D)-세린과 같은 분리하고자하는 특정 광학 이성질체를 복합막의 활성층에 분자 각인(Molecular Imprinting)시킴으로써 특정 이성질체만을 효과적으로 분리할 수 있으며 장시간 높은 분리효율을 유지시킬 수 있는 분리막을 제공하는데 그 목적이 있다.In order to solve the above problems, the present invention uses a separation membrane method having a high capacity and high efficiency and low cost, which can be processed at a time, and during the manufacturing process of a nanocomposite membrane having high physicochemical stability and excellent permeation characteristics (D The purpose of the present invention is to provide a separation membrane capable of effectively separating only specific isomers and maintaining high separation efficiency for a long time by molecular imprinting specific optical isomers such as) -serine to the active layer of the composite membrane.
상기의 목적을 달성하기 위하여 ,본 발명은 다공성 지지체에 폴리아마이드 활성층을 갖는 나노복합막의 제조과정에서 복합막의 활성층에 특정 광학이성질체를 분자 각인(Molecular Imprinting)시킨 순수광학이성질체 제조용 분리막의 제조방법을 사용하는 것이다.In order to achieve the above object, the present invention uses a method for preparing a separation membrane for producing pure optical isomers by molecular imprinting a specific optical isomer in the active layer of the composite membrane in the manufacturing process of the nanocomposite membrane having a polyamide active layer on the porous support. It is.
본 발명을 더욱 구체적으로 설명하면 다음과 같다.The present invention is explained in more detail as follows.
본 발명은 지지체는 그 재질에 크게 제한을 받지 않지만, 통상적으로 폴리설폰(PSF), 폴리이서설폰(PESF), 폴리이서이미드(PEI), 방향족폴리에스테르(PAR) 등 통상의 다공성 막을 제조하는 물질이라면 크게 제한을 받지 않으며, 용매에 대한 안정성이나 복합막의 활성층의 재질에 따라 변경하여 사용할 수 있는 것이지만, 통 상적으로는 폴리설폰이 사용하기에 좋다. 다공성지지체는 구체, 면상, 필름, 중공사형 등의 다양한 형태로 사용가능하지만, 면상 및 중공사형의 분리막으로 사용하는 것이 표면적을 넓히는 점에서 좋다. 제조방법으로 통상적인 상분리법을 이용하여 평막 형태의 다공성 지지체를 사용하였다. 폴리설폰/N-메칠피로리돈(NMP) 용액(15/85)을 폴리에스터 부직포면에 캐스팅나이프를 이용하여 일정두께로 캐스팅한 다음, 준비된 비용매인 물에 담구어서 다공성 지지체를 제조하였으며, 제조된 지지체를 50도 정도의 따뜻한 물에 수 시간동안 담구어 지지체로부터 NMP를 완전히 제거하였다.In the present invention, the support is not greatly limited in its material, but is generally a material for preparing a conventional porous membrane such as polysulfone (PSF), polyisulfone (PESF), polyisimide (PEI), aromatic polyester (PAR), etc. If it is not greatly limited, and can be used depending on the stability of the solvent or the material of the active layer of the composite membrane, polysulfone is generally good to use. Porous support can be used in various forms such as sphere, surface, film, hollow fiber, etc., but it is good to use the surface and hollow fiber membrane in terms of widening the surface area. As a manufacturing method, a porous support in the form of a flat membrane was used by using a conventional phase separation method. A polysulfone / N-methylpyrrolidone (NMP) solution (15/85) was cast on the polyester nonwoven surface using a casting knife to a certain thickness, and then immersed in water, a prepared non-solvent, to prepare a porous support. The support was immersed in warm water at about 50 degrees for several hours to completely remove NMP from the support.
상기에 제조된 다공성 지지체위에 분리막의 광학이성체 분리효율을 증가시키기 위하여 광학이성질체를 분자각인시킨 활성층을 형성시킨다. 본 발명의 활성층은 그 종류에서 광학물질이 각인된 것이라면 크게 제한을 받지 않지만, 활성층의 형성용이성 등을 고려할 때, 즉 계면중합 등에 의한 중합방법의 간단성을 고려할 때, 폴리아마이드 활성층을 적층시키는 것이 효과적이다. 폴리아마이드 활성층은 다공성지지체 예를 들면 폴리설폰 지지체 위에 폴리아민과 폴리아실클로라이드의 가교중합에 의해 제조할 수 있다. 상기 폴리아민과 폴리아실클로리드의 예를 들면 피페라진(PIP)과 트리메소일 클로라이드(TMC) 단량체를 계면중합하여 형성시킬 수 있으며, 이렇게 형성된 분리막은 치밀한 가교를 지니며 0.001㎛이하의 기공크기를 갖는 활성층을 형성하고 있어 (D)-세린 및 아미노산계 광학이성질체 분리에 적용가능 하나 이러한 나노분리막의 경우 분리막 자체에 어떠한 키랄환경도 제공하고 있지 않기 때문에 라세믹(Racemic) 화합물의 분리에 제한을 줄 수 있다.On the porous support prepared above, in order to increase the separation efficiency of the optical isomer of the separator, an active layer in which the optical isomer is imprinted is formed. The active layer of the present invention is not particularly limited as long as the optical material is imprinted in its kind. However, in consideration of the ease of formation of the active layer, that is, in consideration of the simplicity of the polymerization method by interfacial polymerization or the like, it is preferable to laminate the polyamide active layer. effective. The polyamide active layer can be prepared by crosslinking polymerization of polyamine and polyacyl chloride on a porous support such as a polysulfone support. For example, the polyamine and polyacyl chloride may be formed by interfacial polymerization of piperazine (PIP) and trimethoyl chloride (TMC) monomers, and the separator thus formed has a dense crosslinking and has a pore size of 0.001 μm or less. It is applicable to the separation of (D) -serine and amino acid-based optical isomers, but this nano-separation membrane does not provide any chiral environment to the membrane itself. Can be.
본 발명에서 활성층에 분자각인 시키는 물질로는 분리하고자 하는 어떤 광학이성질체라도 가능한데, 예를 들면 상기와 같이 활성층을 형성시킬때 분자각인 시키는 광학이성질체를 투입하여 광학이성질체가 활성층 내에 침투되어 있는 상태가 되고, 이를 다시 추출 등의 방법을 사용함으로써 활성층 내에 분자각인 사이트를 형성하게 된다. 본 발명의 분자각인 물질은 활성층 중합시 중합체 참여하지 않아야 하고, 또한 용매 추출이 가능한 것일 경우에는 어떠한 제한도 있지 않다.In the present invention, any of the optical isomers to be separated may be used as the material for imprinting the active layer. For example, when the active layer is formed as described above, the optical isomer is introduced into the active layer so that the optical isomer penetrates into the active layer. By using a method such as extraction again, a molecular imprinted site is formed in the active layer. The molecular imprinting material of the present invention should not participate in the polymer during the active layer polymerization, and there is no limitation when solvent extraction is possible.
따라서 본 발명에서는 이러한 복합막 제조과정에서 분리하고자 하는 특정 광학이성질체를 분리막 활성층에 분자각인(Molecular Imprinting)시키게 되는데 이때 각인시키는 이성질체로는 물에 추출하는 경우에는 수용성 아미노산 또는 수용성 광학물질이라면 어떠한 광학이성질체도 적용가능 하다. 분리막 활성층에 분자각인(Molecular Imprinting)시키는 방법으로는 폴리설폰 지지체 위에 피페라진(PIP)과 트리메소일 클로라이드(TMC) 단량체를 계면중합 하여 나노 분리막을 제조하는 과정에서 피페라진(PIP) 수용액에 분리하고자 하는 특정 광학이성질체, 예를들어 (D)-세린을 첨가하여 중합한 다음 다시 (D)-세린을 추출함으로써 분리막 활성층에 분자각인(Molecular Imprinting) 사이트가 생성되게 된다. 상기 피페라진(PIP)과 (D)-세린의 중량비는 1~5:1 범위에서 사용하는 것이 바람직하며 피페라진(PIP)에 대한 (D)-세린의 중량비가 1:1 이상으로 (D)-세린이 많은 경우 분리막 활성층의 형성에 방해가 되며 5:1 이하로 (D)-세린을 적게 사용할 경우 (D)-세린에 대한 분리효율이 저하되는 결과를 초래한다. Therefore, in the present invention, the specific optical isomers to be separated in the composite membrane manufacturing process are molecularly imprinted on the active layer of the membrane. In this case, the isomers to be imprinted are water soluble amino acids or optical isomers if they are extracted in water. Is also applicable. The method of molecular imprinting on the membrane active layer is performed by interfacial polymerization of piperazine (PIP) and trimesoyl chloride (TMC) monomers on a polysulfone support, and then separated from the piperazine (PIP) aqueous solution in the process of preparing a nano separator. Molecular Imprinting sites are generated in the membrane active layer by polymerizing by adding a specific optical isomer, for example, (D) -serine, and then extracting (D) -serine. The weight ratio of the piperazine (PIP) and (D) -serine is preferably used in the range of 1 to 5: 1, and the weight ratio of (D) -serine to the piperazine (PIP) is 1: 1 or more (D). -If there is a large amount of serine will interfere with the formation of the membrane active layer, the use of less (D) -serine below 5: 1 will result in a reduction in the separation efficiency for (D) -serine.
본 발명에 따른 복합분리막의 제조방법을 폴리아마이드를 활성층으로 하는 경우에, 그리고 중합을 계면중합방법으로 제조하고, 각인되는 광학이성질체가 수용성일 경우에 대하여 구체적으로 설명하면 다음과 같은 단계로 제조될 수 있다.When the composite separator according to the present invention is prepared using polyamide as an active layer, and the polymerization is prepared by the interfacial polymerization method, and the optical isomers imprinted thereon are specifically described as follows. Can be.
(a)다공성지지체를 제조하는 단계;(a) preparing a porous support;
(b)상기 다공성지지체를 아민단량체와 분자각인을 위한 수용성 광학이성질체의 혼합물 수용액에 침지하는 단계;(b) immersing the porous support in an aqueous solution of a mixture of amine monomers and water-soluble optical isomers for molecular imprinting;
(c)상기 침지된 다공성지지체의 표면에 과량으로 존재하는 수용액을 제거하는 단계;(c) removing the aqueous solution present in excess on the surface of the immersed porous support;
(d)상기 (c)의 다공성지지체를 아실할라이드가 용해된 용매에 침지, 계면중합하여 폴리아마이드층을 형성 하는 단계;(d) immersing the porous support of (c) in a solvent in which acyl halide is dissolved and interfacially polymerizing to form a polyamide layer;
(e)상기 폴리아마이드층으로부터 수용성 광학이성질체를 핵산 등의 유기용매에서 추출하여 분자각인하는 단계;(e) extracting the water-soluble optical isomer from the polyamide layer in an organic solvent such as a nucleic acid to imprint a molecule;
로 구성되는 광학이성질체 분리용 고분자 분리막의 제조방법을 예시할 수 있다.It can be exemplified a method for producing a polymer separation membrane for separating optical isomers.
본 발명은 폴리아마이드를 활성층으로 하는 경우 분자각인 물질로 (D)-세린 이외에 수용성인 아미노산계 광학이성질체에 모두 적용 가능하다. The present invention is applicable to all of the water-soluble amino acid optical isomers in addition to (D) -serine as the molecular imprinting material when the polyamide is an active layer.
이하에서 본 발명을 실시 예를 들어 좀 더 상세히 설명하나 본 발명이 실시 예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.
[실시예 1] 각인된 분리막의 제조Example 1 Preparation of Engraved Separator
폴리설폰/N-메칠피로리돈(NMP) 용액(15/85)을 폴리에스터 부직포면에 캐스팅나이프를 이용하여 일정두께로 캐스팅한 다음, 준비된 비용매인 물에 1시간 담구어서 다공성 지지체를 제조한다. 제조된 지지체는 50도 정도의 따뜻한 물에서 수 시간동안 담구어져 지지체로부터 NMP를 완전히 제거한다. 이렇게 제조된 폴리설폰 다공성 지지체의 분리투과특성은 분획분자량(MWCO) 50,000, 5.0 m3/m2day (1기압에서) 정도의 투수성을 지니게 된다.A polysulfone / N-methylpyrrolidone (NMP) solution (15/85) is cast on the polyester nonwoven surface using a casting knife to a predetermined thickness, and then immersed in water, which is a nonsolvent prepared, for 1 hour to prepare a porous support. The prepared support is immersed in warm water at about 50 degrees for several hours to completely remove NMP from the support. The separation permeation characteristics of the polysulfone porous support thus prepared have a permeability of about 50,000 molecular weight fraction (MWCO) and 5.0 m 3 / m 2 day (at 1 atm).
피페라진/(D)-세린의 조성이 5/1의 중량비인 수용액을 제조하여 상기에 언급한 폴리설폰 지지체로 형성된 평막을 2분간 침지시킨 후 분리막 표면에 과잉으로 존재하는 수용액을 롤러를 이용하여 제거시켜준다. 피페라진과 (D)-세린이 코팅된 분리막을 다시 준비된 1/99 중량 %의 트리메소일클로라이드(Trimesoylchloride)/헥산 용액에 10초간 담구어 상온에서 계면중합시킨다. 제조된 분리막을 40℃의 물에 40시간 담구어 (D)-세린을 추출해 낸다. 이렇게 하여 분리막 활성층에 (D)-세린이 분자 각인된 나노분리막을 제조하였다.A solution of piperazine / (D) -serine in a weight ratio of 5/1 was prepared, the flat membrane formed of the polysulfone support mentioned above was immersed for 2 minutes, and then an aqueous solution that was excessively present on the surface of the separator using a roller. Remove it. The piperazine and (D) -serine-coated separators were immersed in the prepared 1/99 wt% trimesoylchloride / hexane solution for 10 seconds and interfacially polymerized at room temperature. The prepared membrane was immersed in water at 40 ° C. for 40 hours to extract (D) -serine. In this way, (D) -serine-molecule engraved nanoseparation membrane was prepared in the membrane active layer.
[시험예 1][Test Example 1]
상기 실시예 1의 분리막은 적외선 분광법(IR)을 통해 분리막 활성층에 (D)-세린이 각인되어 있음을 확인하였으며, (D)-세린 추출 전 분리막과 (D)-세린 추출 후 분리막의 물에 대한 투과성능을 테스트해본 결과를 다음 표1에 나타내었다. 그 결과, 추출후의 투과량이 전체적으로 매우 증가된 것을 볼 수 있어, (D)-세린이 잘 각인되어 있음을 알 수 있었다. The separator of Example 1 confirmed that (D) -serine was imprinted on the active layer of the separator through infrared spectroscopy (IR), and the membrane before (D) -serine extraction and after the (D) -serine extraction were separated into water. The results of testing the permeability of the test are shown in Table 1 below. As a result, it was found that the amount of permeation after extraction was greatly increased as a whole, indicating that (D) -serine was well imprinted.
[표 1]TABLE 1
[시험예 2][Test Example 2]
상기 실시예 1의 분리막을 이용하여 0.2 중량%의 D,L-세린을 1bar의 압력으로 분리막의 투과실험을 실시하여 광학이성질체의 분리실험을 실시하여 그 결과를 표 2에 나타내었다. 표 2에서 보듯이 본 발명의 분리막을 이용할 경우, (D)-세린이 각인된 분리막을 이용하여 광학이성질체를 분리한 결과, 분리의 선택도가 5배이상 현저히 증가되었음을 알 수 있어 본 발명의 분리막으로 광학이성질체의 분리효율을 매우 향상시킬 수 있음을 알 수 있었다.Using the separator of Example 1, 0.2 wt% D, L-serine was subjected to permeation experiment of the separator at a pressure of 1 bar to perform the separation experiment of the optical isomer, and the results are shown in Table 2. As shown in Table 2, when using the separation membrane of the present invention, the separation of the optical isomer using the (D) -serine imprinted separation, it can be seen that the selectivity of the separation is significantly increased more than five times the separation membrane of the present invention It can be seen that the separation efficiency of the optical isomer can be greatly improved.
[표 2]TABLE 2
이상에서 설명한 바와 같이, 본 발명에 따라 제조된 특정분자가 각인된 분리막은 (D)-세린을 포함한 다양한 광학이성질체 분리에 응용가능하며, 특정분자에 대한 선택적 분리효율을 극대화 시킬 수 있고 장시간 높은 분리효율을 유지할 수 있으므로 연속적 대량생산의 기능성과 경제성을 증가시킬 수 있을 것이다.As described above, the separation membrane imprinted with specific molecules prepared according to the present invention is applicable to the separation of various optical isomers including (D) -serine, can maximize the selective separation efficiency for specific molecules and high separation for a long time Efficiency can be maintained to increase the functionality and economics of continuous mass production.
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| KR0170072B1 (en) * | 1996-03-11 | 1999-01-15 | 박홍기 | Method for manufacturing polyamide nano composite membrane |
| KR20020007591A (en) | 2000-07-18 | 2002-01-29 | 김충섭 | Inter-Penetrating Polyvalent Ion Complex Membrane For Separating Organic Mixture And Method For Preparing The Same |
| KR20030022915A (en) | 2001-09-11 | 2003-03-19 | 주식회사 새 한 | Producing method of composite polyamide reverse osmosis membrane |
| KR100516203B1 (en) * | 2004-03-24 | 2005-09-23 | 한국화학연구원 | Water treatment membranes containing photo-catalysts and their preparation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101118760B1 (en) * | 2009-12-29 | 2012-03-13 | 재단법인대구경북과학기술원 | Molecular imprinted polymers for detecting Pentraxin protein and the methods thereof |
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| KR20070096705A (en) | 2007-10-02 |
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