CN103585900A - Polysulfone chiral-separation membrane grafted by cyclodextrin through SI-ATRP method, and making method thereof - Google Patents
Polysulfone chiral-separation membrane grafted by cyclodextrin through SI-ATRP method, and making method thereof Download PDFInfo
- Publication number
- CN103585900A CN103585900A CN201310511941.7A CN201310511941A CN103585900A CN 103585900 A CN103585900 A CN 103585900A CN 201310511941 A CN201310511941 A CN 201310511941A CN 103585900 A CN103585900 A CN 103585900A
- Authority
- CN
- China
- Prior art keywords
- polysulfones
- cyclodextrin
- membrane
- chiral
- chiral separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of polymer membrane materials, and discloses a polysulfone chiral-separation membrane grafted by cyclodextrin through an SI-ATRP method, and a making method and an application thereof. The method includes the following concrete steps: adding a chloromethylpolysulfone membrane, allyl-beta-cyclodextrin and a catalyst into a solvent, sealing, adding a ligand, heating for reacting, washing, and drying to obtain the polysulfone chiral-separation membrane grafted by cyclodextrin through an SI-ATRP method. Chiral recognition sites are introduced into the surface of the membrane and the inner walls of apertures of the membrane through the surface-initiated atom transfer radical polymerization (SI-ATRP) method on the premise that the matrix membrane structure is not destroyed and the use performances of the membrane are not influenced, and the combination between the chiral sites and the membrane matrix are firm; and the grafting density, the length of a graft polymer and the chemical composition of the surface of the membrane can be effectively controlled by adopting a polymerization technology. The Polysulfone chiral-separation membrane grafted by cyclodextrin through the SI-ATRP method can be used in the separation of racemes.
Description
Technical field
The invention belongs to macromolecule member material technical field, particularly a kind of polysulfones chiral separation film and preparation method and application of SI-ATRP method grafted cyclodextrin.
Background technology
Separating chiral compound has been endowed more concern now, and this is mainly in organism, to have different metabolism because people understand enantiomers different in chipal compounds gradually.When a chipal compounds enters life entity, its two enantiomters can show different biologically actives conventionally.Molecular pharmacology research is found, the chemicals enantiomer that contains chirality factor, and the pharmacologically active in human body, metabolic process and toxicity exist significant difference.Under normal conditions, only have an enantiomer to there is pharmacological action, and another enantiomer is not only without pharmacological action, also can produce certain side effect.As far back as nineteen sixty, just there is the chiral drug teratogenesis accident that ' phocomelus ' is such.Continue U.S. food drug safety office in 1992, promulgate after the regulations about chiral drug, the relevant authentication mechanism of Europe, China and Japan proposes the guilding principle about chiral drug in succession, only have the enantiomer of result for the treatment of just can render to market, and every kind of enantiomer of drugs should be studied respectively its pharmacology and metabolic pathway.
Obtain single chiral enantiomer method a lot of as: the synthetic and dissymmetric synthesis of chiral source, but it faces chiral source restriction, route steps is various, productive rate is low, product is with high costs challenge.Comparatively speaking, DL body splits and is obtaining the equal tool advantages in aspect such as single chiral material kind, quantity and cost.Tradition chiral resolution technology (crystallisation, chemical method, extraction, chromatography etc.) exists that treating capacity is few, operation is more loaded down with trivial details, cost is high and the narrow restriction of fractionation object more.And embrane method fractionation has low cost, low energy consumption, successive operation mode and is easy to the advantages such as scale, be generally considered and carry out one of very potential method of extensive chiral resolution, have a good application prospect.Therefore, chiral resolution membrane technology has caused domestic and international researchers' extensive concern, and becomes the new focus of hymenology circle research.
The method of film being carried out to chirality modification has a lot.Such as blend, compound, Inducing Graft Polymerization etc.But blend may change the physical property of original membrane matrix; After composite modified, coating may depart from film base material gradually along with the carrying out of using.Therefore, need to develop a kind of chiral separation membrane preparation method that can secure adhesion change again membrane matrix performance.
Summary of the invention
For the shortcoming that overcomes above-mentioned prior art is with not enough, primary and foremost purpose of the present invention is to provide a kind of preparation method of polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin.In order to overcome the problems referred to above, the present invention uses the method for surperficial Atom Transfer Radical Polymerization " SI-ATRP ", introduces firmly chiral Recognition site on the surface of film, and does not change the physical property of film.
Another object of the present invention is to provide the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin prepared by said method.
The application of the polysulfones chiral separation film that still a further object of the present invention is to provide above-mentioned SI-ATRP method grafted cyclodextrin in separation of racemic body.
Object of the present invention realizes by following proposal:
A preparation method for the polysulfones chiral separation film of method grafted cyclodextrin, comprises following concrete steps:
Chloromethyl PS membrane, allyl group-beta-cyclodextrin, catalyst are added in solvent, and sealing, adds aglucon, adds thermal response, washs, is dried, and obtains the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin.
Preferably, the mass ratio of chloromethyl PS membrane used, allyl group-beta-cyclodextrin, catalyst and aglucon is (100～150): (800～2200): (10～24): (12～33).
Described catalyst refers to surperficial Atom Transfer Radical Polymerization catalysts.
Preferably, described catalyst refers to cuprous bromide or copper sulphate.
Preferably, described aglucon refers to pentamethyl-diethylenetriamine (PMEDTA), 2, at least one in 2 '-bipyridyl (bpy) and sodium ascorbate.
More preferably, when catalyst is cuprous bromide, described aglucon is pentamethyl-diethylenetriamine or 2,2 '-bipyridyl.
More preferably, when catalyst is copper sulphate, described aglucon is sodium ascorbate.
The described condition that adds thermal response is to react 24～48h at 45～70 ℃.
Described solvent nail alcohol/water mixed solution, ethanol/water mixed solution or isopropanol/water mixed solution.
In described methanol/water mixed solution, the volume ratio of first alcohol and water is (0～100): (100～0).
In described ethanol/water mixed solution, the volume ratio of second alcohol and water is (0～100): (100～0).
In described isopropanol/water mixed solution, the volume ratio of isopropyl alcohol and water is (0～100): (100～0).
Described washing refers to after above-mentioned solvent wash, then uses pure water rinsing.
Preferably, described in, add the bubbling deoxygenation of aglucon front and back.
Described chloromethyl PS membrane is prepared by following methods:
(1) preparation of chloromethyl polysulfones: 1～10g polysulfones is dissolved in 20～450mL carrene, adds successively 0.8～10g paraformaldehyde, 0.01～0.3ml SnCl
4with 2～35ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours, is deposited in methyl alcohol, filters, and is dissolved in chloroform and is deposited in methyl alcohol again, and lyophilized overnight, obtains chloromethyl polysulfones (PSF-CH
2cl);
(2) by 10～100 weight portion chloromethyl polysulfones, 5～50 weight portion pore-foaming agents, are dissolved in 100～500 weight portion organic solvents, prepare even casting solution, place after deaeration, are poured on glass plate, and striking is even, standing in air; Glass plate is immersed in pure water, soak half an hour, take out and be dried, obtain chloromethyl PS membrane.
The described pore-foaming agent of step (2) refers at least one in polyethylene glycol (PEG), polyvinyl alcohol (PVA) and polyvinylpyrrolidone (PVP).
The described organic solvent of step (2) refers at least one in dimethyl formamide (DMF), dimethylacetylamide (DMAc) and 1-METHYLPYRROLIDONE (NMP).
Preferably, the preparation of described allyl group-beta-cyclodextrin, first prepares intermediate 6-tosyl group-beta-cyclodextrin according to document Advance Functional Materials18 (2008) 652 – 663 methods; According to document Journal of Carbohydrate Chemistry9 (1998) 1359, prepare allyl group-beta-cyclodextrin again.
The polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin prepared by said method.
The application of the polysulfones chiral separation film of above-mentioned SI-ATRP method grafted cyclodextrin in separation of racemic body.
Mechanism of the present invention is:
The present invention uses the polysulfones (PSF-CH of chloromethylation
2cl) as film base material, by phase transfer method, prepare Flat Membrane, " the CH on film surface
2cl " group is as the priming site of " SI-ATRP ", carries out polymerisation with the chiral Recognition site of containing thiazolinyl in the mixed solution of water/alcohol.Thereby prepare the chiral resolution PS membrane that there is firm chiral Recognition site on surface.
The present invention, with respect to prior art, has following advantage and beneficial effect:
(1) the present invention is not destroying the structure of base film, do not affect under the prerequisite of film serviceability, utilize the method for surperficial Atom Transfer Radical Polymerization to introduce chiral Recognition site on film surface and fenestra inwall, and between chirality site and film matrix, combination is firm.
(2) the surperficial Atom Transfer Radical Polymerization that the present invention uses, is a kind of controlled polymerization, can be by regulating the technique of polymerization, and effectively the grafting density of controlling diaphragm is, the chemical composition on the length of graft polymers and film surface.
(3) preparation method of the present invention, under comparatively gentle reaction condition, can introduce firmly chiral Recognition site on film, for the chirality of film, modifies more reference is provided.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
The preparation of the polysulfones chiral separation film of embodiment 1:SI-ATRP method grafted cyclodextrin
(1) preparation of chloromethyl polysulfones: the CH that 1g polysulfones (the S3010 type polysulfones of BASF Aktiengesellschaft, shearing molecular weight is 50000Da) is dissolved in to 20mL
2cl
2in, add successively 0.8g paraformaldehyde (Aladdin reagent Co., Ltd), 0.01ml SnCl
4and 2ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours.After completion of the reaction, be deposited in methyl alcohol, filter, be dissolved in chloroform and be deposited in methyl alcohol again, lyophilized overnight obtains white powder P (SF-CH
2cl).
(2) by 10 parts of chloromethyl polysulfones, 5 parts of PEG2000(Aladdin reagent Co., Ltds), be dissolved in 100 parts of DMF, prepare even casting solution.Place after deaeration, casting solution is poured on glass plate, regulating thickness is 100 μ m, and striking is even, in air, after standing 30s, glass plate is immersed in pure water, soaks half an hour, takes out the dry chloromethyl polysulfones Flat Membrane that obtains.
(3) preparation of allyl group-beta-cyclodextrin, joins 12.0g beta-schardinger dextrin-in the distilled water of 100mL, and 1.32g NaOH is dissolved in 4mL water, is added drop-wise in beta-schardinger dextrin-solution the homogeneous that becomes gradually of suspension originally.Again 2.24g paratoluensulfonyl chloride is dissolved in the acetonitrile of 8mL, is added drop-wise in the solution of cyclodextrin, occur white precipitate, at 25 ℃, react after 2h, be positioned at 4 ℃ and spend the night.Filtration obtains white solid, after soaking, filters with hot wash twice with ether, dry under vacuum, obtains intermediate 6-tosyl group-beta-cyclodextrin.Get 1.0g6-tosyl group-beta-cyclodextrin again and react with the allyl amine of 10g, back flow reaction 4h at 70 ℃, after the solution obtaining slightly dilutes with a certain amount of methyl alcohol; be deposited in acetonitrile solution; obtain white solid, dried overnight under vacuum, obtains allyl group-beta-cyclodextrin.
(4) film surface initiating activity radical polymerization, the mixed solvent 10mL of 100mg chloromethyl PS membrane, 1.5g allyl group-beta-cyclodextrin, 17.2mg cuprous bromide, V methyl alcohol/V water=1/1 is added in glass tube and sealed, under nitrogen after bubbling 15min, add 20.8mg pentamethyl-diethylenetriamine (PMEDTA), then bubbling 10min.After bubbling, at 45 ℃, react 24h.After completion of the reaction, with the mixed solvent of V methyl alcohol/V water=1/1, repeatedly rinse, finally with pure water cleaning, drying, obtain chiral resolution PS membrane.
(5) by film at 1kg/cm
2pressure under the D to 10mg/L respectively, L-Trp and D, L-Histidine carries out chiral resolution experiment, obtains chiral separation effect.
The polysulfones chiral separation film flow preparing is 150Lm
-2h
-1, water contact angle is 45 °.To D, the fractionation efficiency (e.e%) of L-Histidine is 25%, and to D, the fractionation efficiency (e.e%) of L-Trp is 37%.
The preparation of the polysulfones chiral separation film of embodiment 2:SI-ATRP method grafted cyclodextrin
(1) preparation of chloromethyl polysulphone: the CH that 3g polysulfones is dissolved in to 120mL
2cl
2in, add successively 3g paraformaldehyde, 0.04ml SnCl
4and 7ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours.After completion of the reaction, be deposited in methyl alcohol, filter, be dissolved in chloroform and be deposited in methyl alcohol again, lyophilized overnight obtains white powder P (SF-CH
2cl).
(2), by 30 weight portion chloromethyl polysulfones, 10 weight portion PVA10000, are dissolved in 200 weight portion DMAc, prepare even casting solution.Place after deaeration, casting solution is poured on glass plate, regulating thickness is 150 μ m, and striking is even, in air, after standing 100s, glass plate is invaded and is immersed in pure water, soaks half an hour, takes out the dry chloromethyl polysulfones Flat Membrane that obtains.
(3) preparation of allyl group-beta-cyclodextrin: 20.0g beta-schardinger dextrin-is joined in the distilled water of 150mL, 2.51g NaOH is dissolved in 5mL water, be added drop-wise in beta-schardinger dextrin-solution, the homogeneous that becomes gradually of suspension originally.Again 3.55g paratoluensulfonyl chloride is dissolved in the acetonitrile of 8mL, is added drop-wise in the solution of cyclodextrin, occur white precipitate, at 25 ℃, react after 3h, be positioned at 4 ℃ and spend the night.Filtration obtains white solid, after soaking, filters with hot wash twice with ether, dry under vacuum, obtains intermediate 6-tosyl group-beta-cyclodextrin.Get 2.0g6-tosyl group-beta-cyclodextrin again and react with the allyl amine of 30g, back flow reaction 4h at 70 ℃, after the solution obtaining slightly dilutes with a certain amount of methyl alcohol; be deposited in acetonitrile solution; obtain white solid, dried overnight under vacuum, obtains allyl group-beta-cyclodextrin.
(4) film surface initiating activity radical polymerization, the mixed solvent 12mL of 150mg chloromethyl PS membrane, 2.2g allyl group-beta-cyclodextrin, 21.3mg copper sulphate, V ethanol/V water=2/1 is added in glass tube and sealed, under nitrogen after bubbling 15min, add 24.8mg sodium ascorbate, then bubbling 10min.After bubbling, at 70 ℃, react 48h.After completion of the reaction, with the mixed solvent of V ethanol/V water=2/1, repeatedly rinse, finally with pure water cleaning, drying, obtain chiral resolution PS membrane.
(5) by film at 1kg/cm
2pressure under the D to 5mg/L respectively, L-Trp and D, L-Histidine carries out chiral resolution experiment, obtains chiral separation effect.
The polysulfones chiral separation film flow preparing is 210Lm
-2h
-1, water contact angle is 40 °.To D, the fractionation efficiency (e.e%) of L-Histidine is 29%, and to D, the fractionation efficiency (e.e%) of L-Trp is 42%.
The preparation of the polysulfones chiral separation film of embodiment 3:SI-ATRP method grafted cyclodextrin
(1) preparation of chloromethyl polysulphone: the CH that 5g polysulfones is dissolved in to 250mL
2cl
2in, add successively 7g paraformaldehyde, 0.2ml SnCl
4and 21ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours.After completion of the reaction, be deposited in methyl alcohol, filter, be dissolved in chloroform and be deposited in methyl alcohol again, lyophilized overnight obtains white powder P (SF-CH
2cl).
(2), by 50 weight portion chloromethyl polysulfones, 20 weight portion PVP20000, are dissolved in 300 weight portion NMP, prepare even casting solution.Place after deaeration, casting solution is poured on glass plate, regulating thickness is 120 μ m, and striking is even, in air, after standing 60s, glass plate is invaded and is immersed in pure water, soaks half an hour, takes out the dry chloromethyl polysulfones Flat Membrane that obtains.
(3) preparation of allyl group-beta-cyclodextrin, joins 8.0g beta-schardinger dextrin-in the distilled water of 50mL, and 1.11g NaOH is dissolved in 3mL water, is added drop-wise in beta-schardinger dextrin-solution the homogeneous that becomes gradually of suspension originally.Again 2.17g paratoluensulfonyl chloride is dissolved in the acetonitrile of 4mL, is added drop-wise in the solution of cyclodextrin, occur white precipitate, at 25 ℃, react after 2.5h, be positioned at 4 ℃ and spend the night.Filtration obtains white solid, after soaking, filters with hot wash twice with ether, dry under vacuum, obtains intermediate 6-tosyl group-beta-cyclodextrin.Get 1.5g6-tosyl group-beta-cyclodextrin again and react with the allyl amine of 30g, back flow reaction 6h at 70 ℃, after the solution obtaining slightly dilutes with a certain amount of methyl alcohol; be deposited in acetonitrile solution; obtain white solid, dried overnight under vacuum, obtains allyl group-beta-cyclodextrin.
(4) film surface initiating activity radical polymerization: the mixed solvent 12mL of 120mg chloromethyl PS membrane, 1.4g allyl group-beta-cyclodextrin, 20.1mg cuprous bromide, V isopropyl alcohol/V water=1/2 is added in glass tube and sealed, under nitrogen after bubbling 15min, add 19.3mg2,2 '-bipyridyl, then bubbling 10min.After bubbling, at 50 ℃, react 36h.After completion of the reaction, with the mixed solvent of V isopropyl alcohol/V water=1/2, repeatedly rinse, finally with pure water cleaning, drying, obtain chiral resolution PS membrane.
(5) by film at 1kg/cm
2pressure under the D to 15mg/L respectively, L-Trp and D, L-Histidine carries out chiral resolution experiment, obtains chiral separation effect.
The polysulfones chiral separation film flow preparing is 120Lm
-2h
-1, water contact angle is 49 °.To D, the fractionation efficiency (e.e%) of L-Histidine is 21%, and to D, the fractionation efficiency (e.e%) of L-Trp is 31%.
The preparation of the polysulfones chiral separation film of embodiment 4:SI-ATRP method grafted cyclodextrin
(1) preparation of chloromethyl polysulphone: the CH that 10g polysulfones is dissolved in to 450mL
2cl
2in, add successively 10g paraformaldehyde, 0.3ml SnCl
4and 35ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours.After completion of the reaction, be deposited in methyl alcohol, filter, be dissolved in chloroform and be deposited in methyl alcohol again, lyophilized overnight obtains white powder PSF-CH
2cl.
(2), by 100 weight portion chloromethyl polysulfones, 30 weight portion PEG20000, are dissolved in 500 weight portion NMP, prepare even casting solution.Place after deaeration, casting solution is poured on glass plate, regulating thickness is 140 μ m, and striking is even, in air, after standing a period of time, glass plate is invaded and is immersed in pure water, soaks half an hour, takes out the dry chloromethyl polysulfones Flat Membrane that obtains.
(4) preparation of allyl group-beta-cyclodextrin, joins 16g beta-schardinger dextrin-in the distilled water of 130mL, and 3.11g NaOH is dissolved in 5mL water, is added drop-wise in beta-schardinger dextrin-solution the homogeneous that becomes gradually of suspension originally.Again 5.17g paratoluensulfonyl chloride is dissolved in the acetonitrile of 8mL, is added drop-wise in the solution of cyclodextrin, occur white precipitate, at 25 ℃, react after 2h, be positioned at 4 ℃ and spend the night.Filtration obtains white solid, after soaking, filters with hot wash twice with ether, dry under vacuum, obtains intermediate 6-tosyl group-beta-cyclodextrin.Get 2.3g6-tosyl group-beta-cyclodextrin again and react with the allyl amine of 35g, back flow reaction 6h at 70 ℃, after the solution obtaining slightly dilutes with a certain amount of methyl alcohol; be deposited in acetonitrile solution; obtain white solid, dried overnight under vacuum, obtains allyl group-beta-cyclodextrin.
(4) film surface initiating activity radical polymerization, the mixed solvent 12mL of 110mg chloromethyl PS membrane, 1.7g allyl group-beta-cyclodextrin, 10.1mg CuBr, V isopropyl alcohol/V water=1/1 is added in glass tube and sealed, under nitrogen after bubbling 15min, add 12.3mg PMDETA, then bubbling 10min.After bubbling, at 60 ℃, react 40h.After completion of the reaction, with the mixed solvent of V isopropyl alcohol/V water=1/1, repeatedly rinse, finally with pure water cleaning, drying, obtain chiral resolution PS membrane.
(5) by film at 1kg/cm
2pressure under the D to 10mg/L respectively, L-Trp and D, L-Histidine carries out chiral resolution experiment, obtains chiral separation effect.
The polysulfones chiral separation film flow preparing is 180Lm
-2h
-1, water contact angle is 40 °.To D, the fractionation efficiency (e.e%) of L-Histidine is 31%, and to D, the fractionation efficiency (e.e%) of L-Trp is 48%.
The preparation of the polysulfones chiral separation film of embodiment 5:SI-ATRP method grafted cyclodextrin
(1) preparation of chloromethyl polysulphone: the CH that 7g polysulfones is dissolved in to 400mL
2cl
2in, add successively 6g paraformaldehyde, 0.21ml SnCl
4and 26ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours.After completion of the reaction, be deposited in methyl alcohol, filter, be dissolved in chloroform and be deposited in methyl alcohol again, lyophilized overnight obtains white powder PSF-CH
2cl.
(2), by 70 weight portion chloromethyl polysulfones, 20 weight portion PVP5000, are dissolved in 500 weight portion DMF, prepare even casting solution.Place after deaeration, casting solution is poured on glass plate, regulating thickness is 130 μ m, and striking is even, in air, after standing a period of time, glass plate is invaded and is immersed in pure water, soaks half an hour, takes out the dry chloromethyl polysulfones Flat Membrane that obtains.
(3) preparation of allyl group-beta-cyclodextrin, joins 24g beta-schardinger dextrin-in the distilled water of 160mL, and 3.20g NaOH is dissolved in 5mL water, is added drop-wise in beta-schardinger dextrin-solution the homogeneous that becomes gradually of suspension originally.Again 6.03g paratoluensulfonyl chloride is dissolved in the acetonitrile of 8mL, is added drop-wise in the solution of cyclodextrin, occur white precipitate, at 25 ℃, react after 2h, be positioned at 4 ℃ and spend the night.Filtration obtains white solid, after soaking, filters with hot wash twice with ether, dry under vacuum, obtains intermediate 6-tosyl group-beta-cyclodextrin.Get 1.9g6-tosyl group-beta-cyclodextrin again and react with the allyl amine of 20g, back flow reaction 4h at 70 ℃, after the solution obtaining slightly dilutes with a certain amount of methyl alcohol; be deposited in acetonitrile solution; obtain white solid, dried overnight under vacuum, obtains allyl group-beta-cyclodextrin.
(4) film surface initiating activity radical polymerization, the mixed solvent 10mL of 140mg chloromethyl PS membrane, 1.0g allyl group-beta-cyclodextrin, 20.1mg copper sulphate, V methyl alcohol/V water=2/1 is added in glass tube and sealed, under nitrogen after bubbling 15min, add 23.9mg sodium ascorbate, then bubbling 10min.After bubbling, at 45 ℃, react 42h.After completion of the reaction, with the mixed solvent of V methyl alcohol/V water=2/1, repeatedly rinse, finally with pure water cleaning, drying, obtain chiral resolution PS membrane.
(5) by film at 1kg/cm
2pressure under the D to 15mg/L respectively, L-Trp and D, L-Histidine carries out chiral resolution experiment, obtains chiral separation effect.
The polysulfones chiral separation film flow preparing is 100Lm
-2h
-1, water contact angle is 50 °.To D, the fractionation efficiency (e.e%) of L-Histidine is 22%, and to D, the fractionation efficiency (e.e%) of L-Trp is 34%.
The preparation of the polysulfones chiral separation film of embodiment 6:SI-ATRP method grafted cyclodextrin
(1) preparation of chloromethyl polysulphone, is dissolved in 10g polysulfones the CH of 350mL
2cl
2in, add successively 5g paraformaldehyde, 0.16ml SnCl
4and 23ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours.After completion of the reaction, be deposited in methyl alcohol, filter, be dissolved in chloroform and be deposited in methyl alcohol again, lyophilized overnight obtains white powder PSF-CH
2cl.
(2), by 60 weight portion chloromethyl polysulfones, 20 weight portion PVA8000, are dissolved in 360 weight portion DMAc, prepare even casting solution.Place after deaeration, casting solution is poured on glass plate, regulating thickness is 145 μ m, and striking is even, in air, after standing a period of time, glass plate is invaded and is immersed in pure water, soaks half an hour, takes out the dry chloromethyl polysulfones Flat Membrane that obtains.
(3) preparation of allyl group-beta-cyclodextrin, joins 14g beta-schardinger dextrin-in the distilled water of 150mL, and 1.60g NaOH is dissolved in 5mL water, is added drop-wise in beta-schardinger dextrin-solution the homogeneous that becomes gradually of suspension originally.Again 3.03g paratoluensulfonyl chloride is dissolved in the acetonitrile of 8mL, is added drop-wise in the solution of cyclodextrin, occur white precipitate, at 25 ℃, react after 2h, be positioned at 4 ℃ and spend the night.Filtration obtains white solid, after soaking, filters with hot wash twice with ether, dry under vacuum, obtains intermediate 6-tosyl group-beta-cyclodextrin.Get 1.4g6-tosyl group-beta-cyclodextrin again and react with the allyl amine of 10g, back flow reaction 4h at 70 ℃, after the solution obtaining slightly dilutes with a certain amount of methyl alcohol; be deposited in acetonitrile solution; obtain white solid, dried overnight under vacuum, obtains allyl group-beta-cyclodextrin.
(4) film surface initiating activity radical polymerization, the mixed solvent 10mL of 145mg chloromethyl PS membrane, 0.8g allyl group-beta-cyclodextrin, 23.1mg cuprous bromide, V ethanol/V water=1/3 is added in glass tube and sealed, under nitrogen after bubbling 15min, add 32.8mg2,2 '-bipyridyl, then bubbling 10min.After bubbling, at 65 ℃, react 30h.After completion of the reaction, with the mixed solvent of V ethanol/V water=1/3, repeatedly rinse, finally with pure water cleaning, drying, obtain chiral resolution PS membrane.
(5) by film at 1kg/cm
2pressure under the D to 15mg/L respectively, L-Trp and D, L-Histidine carries out chiral resolution experiment, obtains chiral separation effect.
The polysulfones chiral separation film flow preparing is 110Lm
-2h
-1, water contact angle is 50 °.To D, the fractionation efficiency (e.e%) of L-Histidine is 25%, and to D, the fractionation efficiency (e.e%) of L-Trp is 37%.
Embodiment 7: comparative example
The people (J.Am.Chem.Soc.2011,133,7644 – 7647) such as Lei Jiang, are grafted to cyclodextrin on the film of PET for chiral resolution by esterification, to the fractionation efficiency of D-His, be 21.0%, and the fractionation efficiency of L-Histidine is 0.05%; To the fractionation efficiency of D-phenylalanine acid, be 1.5%, the fractionation efficiency of L-Histidine is 1.0%; To the fractionation efficiency of D-Tyrosine, be 1.5%, the fractionation efficiency of L-Histidine is 1.2%.The people (Adv.Funct.Mater.2008,18,652 – 663) such as Liang-Yin Chu, by cyclodextrin and epoxide group reactive grafting on the film of nylon-6 for chiral resolution, to D, after L-Trp splits, obtain the superfluous value of ee%(enantiomer) be 21%.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (10)
1. a preparation method for the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin, is characterized in that comprising following concrete steps:
Chloromethyl PS membrane, allyl group-beta-cyclodextrin, catalyst are added in solvent, sealing, deoxygenation, adds aglucon, then deoxygenation, adds thermal response, washs, is dried, and obtains the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin.
2. the preparation method of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 1, is characterized in that: the mass ratio of chloromethyl PS membrane used, allyl group-beta-cyclodextrin, catalyst and aglucon is (100～150): (800～2200): (10～24): (12～33).
3. the preparation method of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 1, is characterized in that: described catalyst refers to surperficial Atom Transfer Radical Polymerization catalysts.
4. the preparation method of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 1, is characterized in that: described catalyst refers to cuprous bromide or copper sulphate; Described aglucon refers to pentamethyl-diethylenetriamine, 2, at least one in 2 '-bipyridyl and sodium ascorbate.
5. the preparation method of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 4, is characterized in that: when catalyst is cuprous bromide, described aglucon is pentamethyl-diethylenetriamine or 2,2 '-bipyridyl; When catalyst is copper sulphate, described aglucon is sodium ascorbate.
6. the preparation method of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 1, is characterized in that: described in add thermal response condition be to react 24～48h at 45～70 ℃; Described solvent nail alcohol/water mixed solution, ethanol/water mixed solution or isopropanol/water mixed solution; Described washing refers to after solvent wash, then uses pure water rinsing.
7. the preparation method of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 1, is characterized in that: described chloromethyl PS membrane is prepared by following methods:
(1) preparation of chloromethyl polysulfones: 1～10g polysulfones is dissolved in 20～450mL carrene, adds successively 0.8～10g paraformaldehyde, 0.01～0.3ml SnCl
4with 2～35ml (CH
3)
3siCl reflux condensation mode at 50 ℃ stirs 72 hours, is deposited in methyl alcohol, filters, and is dissolved in chloroform and is deposited in methyl alcohol again, and lyophilized overnight, obtains chloromethyl polysulfones;
(2) by 10～100 weight portion chloromethyl polysulfones, 5～50 weight portion pore-foaming agents, are dissolved in 100～500 weight portion organic solvents, prepare even casting solution, place after deaeration, are poured on glass plate, and striking is even, standing in air; Glass plate is immersed in pure water, soak half an hour, take out and be dried, obtain chloromethyl PS membrane.
8. the preparation method of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 1, is characterized in that: the described pore-foaming agent of step (2) refers at least one in polyethylene glycol, polyvinyl alcohol and polyvinylpyrrolidone; Described organic solvent refers at least one in dimethyl formamide, dimethylacetylamide and 1-METHYLPYRROLIDONE.
9. a polysulfones chiral separation film for SI-ATRP method grafted cyclodextrin, is characterized in that: according to the preparation method of the polysulfones chiral separation film of the SI-ATRP method grafted cyclodextrin described in claim 1～8 any one, prepare.
10. the application of the polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin according to claim 9 in separation of racemic body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511941.7A CN103585900B (en) | 2013-10-25 | 2013-10-25 | The polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310511941.7A CN103585900B (en) | 2013-10-25 | 2013-10-25 | The polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103585900A true CN103585900A (en) | 2014-02-19 |
| CN103585900B CN103585900B (en) | 2016-01-20 |
Family
ID=50076340
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310511941.7A Active CN103585900B (en) | 2013-10-25 | 2013-10-25 | The polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103585900B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897121A (en) * | 2014-04-08 | 2014-07-02 | 西南石油大学 | AM/AA/N-beta-CD polymer-ionic liquid [bquin]BF4 composite clay stabilizer and synthesis method thereof |
| CN104128102A (en) * | 2014-08-04 | 2014-11-05 | 郑州大学 | Cyclodextrin modified composite organic solvent nanofiltration membrane and preparation method thereof |
| CN104826506A (en) * | 2015-05-18 | 2015-08-12 | 天津工业大学 | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof |
| CN114957024A (en) * | 2022-05-30 | 2022-08-30 | 厦门理工学院 | Chiral resolution method of DL-phenylalanine enantiomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431035A (en) * | 2003-01-27 | 2003-07-23 | 四川大学 | Intelligent chiral separation affinity membrane and its preparing method |
| CN102512993A (en) * | 2011-11-18 | 2012-06-27 | 天津工业大学 | Boron-removed polysulphone modified affinitive membrane as well as preparation method and application |
| CN103204977A (en) * | 2013-04-03 | 2013-07-17 | 浙江大学 | Sulphobetaine metacrylic acid ester grafted polysulfone copolymer as well as preparation method and application of polysulfone copolymer |
-
2013
- 2013-10-25 CN CN201310511941.7A patent/CN103585900B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1431035A (en) * | 2003-01-27 | 2003-07-23 | 四川大学 | Intelligent chiral separation affinity membrane and its preparing method |
| CN102512993A (en) * | 2011-11-18 | 2012-06-27 | 天津工业大学 | Boron-removed polysulphone modified affinitive membrane as well as preparation method and application |
| CN103204977A (en) * | 2013-04-03 | 2013-07-17 | 浙江大学 | Sulphobetaine metacrylic acid ester grafted polysulfone copolymer as well as preparation method and application of polysulfone copolymer |
Non-Patent Citations (2)
| Title |
|---|
| 戴荣继等: "膜拆分法分离制备手性药物", 《膜科学与技术》 * |
| 杨座国等: "固膜手性拆分机理及其应用", 《膜科学与技术》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103897121A (en) * | 2014-04-08 | 2014-07-02 | 西南石油大学 | AM/AA/N-beta-CD polymer-ionic liquid [bquin]BF4 composite clay stabilizer and synthesis method thereof |
| CN104128102A (en) * | 2014-08-04 | 2014-11-05 | 郑州大学 | Cyclodextrin modified composite organic solvent nanofiltration membrane and preparation method thereof |
| CN104128102B (en) * | 2014-08-04 | 2016-03-09 | 郑州大学 | A kind of cyclo-dextrin-modified compounded organic solvent NF membrane and preparation method thereof |
| CN104826506A (en) * | 2015-05-18 | 2015-08-12 | 天津工业大学 | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof |
| CN104826506B (en) * | 2015-05-18 | 2017-02-22 | 天津工业大学 | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof |
| CN114957024A (en) * | 2022-05-30 | 2022-08-30 | 厦门理工学院 | Chiral resolution method of DL-phenylalanine enantiomer |
| CN114957024B (en) * | 2022-05-30 | 2023-08-15 | 厦门理工学院 | Chiral resolution method of DL-phenylalanine enantiomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103585900B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100575368C (en) | The manufacture method of the manufacture method of polyvinyl acetal resin, polyvinyl butyral resin and esterified polyvinyl alcohol resin | |
| CN103585900B (en) | The polysulfones chiral separation film of SI-ATRP method grafted cyclodextrin and preparation method | |
| CN104826506B (en) | Beta-cyclodextrin grafted polymer chiral separation membrane and preparation method thereof | |
| CN104707579B (en) | A kind of preparations and applicatio of the hyperbranched polyetheramine grafting GO adsorbent for heavy metal and Dye Adsorption | |
| EP1871823B1 (en) | Polymer capsule and process for the preparation thereof | |
| CN107652380B (en) | Heterogeneous chiral catalyst based on polyionic liquid and preparation method and application thereof | |
| CN101732998A (en) | Preparation method for cross-linking polyvinyl alcohol furfural nanofiltration membrane | |
| CN112316745B (en) | Metal-organic molecule cage complex mixed matrix membrane and preparation method and application thereof | |
| CN104817663A (en) | Preparation method of polycarboxylate water-reducer capable of inhibiting side-effect of montmorillonite and polymeric monomer | |
| CN110003026A (en) | A kind of covalent organic frame material Py-COF and preparation method | |
| CN103709434A (en) | Preparation method and application of arteannuin molecularly imprinted membrane | |
| CN104629073B (en) | A kind of supermolecule chirality film of amino acid induction and preparation method thereof | |
| CN103849000B (en) | The chemical graft of PVDF base homogeneous phase cation exchange films prepares method | |
| CN113457736B (en) | Application of chitosan/cellulose composite microsphere immobilized copper in catalyzing silicon addition reaction of alpha, beta-unsaturated carbonyl compound | |
| CN106111086A (en) | A kind of absorption Pd2+ion-type polymeric sorbent of metal ion and preparation method thereof | |
| CN104028125B (en) | A kind of difunctionalization graphene oxide is filled hybridized film and preparation method and application | |
| WO2018211389A1 (en) | Molecularly imprinted polymers for selective adsorption of urea for dialysis | |
| CN106478975B (en) | The method of the preparation method and its modified polyvinilidene fluoride microfiltration membranes of difunctional block polymer | |
| CN103585902B (en) | A kind of hydrophilic chiral separation PS membrane and its preparation method and application | |
| CN103788380A (en) | Method for cleanly preparing chitosan grafted polyethylenimine non-viral gene vector | |
| CN102059059B (en) | Preparation method of protein adsorption resistant ceramic composite membrane | |
| CN104014251B (en) | A kind of preparation method based on inorganic supporting body assembled inorganic particle hydridization polyelectrolyte NF membrane | |
| CN110052177A (en) | A kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane | |
| CN103857692B (en) | Method of purifying protein | |
| CN105126658B (en) | A kind of smart membrane and preparation method thereof based on supermolecule |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP03 | Change of name, title or address |
Address after: 510650 Guangdong city of Guangzhou province Tianhe District Xing Branch Road No. 368 Patentee after: Guangzhou Chemistry Co., Ltd. Chinese Academy of Sciences Address before: 510000 Guangdong city of Guangzhou province Tianhe District Xing Branch Road No. 368 Patentee before: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences |