CN102438734B - A method for preparation of enantioselective composite membrane - Google Patents
A method for preparation of enantioselective composite membrane Download PDFInfo
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- CN102438734B CN102438734B CN201080022405.5A CN201080022405A CN102438734B CN 102438734 B CN102438734 B CN 102438734B CN 201080022405 A CN201080022405 A CN 201080022405A CN 102438734 B CN102438734 B CN 102438734B
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- film
- enantioselectivity
- composite membrane
- amino acid
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- 239000012528 membrane Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000001413 amino acids Chemical class 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 239000000243 solution Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 27
- 239000004475 Arginine Substances 0.000 claims description 19
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 19
- 238000000108 ultra-filtration Methods 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical class C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 15
- 150000001412 amines Chemical class 0.000 claims description 13
- -1 carboxylic acid halides Chemical class 0.000 claims description 12
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- 238000000576 coating method Methods 0.000 claims description 12
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 238000013507 mapping Methods 0.000 claims description 4
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- 150000003141 primary amines Chemical group 0.000 claims description 4
- 238000001223 reverse osmosis Methods 0.000 claims description 4
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- 238000009736 wetting Methods 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 10
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 97
- 235000001014 amino acid Nutrition 0.000 description 33
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 18
- 239000007788 liquid Substances 0.000 description 14
- 238000001764 infiltration Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 230000008595 infiltration Effects 0.000 description 9
- 239000003814 drug Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000007605 air drying Methods 0.000 description 6
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- 229940079593 drug Drugs 0.000 description 5
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- 238000001228 spectrum Methods 0.000 description 5
- UEJJHQNACJXSKW-UHFFFAOYSA-N 2-(2,6-dioxopiperidin-3-yl)-1H-isoindole-1,3(2H)-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1C1CCC(=O)NC1=O UEJJHQNACJXSKW-UHFFFAOYSA-N 0.000 description 4
- 230000005526 G1 to G0 transition Effects 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
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- AQHHHDLHHXJYJD-UHFFFAOYSA-N propranolol Chemical compound C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 AQHHHDLHHXJYJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- 229960003433 thalidomide Drugs 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- SGTNSNPWRIOYBX-MHZLTWQESA-N (S)-verapamil Chemical compound C1=C(OC)C(OC)=CC=C1CCN(C)CCC[C@](C#N)(C(C)C)C1=CC=C(OC)C(OC)=C1 SGTNSNPWRIOYBX-MHZLTWQESA-N 0.000 description 2
- KDXKERNSBIXSRK-RXMQYKEDSA-N D-lysine Chemical compound NCCCC[C@@H](N)C(O)=O KDXKERNSBIXSRK-RXMQYKEDSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
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- 150000004676 glycans Chemical class 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 230000000144 pharmacologic effect Effects 0.000 description 2
- 229920001197 polyacetylene Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229960003712 propranolol Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229940127291 Calcium channel antagonist Drugs 0.000 description 1
- QNAYBMKLOCPYGJ-UWTATZPHSA-N D-alanine Chemical compound C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 description 1
- ODKSFYDXXFIFQN-SCSAIBSYSA-N D-arginine Chemical compound OC(=O)[C@H](N)CCCNC(N)=N ODKSFYDXXFIFQN-SCSAIBSYSA-N 0.000 description 1
- 238000012696 Interfacial polycondensation Methods 0.000 description 1
- 108010038807 Oligopeptides Proteins 0.000 description 1
- 102000015636 Oligopeptides Human genes 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 239000000480 calcium channel blocker Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000747 cardiac effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005557 chiral recognition Methods 0.000 description 1
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- 230000001112 coagulating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SGTNSNPWRIOYBX-HHHXNRCGSA-N dexverapamil Chemical compound C1=C(OC)C(OC)=CC=C1CCN(C)CCC[C@@](C#N)(C(C)C)C1=CC=C(OC)C(OC)=C1 SGTNSNPWRIOYBX-HHHXNRCGSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000018977 lysine Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000344 molecularly imprinted polymer Polymers 0.000 description 1
- QRYWJFOBXFDERP-UHFFFAOYSA-N n-[(2-amino-6-methylpyridin-3-yl)methyl]-3,4,5-trimethoxybenzamide Chemical compound COC1=C(OC)C(OC)=CC(C(=O)NCC=2C(=NC(C)=CC=2)N)=C1 QRYWJFOBXFDERP-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
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- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003087 receptor blocking agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/007—Separation by stereostructure, steric separation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/30—Preparation of optical isomers
- C07C227/34—Preparation of optical isomers by separation of optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C277/00—Preparation of guanidine or its derivatives, i.e. compounds containing the group, the singly-bound nitrogen atoms not being part of nitro or nitroso groups
- C07C277/06—Purification or separation of guanidine
Abstract
The present invention provides an enantioselective composite membrane useful for separation of optical isomers and the process for the preparation thereof. The invention further provides a membrane based pressure driven separation process for separation of enantiomers from their mixture to obtain optical pure isomers. The present invention also provides a membrane based method for optical resolution of racemic mixtures of amino acids to obtain optically pure amino acids.
Description
Invention field
The present invention relates to a kind of preparation method of enantioselectivity composite membrane, this enantioselectivity composite membrane is for separating amino acid and for the optical resolution of racemic mixture from their aqueous solution.The invention particularly relates to a kind of preparation method of enantioselectivity composite nanometer filtering film, this enantioselectivity composite nanometer filtering film is for the separation of amino acid whose optical isomer.
Enantioselectivity composite membrane of the present invention is for separating enantiomter to obtain optically pure isomers from enantiomeric mixture.Enantioselectivity composite membrane of the present invention is used in pressure-driven membrane process, and as counter-infiltration, in the membrane process such as nanofiltration, the racemic mixture of optical resolution amino acid and chipal compounds is to obtain the pure enantiomter of optically-active.
Background of invention
Stereoisomer refers to those molecules that atom wherein only spatially differs from one another on arrangement mode.Stereoisomer is generally divided into diastereoisomer or enantiomter; The latter comprises each other the relation for mirror image, and the former is not for being those of mirror image.Enantiomter (mirror image), claims again optical isomer, has identical physics and chemistry character.Therefore, the mixture of enantiomter can not be separated by common separation method conventionally, and common separation method is as fractionation (boiling point is identical); As traditional crystallization, except non-solvent is optically active (because solubility is identical); As traditional chromatogram, unless adsorbent has optical activity (because they are identical for common adsorbent suction-operated).In fact,, because traditional synthetic technology almost always produces the mixture of enantiomter, therefore, the problem that separates enantiomter becomes further serious.Therefore, the separation of the mixture of enantiomter is challenging problem of tool in analytical chemistry.
For organic compound, as amino acid, medicine, agricultural chemicals, agrochemical, the separation of enantiomter is very important, because major part is to have optically actively in them, and exists in pairs as optical isomer (enantiomter).Between the enantiomter of many chiral drugs, aspect biology and pharmacological property, there is significant difference.An enantiomter may have pharmaceutically active, and other may be inertia or even harmful, for example, (S)-Verapamil ((S)-verapamil) is effective calcium channel blocker, and (R)-Verapamil has cardiac side effects, the activity of the l-enantiomter of receptor blocking agent Propranolol (propranolol) is more than its d-type～100 times, (R) (+)-enantiomter of Thalidomide (thalidomide) has the effect of sleeping, and its (S) (-)-enantiomter has teratogenesis, the difference of finding the pharmacologically active of Thalidomide has been used medicine and has caused neonate to occur that severe deformities (" the Thalidomide tragedy " of nineteen sixties etc.) is responsible at period of gestation for women.Therefore, " Food and Drug Administration (The United States Food and Drug Administration) " promulgated the marketing of new regulation management chiral drug recently.According to new regulation, the pharmacological property of each enantiomter to chiral drug should be carried out separately efficacy and saferry test.
Known have the separation of several different methods for enantiomter, for example application of diastereoisomer fractionation, enzymic catalytic reaction, chromatography, liquid film, molecular recognition technology and an inclusion compounding technique.Preferential crystallisation, diastereoisomer splits, and enzymic catalytic reactions etc., are combined and convert them to diastereoisomer with an auxiliary chiral reagent thereby relate to enantiomter, then can be by any conventional isolation technics separately.Relevant diastereoisomer splits, referring to " CRC Handbook ofOptical Resolutions via Diasteromeric Salt Formation " Kozma D., 2002ISBN:0849300193.The major defect that diastereoisomer splits is to need a large amount of pure derivating agents of optically-active (chiral reagent or solvent), and they are expensive and conventionally cannot reclaim.
Can reference color spectral technology (GC, HPLC, CE etc.), it is described in, and " Chiral Separation Techniques-A Practical Approach is " in the second edition, G.Subramanian chief editor, ISBN3-527-29875-4, wherein chromatographic process require suitable chiral selector be attached to fixing mutually in (chiral stationary phase) or be coated in the surface (chirality coated stationary phase) of column material.The enantioselectivity chiral chromatographic column with chiral stationary phase is expensive, and working life is limited, and therefore, the cost of separation is quite high.
Can be with reference to the molecular recognition phenomenon for stage enantiomer separation, it is reported in " Chiral Separation Techniques-A Practical Approach " in the second edition, G.Subramanian chief editor, ISBN3-527-29875-4.Chiral stationary phase, the complex etc. of different model have been developed based on molecular recognition.
Can be with reference to the United States Patent (USP) 6759488 that is entitled as " Molecularly imprinted polymers grafted on solid supports ", wherein stage enantiomer separation is based on molecular recognition phenomenon.The shortcoming of MIP technology is that crosslinkable monomers can only be for the preparation of molecular imprinting film.
Can be with reference to the United States Patent (USP) 5 that is entitled as " Supported chiral liquid membrane for the separation of enantiomers ", 080,795, the chirality liquid film that wherein comprises chiral support optionally coordinates and it is separated with other with the one in two kinds of enantiomters.The major defect of this film is poor stability, As time goes on enantioselectivity variation.
Can be with reference to the United States Patent (USP) 6 that is entitled as " Liquid membrane separation of enantiomers ", 485,650, wherein in the liquid film supporting module that comprises carrier and phase transfer reagent, separate the method for enantiomter by the feed liquid that comprises racemic mixture, describe enantiomter has been transported to liquid film, thereafter liquid film has been contacted with sweeping fluid.Then from sweeping fluid, reclaim this enantiomter.Membrane module is like this operation: feeding liquid and sweeping fluid are adjacent, but on opposing face, and liquid film and feeding liquid and sweeping fluid have substantially continuous interface along liquid film length and contact.The shortcoming of this liquid-liquid technique is that the chance that productive rate is lower, two kinds of solution mixes mutually at membrane interface place is less.
Can be with reference to the United States Patent (USP) 4 that is entitled as " Interfacially synthesized reverse osmosis membrane ", 277,344, wherein relate to a kind of aromatic polyamide film, this film is that the aromatic polyamine by least containing two primary amine groups obtains by interfacial reaction with the aromatic acyl halides that at least contains three acyl halide groups.According to this patent, first the polysulfones carrier of porous uses the m-phenylene diamine (MPD) coating in water.From coating carrier, drop falls unnecessary m-phenylene diamine (MPD) solution, then covers the carrier being coated with the solution that pyromellitic trimethylsilyl chloride is dissolved in " FREON " TF solvent.Be 10 seconds the time of contact of interfacial reaction, and reaction roughly completed at 1 second.Subsequently by air-dry consequent polysulfones/polyamide composite film.It is said that this film has good flux and salt rejection rate.But in order to improve the performance of film, adding polytype additive for the solution of interfacial polycondensation reaction.The shortcoming of this film is not have enantioselectivity.
Can, with reference to the United States Patent (USP) 5,205,934 that is entitled as " Silicone-derived solvent stable membranes ", the preparation method of composite nanometer filtering film wherein be described, comprising one deck siloxanes is fixed on carrier, optimization polypropylene nitrile carrier.It is said that these composite membranes have solvent stability, and it is said and can be used for the solute of separation of high molecular weight from solvent, include organic metal catalyst complex.But these films do not have enantioselectivity.
Can be with reference to the United States Patent (USP) 6 that is entitled as " Process for the separation of enantiomers and enantiopure reagent ", 743,373, the mixture that wherein comprises enantiomter in alkaline medium with a kind of reagent reacting based on mapping pure amino acid, then the non-enantiomer mixture of gained is carried out to lock out operation.The shortcoming of the method is, for enantiomter to be separated, enantiomter must have at least one free functional group, and comprise amino acid whose at least one amino reagent with activated group to form the active precursor of isocyanates, and therein, it is substituted that amino acid has a carboxyl at least.
Enantioselectivity polymer film described in prior art is as detailed above all asymmetric dense film, and these films are to use chiral polymer as polysaccharide and derivative, poly-a-amino acid, and Polyacetylene Derivatives etc. are manufactured.These polymer great majority are crystal form under field conditions (factors), do not have film and form ability.Thereby the film that uses these polymer to prepare is fragile, thereby be difficult to process.Poor mechanical performance causes their use to be limited to the separation of dialysis mode.In dialysis clastotype, driving force is only solute concentration gradient, and therefore, these films show low-down infiltration rate.Other type stage enantiomer separation film is made with achiral polymer, and these polymer have the enantiomter identification molecule of grafting, that is, and and amino acid, protein, oligopeptides etc.These films have compared with high-mechanical property, become rapidly saturated but be fixed on film in polymeric matrix at infiltration recognizing site, thus As time goes on this film selectively sharply decline.
The common preparation method of composite membrane is: by the applying porous carrier film of the aqueous solution of polyfunctional amine, adopt subsequently the solution of multifunctional carboxylic acid halides in organic solvent to be coated with, the film on polyamide identification layer is prepared in the interface condensation reaction by polyfunctional amine and multifunctional carboxylic acid halides as described in many patents.
Innovation of the present invention is: the identification layer that i) obtains composite membrane by chiral amino acid and polyfunctional amine and multifunctional acyl chlorides generation interface polymerization reaction; (ii) prepare the very small amount of chipal compounds of chirality enantioselectivity layer needs by interfacial process, and can generate the film that has in a large number same chiral environment; (iii) method minimizes the demand of necessary separation for racemic mixture optically-active homochiral reagent; (iv) mapping of method load on ultrafiltration layer is selected to have brought chirality microenvironment in the polymer film of thin layer form, and this has caused, and higher flux and Geng Gao's is selective.
Goal of the invention
Main purpose of the present invention is to provide a kind of preparation method who prepares from the permoselective membrane of load, and this film is by pressure-driven membrane process, and as counter-infiltration, the separation of enantiomter is carried out in nanofiltration etc.
Another object of the present invention is to provide a kind of composite membrane based on piperazine and pyromellitic trimethylsilyl chloride, due to piperazine and pyromellitic trimethylsilyl chloride be cis-selectivity therefore do not carry out stage enantiomer separation.
Another object of the present invention is to provide high stability and the As time goes on maintenance of enantioselectivity.
Another object of the present invention is to provide a kind of preparation method of enantioselectivity composite nanometer filtering film, and this film is for separating of the enantiomter of chiral molecules.
It is the method based on film of optically-active pure isomer by racemic mixture optical resolution that an also object of the present invention is to provide a kind of.
Accompanying drawing summary
Fig. 1: Fig. 1 shows the chemical constitution ATR-FTIR spectrum of the enantioselectivity layer of enantioselectivity composite membrane.
Summary of the invention
Therefore, the invention provides a kind of method for the preparation of enantioselectivity composite membrane, described enantioselectivity composite membrane is for separating enantiomter to obtain optically-active pure isomer from the mixture of enantiomter, and described method comprises:
(a) provide ultrafiltration (UF) film preparing by wetting phase conversion method;
(b) the milipore filter impregnation mixture coating time of 1 to 5 minute that will obtain from step (a), described mixture comprises the following 1-2% aqueous solution: amino acid or amino acid whose mixture, polyfunctional amine and acid acceptor; Keep pH value in 10 to 13 scope;
(c) from step (b) gained mixture, shift out the UF film of coating, drop falls redundant solution in this UF film 5 to 30 minutes;
(d) film of the coating of gained from step (c) is flooded to 1-5 minute again in the hexane solution of three carboxylic acid halides of 0.1-1%, drop falls unnecessary solution 1-5 minute;
(e) film of gained in step (d) is dried to 1 to 4 hour;
(f) the film of the temperature heating gained from step (e) of 70 ℃-100 ℃ 1 to 15 minute, cooling and air was dried 1 to 2 hour subsequently;
(g) film of gained from step (f) is soaked 24 hours in deionized water, on milipore filter, comprise the enantioselectivity composite membrane of enantioselectivity layer to obtain, and described enantioselectivity composite membrane is carried out to the discrete testing of amino acid from their aqueous solution.
In one embodiment of the invention, the enantioselectivity layer of composite membrane used has enantioselectivity, its thickness range be 400 to
In another embodiment of the invention, the freely group of at least two primary amine group compositions of amino acid used or ispol choosing.
In another embodiment, the enantioselectivity layer of composite membrane used has the crosslinked polyamide polymer that comprises at least one asymmetric carbon atom.
In another embodiment, polyfunctional amine used is selected from m-phenylene diamine (MPD), piperazine, and acid acceptor used is selected from triethylamine or NaOH.
In another embodiment also, multifunctional three carboxylic acid halides used are pyromellitic trimethylsilyl chloride.
In another embodiment, milipore filter used selects the polysulfones of free thickness in the scope of 20-60 μ m, polyether sulfone, the group of polyvinylidene fluoride composition.
In another embodiment again, the composite membrane of enantioselectivity separates arginine and the 80-90% lysine of 50-70% from the aqueous solution.
In another embodiment also, the method that uses the composite membrane of enantioselectivity amino acid racemization mixture to be carried out to mapping separation, wherein said method is carried out under the following conditions on reverse osmosis membrane test cell: transmembrane pressure is in the scope of 345KPa to 862KPa, use amino acid solution and/or buffer solution in 0.1 to 1% scope, at 20-30 ℃ with the flow rate charging within the scope of per minute 300 to 800ml.
Going back in another embodiment, wherein measure amino acid whose concentration in penetrant by UV-Vis spectrophotometer, by using chiral column, the ratio of d and l-enantiomter in the HPLC that is equipped with PDA detector assesses penetrant.
Detailed Description Of The Invention
Enantioselectivity thin-film composite membrane of the present invention is by progressively using following coating porous carrier to prepare: basic amino acid (has the amino acid of two primary amine groups, as arginine, lysine etc.) or the mixture of basic amino acid, polyfunctional amine (as m-phenylene diamine (MPD), piperazine, preferably piperazine) and acid acceptor (triethylamine, NaOH, preferably NaOH); And multifunctional carboxylic acid halides (having more than one active site), preferably pyromellitic trimethylsilyl chloride.The not specific order of application step, but be preferably first coated with amino acid or amino acid whose mixture, polyfunctional amine and acid acceptor, be coated with subsequently multifunctional carboxylic acid halides.Amino acid or amino acid whose mixture and polyfunctional amine are coated with the aqueous solution, and multifunctional carboxylic acid halides uses organic solution to be coated with.
First, use such as polysulfones of polymeric material, polyether sulfone, polyvinylidene fluoride, preferably polysulfones, prepares milipore filter by phase transfer of technology.In this technology, by above-mentioned polymer at aprotic solvent (as dimethyl formamide, N, N-dimethylacetylamide etc.) in suitable concentration 12 to 18%w/w (more properly, solution 18%w/w) spreads upon in non-woven polyester fabric (carrier) with uniform thickness, then after the 10-40 stipulated time of second, by this carrier impregnation in the coagulating bath of the dimethyl formamide aqueous solution that accommodates 2%.With deionized water flushing membrane several.
With as stated above preparation milipore filter prepare enantioselectivity composite nanometer filtering film of the present invention, described preparation is carried out by the following method: on the enantioselectivity layer of milipore filter, by interfacial polymerization technology, make the 1-2% reactant aqueous solution of the following: amino acid or amino acid whose mixture (arginine), the preferred piperazine of polyfunctional amine (ratio of arginine and piperazine is 50-50%) and acid acceptor (are triethylamine, NaOH etc., preferably NaOH), and original position is prepared enantioselectivity thin layer.The pH value of the aqueous solution is remained on 10-13 by 0.1-1% solution with pyromellitic trimethylsilyl chloride in hexane, and preferably 12.
In order to prepare enantioselectivity layer on the enantioselectivity layer at milipore filter, first by its dipping of aqueous solution with amino acid or amino acid whose mixture, the preferred piperazine of polyfunctional amine (ratio of arginine and piperazine is 50-50%) and acid acceptor (being triethylamine and NaOH) 1-5 minute, be 3 minutes definitely.From solution, shift out coating UF film, and last 5-30 minute, 15 minutes drops fall solution unnecessary on UF film to retain the monomer of aequum definitely.
Then use the 0.1-1% solution of pyromellitic trimethylsilyl chloride in hexane, 0.5% solution definitely, dipping UF film 1-5 minute, 3 minutes definitely.From the solution mixture of pyromellitic trimethylsilyl chloride, shift out the UF film of coating, and last 1-5 minute, 5 minutes drops fall pyromellitic trimethylsilyl chloride solution unnecessary on film definitely.By filter membrane at air drying 1-4 hour, 4 hours definitely, then at 70-100 ℃, the temperature of the 90 ℃ 1-15 minute that is heating and curing definitely, 10 minutes definitely, subsequently that gained film is cooling and dry 2 hours in air, be then immersed in the water reach 24 hours with required enantioselectivity composite membrane.
Fig. 1. the chemical constitution of the enantioselectivity layer with the spectrophotometer of ATR-FTIR to enantioselectivity composite membrane characterizes.With Perkin-Elmer spectrometer (Perkin-Elmer Spectrum GX, ATR-FTIR) record the ATR-FTIR spectrum that is coated with the PS membrane before and after coating, test condition is: use germanium crystal, 45 ° of nominal incidence angles, speed 100scans, resolution ratio 2cm
-1.The ATR-FTIR spectrum of (B) after having provided PS membrane (A) below and having been used poly-(the equal benzene trimethamide of piperazine arginine) pleurodiaphragmatic in terspace position to be coated with.1487-90cm
-1and 1584cm
-1the peak at place is the characteristic peak of polysulfones carrier.1472-1644cm
-1the absorption band occurring in region is C=O, and C=N stretching vibration produces.1667cm on the spectrum of the film of coating
-1the formation of the peak indication acid amides at place.1731cm
-1(C=O of imide ring), 1369cm
-1(C-N-C, the acid imide of plane), and 747cm
-1the characteristic absorption that (C-N-C, out-of-plane bending, acid imide) located.
About carrying out separating of enantiomter with amino acid separation cushioning liquid and from amino acid whose racemic mixture from the aqueous solution of the preferred arginine of amino acid, lysine, alanine etc., on reverse osmosis membrane test cell, film is tested, test condition comprises: transmembrane pressure is 345KPa to 862KPa, 552KPa definitely, use 0.1 to 1% amino acid solution and buffer solution, the temperature of 25 ℃ with per minute 300 to 800ml, the flow rate charging of 500ml per minute definitely.In penetrant, amino acid whose concentration is measured at 290nm by UV-Vis spectrophotometer, determine that the ratio of d and l-enantiomter in the penetrant of enantiomter excessive (ee%) is by having on the HPLC of PDA detector, the chiral column Chrompack (+) that uses the Diacel Chemical Industries of the U.S. to provide assesses.
Enantiomter refers to have identical molecular formula and chemical constitution, and the different chiral molecules of space arrangement mode only.The difference of space arrangement mode is implying that the biology of a lot of chipal compounds is completely different with medicinal actives.Therefore use this compound of the pure form of optically-active to be very important.The separation of enantiomter is a stubborn problem.There are at present a lot of stage enantiomer separation technology based on different technologies.Identify pairing enantiomter but all stage enantiomer separation technology are all near the chirality microenvironments based on raceme mixture.
The existence of same chiral environment is necessary for difference pairing enantiomter.The novel part of film of the present invention is as the polymer film of the enantioselectivity layer thin layer form of load on ultrafiltration layer provides chirality microenvironment, and this has caused, and higher flux and Geng Gao's is selective.
Composite membrane of the present invention has the enantioselectivity layer chiral Recognition layer of preparing at milipore filter surface in situ.Enantioselectivity layer identification layer is to be generated by the interfacial polymerization of chiral amino acid and polyfunctional amine and multifunctional acyl chlorides.Interfacial process is prepared chirality and is selected layer to need very small amount of chipal compounds, and can generate the film that has in a large number same chiral environment.Therefore, the demand of optically-active homochiral the reagent required separation for racemic mixture is minimized.
Following examples are only for better explanation the present invention, therefore should not be construed as limitation of the scope of the invention.
The preparation method of enantioselectivity composite membrane comprises: in the arginine by polysulfones UF film in 1% and piperazine (Piprazine) aqueous solution (50:50), flood 3 minutes, keeping the pH of solution by the NaOH of interpolation 1N is 12, last 15 minutes drops and fall unnecessary solution, then film is flooded 2 minutes in the hexane solution of 0.5% pyromellitic trimethylsilyl chloride, last 2 minutes drops and fall unnecessary solution, then by film air drying 4 hours.Film is heating and curing 5 minutes at the temperature of 90 ℃, is cooled to the temperature of 25 ℃, dry 2 hours of air then soaks and reaches 24 hours in deionized water.Under standard conditions, test film to arginic separation and enantioselectivity: use 0.1% the racemic arginine aqueous solution as charging, flow rate is 500ml per minute under 552KPa.The infiltration rate that film demonstrates is 636l/m
2/ day, arginine rejection (rejection) is 75%, is 65% to the arginic enantioselectivity of d-.
Embodiment 2
The preparation method of enantioselectivity composite membrane comprises: in the arginine by polysulfones UF film in 1% and the aqueous solution of piperazine (50:50), flood 3 minutes, keeping the pH of the aqueous solution by the NaOH of interpolation 1N is 12, last 15 minutes drops and fall unnecessary solution, then film is flooded 2 minutes in the hexane solution of 1% pyromellitic trimethylsilyl chloride, last 5 minutes drops and fall unnecessary solution, then by film air drying 4 hours.Film is heating and curing 5 minutes the temperature of 90 ℃, is cooled to the temperature of 25 ℃, dry 2 hours of air then soaks and reaches 24 hours in deionized water.Under standard conditions, test film to arginic separation and enantioselectivity: use the 0.1% racemic arginine aqueous solution as charging, flow rate is 500ml per minute under 552KPa.The infiltration rate that 6 hours caudacorias demonstrate is 734l/m
2/ day, arginine rejection is 66%, is 50% to the arginic enantioselectivity of d-.
Embodiment 3
The preparation method of enantioselectivity composite membrane comprises: polysulfones UF film is flooded 3 minutes in 1% the piperazine aqueous solution, keeping the pH of the aqueous solution by the NaOH of interpolation 1N is 12, last 15 minutes drops and fall unnecessary solution, then film is flooded 2 minutes in the hexane solution of 0.5% pyromellitic trimethylsilyl chloride, last 5 minutes drops and fall unnecessary solution, then by film air drying 4 hours.Film is heating and curing 5 minutes the temperature of 90 ℃, is cooled to the temperature of 25 ℃, dry 2 hours of air then soaks and reaches 24 hours in deionized water.Under standard conditions, film is tested: use the 0.1% racemic arginine aqueous solution as charging, flow rate is 500ml per minute under 552KPa.The infiltration rate that film demonstrates is 1125l/m
2/ day, arginine rejection is 60%.Film does not demonstrate enantioselectivity to d-arginine.
Embodiment 4
The preparation method of enantioselectivity composite membrane comprises: polysulfones UF film is flooded 3 minutes in 1% the arginine aqueous solution, making the pH of this aqueous solution by the NaOH of interpolation 1N is 12, last 15 minutes drops and fall unnecessary solution, then film is flooded 2 minutes in the hexane solution of 0.5% pyromellitic trimethylsilyl chloride, last 2 minutes drops and fall unnecessary solution, then by film air drying 4 hours.Film is heating and curing 5 minutes the temperature of 90 ℃, is cooled to 25 ℃, dry 2 hours of air then soaks and reaches 24 hours in deionized water.Under standard conditions, film is tested: the racemic arginine aqueous solution of use 0.1% is as charging, and flow rate is 500ml per minute under 552KPa.The infiltration rate that film demonstrates is 1125l/m
2/ day, arginine rejection is 48%, and film to show the arginic enantioselectivity of d-be 50%.
Embodiment 5
The preparation method of enantioselectivity composite membrane comprises: in the situation that pH value is 12, in lysine by polysulfones UF film in 1% and the aqueous solution of piperazine (50:50), flood 5 minutes, last 15 minutes drops and fall unnecessary solution, then film is flooded 5 minutes in the hexane solution of 0.5% pyromellitic trimethylsilyl chloride, last 5 minutes drops and fall unnecessary solution, then by film air drying 4 hours.The temperature of 90 ℃, film is heating and curing 5 minutes, is cooled to the temperature of 25 ℃, dry 2 hours of air then soaks and reaches 24 hours in deionized water.Under standard conditions, film is tested: use 0.1% racemic lysine solution as charging, flow rate is 500ml per minute under 552KPa.The infiltration rate that film demonstrates is 587.19l/m
2/ day, lysine rejection is 83%, it is 90% that film shows d-lysine enantioselectivity.
Embodiment 6
Prepare enantioselectivity composite membrane according to embodiment 1, under standard conditions, film is tested: use 0.1% racemic lysine solution as charging, flow rate is 500ml per minute under 552KPa.The infiltration rate that film demonstrates is 293.54l/m
2/ day, lysine rejection is 46%, is 60% to the enantioselectivity of d-lysine.
Embodiment 7
Prepare enantioselectivity composite membrane according to embodiment 1, under standard conditions, film is tested: use the 0.05% racemic alanine aqueous solution as charging, flow rate is 500ml per minute under 552KPa.The volume flux that film demonstrates is 342.30l/m
2/ day, lysine rejection is 72%, is 56% to the enantioselectivity of d-alanine.
Beneficial effect of the present invention
1) in prior art, related enantioselectivity polymer film is all asymmetric dense film, and these films are to use chiral polymer as polysaccharide and derivative, poly-a-amino acid, and Polyacetylene Derivatives etc. are manufactured.Most of films are fragile, bad mechanical strength, thereby it deals with more difficultly, and therefore their use is only limited to the separation of dialysis form.The driving force of dialysis clastotype is the solute concentration gradient that strides across film, and therefore, these films show low-down infiltration rate.And the film with higher mechanical strength demonstrates enantioselectivity in the time starting, but saturated due to identification point As time goes on, they selectively sharply decline.
2) composite membrane of the present invention has been avoided the shortcoming of above-mentioned film described in the prior.
3) composite membrane of the present invention can be for plant-scale stage enantiomer separation.
4) composite membrane of the present invention depends on transmembrane pressure and shows 6-24 gallon/foot
2the permeation flux in/sky.
5) composite membrane of the present invention can be used for the pressure-driven separation process of 345-862K Pa.Higher transmembrane pressure can make flux improve, thereby productive rate is higher.
6) composite membrane of the present invention has superior stability and mechanical performance, therefore its easy operating and can be converted into Componentized form.
7) stage enantiomer separation relating in prior art batch process often, even continuous, be not suitable for yet large-scale continuous separate from.The separation that uses film of the present invention to carry out enantiomter will be continuous process, and can be adapted to large-scale continuous separate from.
8) stage enantiomer separation process of the present invention will be reasonably demonstrating high transmission rates and separating degree in the time, thus make by amino acid from they the aqueous solution and mixture separate on a large scale become feasible.
Claims (11)
1. for the preparation of a method for enantioselectivity composite membrane, described enantioselectivity composite membrane can be used for separating enantiomter from enantiomeric mixture to obtain optically pure isomers, and wherein said method comprises the following steps:
(a) provide ultrafiltration (UF) film of preparing by wetting phase conversion method;
(b) the milipore filter impregnation mixture coating time of 1 to 5 minute that will obtain from step (a), described mixture comprises the following 1-2% aqueous solution: amino acid or amino acid whose mixture, polyfunctional amine and acid acceptor; Keep pH value in 10 to 13 scope;
(c) the mixture obtaining from step (b), shift out the UF film of coating, and last 5 to 30 minutes and fall unnecessary solution from described UF film drop;
(d) coated film obtaining from step (c) is flooded to the time of 1-5 minute again the hexane solution of three carboxylic acid halides of 0.1-1%, and last 1 to 5 minute drop and fall unnecessary solution;
(e) the film time of dry 1 to 4 hour that will obtain from step (d);
(f) film that will obtain from step (e) is in the temperature heating time of 1 to 15 minute within the scope of 70 ℃ to 100 ℃, cooling subsequently, and air is dried 1 to 2 hour; With
(g) film obtaining from step (f) is soaked and reaches 24 hours deionized water, to obtain enantioselectivity composite membrane, described enantioselectivity composite membrane is included in the enantioselectivity layer on described milipore filter, and described enantioselectivity composite membrane is carried out to the discrete testing of amino acid from their aqueous solution.
2. the method for claim 1, the thickness range of the enantioselectivity layer of wherein said composite membrane be 400 to
3. the method for claim 1, the amino acid wherein using choosing is the group of at least two primary amine group compositions freely.
4. the method for claim 1, the enantioselectivity layer of wherein said composite membrane has the crosslinked polyamide polymer that comprises at least one asymmetric carbon atom.
5. the method for claim 1, the polyfunctional amine wherein using in step (b) is selected from m-phenylene diamine (MPD), piperazine, and the acid acceptor using is selected from triethylamine or NaOH.
6. the method for claim 1, polyfunctional group three carboxylic acid halides that wherein use in step (d) are pyromellitic trimethylsilyl chlorides.
7. the method for claim 1, the milipore filter wherein using for the preparation of composite membrane selects the polysulfones of free thickness in the scope of 20-60 μ m and the group of polyvinylidene fluoride composition.
8. the method for claim 1, the milipore filter wherein using for the preparation of composite membrane selects the polyether sulfone of free thickness in the scope of 20-60 μ m and the group of polyvinylidene fluoride composition.
9. the method for claim 1, wherein enantioselectivity composite membrane separates the arginine of 50-70% and the lysine of 80-90% from the aqueous solution.
10. for the mapping separation method of amino acid racemization mixture, described method is used by the enantioselectivity composite membrane that method obtains as claimed in claim 1, wherein said method is carried out according to following condition on reverse osmosis membrane test cell: transmembrane pressure is in 345 to 862KPa scope, use amino acid solution in 0.1 to 1% scope and/or buffer solution as charging, flow rate is in 300 to 800ml scope per minute.
11. methods as claimed in claim 10, wherein measure amino acid whose concentration in penetrant by UV-Vis spectrophotometer, and with the HPLC that is equipped with PDA detector by assess the ratio of d and l-enantiomter in penetrant with chiral column.
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| IN629/DEL/2009 | 2009-03-27 | ||
| PCT/IN2010/000188 WO2010109490A1 (en) | 2009-03-27 | 2010-03-25 | A method for preparation of enantioselective composite membrane |
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| CN102179185A (en) * | 2011-03-29 | 2011-09-14 | 北京化工大学 | Method for preparing chiral separation solid film |
| WO2013118148A1 (en) * | 2012-02-06 | 2013-08-15 | Council Of Scientific & Industrial Research | "l-enantiomers selective membrane for optical resolution of alpha-amino acids and process for the preparation thereof" |
| CN103357279B (en) * | 2013-07-30 | 2015-09-30 | 云南师范大学 | Teicoplanin chiral composite membrane and the application in D, L-D-pHPG racemate resolution thereof |
| CN104437110B (en) * | 2014-12-15 | 2016-09-28 | 湖南澳维环保科技有限公司 | A kind of big flux polyamide composite film |
| EP3329986A4 (en) * | 2015-07-31 | 2019-04-03 | Toray Industries, Inc. | Separation membrane, separation membrane element, water purifier and method for producing separation membrane |
| CZ308513B6 (en) * | 2019-03-24 | 2020-10-14 | Ústav Chemických Procesů Av Čr, V. V. I. | Composite chiral membrane, preparation method and methods of enrichment of mixtures of enantiomers |
| CN110339724B (en) * | 2019-06-26 | 2021-08-03 | 四川大学 | Composite polyamide membrane with salt concentration responsiveness and preparation method and application thereof |
| KR102646731B1 (en) * | 2021-06-24 | 2024-03-12 | 이화여자대학교 산학협력단 | Method for preparing chiral nanostructures using block copolymers |
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- 2010-03-25 JP JP2012501507A patent/JP5619867B2/en not_active Expired - Fee Related
- 2010-03-25 CN CN201080022405.5A patent/CN102438734B/en not_active Expired - Fee Related
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| CN1772356A (en) * | 2005-11-02 | 2006-05-17 | 华东理工大学 | Composite fiber membrane with chiral molecular imprint and its prepn and application |
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| CN102438734A (en) | 2012-05-02 |
| KR20120012801A (en) | 2012-02-10 |
| JP5619867B2 (en) | 2014-11-05 |
| JP2012521869A (en) | 2012-09-20 |
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| DE112010001374T5 (en) | 2012-07-26 |
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