CN101912771B - Molecular-recognition separation membrane and preparation method and application thereof - Google Patents
Molecular-recognition separation membrane and preparation method and application thereof Download PDFInfo
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- CN101912771B CN101912771B CN2010102620509A CN201010262050A CN101912771B CN 101912771 B CN101912771 B CN 101912771B CN 2010102620509 A CN2010102620509 A CN 2010102620509A CN 201010262050 A CN201010262050 A CN 201010262050A CN 101912771 B CN101912771 B CN 101912771B
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Abstract
The invention discloses a method for preparing a molecular-recognition separation membrane, which comprises the following steps of: (1) adopting a polymer separation membrane of which the surface or body is provided with carboxyl as a base membrane; (2) soaking the base membrane in aqueous solution of 1-ethyl-3-(N,N-dimethyl aminopropyl) carbodiimide and N-hydroxysuccimide for activation, washing, soaking the activated base membrane into the solution of phenyl boronic acid solution for reaction, and washing to prepare a separation membrane for fixing the phenyl boronic acid; and (3) soaking the separation membrane for fixing the phenyl boronic acid into Tris-HCl buffer solution of cyclodextrin for reaction, and washing to prepare the molecular-recognition separation membrane. The method for preparing the molecular-recognition separation membrane has the advantages of simple operation and suitability for industrial production; and the prepared molecular-recognition separation membrane has obvious adsorptive capacity for phenol compounds. The molecular-recognition separation membrane has the advantages of capacity of improving the adsorptive capacity for the phenol compounds, easy regeneration and recovery, no secondary pollution, and practical value in removing phenol pollutants from water.
Description
Technical field
The present invention relates to the diffusion barrier technical field, be specifically related to a kind of reproducible molecular-recognition separation membrane based on phenyl boric acid and cyclodextrin molecular recognition reaction and preparation method thereof and molecular-recognition separation membrane application in the phenolic compound in removing water body.
Background technology
In recent years, along with development economic and society, environmental protection especially fwaater resources protection receives the attention of the whole society.Phenolic compound is common water pollutant.For example, bisphenol-A (Bisphenol A) is to produce material common chemical article such as epoxy resin, Merlon, and itself also is a kind of bactericide, and its toxicity is widely known by the people with a type estrogen active.Bisphenol-A and similar contaminant thereof not only derive from the waste water of production process, also can from finished product such as plastic bottle, leak out, further contaminated environment.Therefore, development detects with the method for removing phenolic compound extremely important.
Cyclodextrin (Cyclodextrin) is the general name of amylose a series of cyclic oligosaccharides of generation under the cyclodextrin glycosyltransferase effect that is produced by bacillus, contains 6～12 D-glucopyranose units usually.Wherein study more and what have important practical usage is the molecule that contains 6,7,8 glucose units, be called alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin respectively.Inner chamber is hydrophobic because the cyclodextrin outer rim is hydrophilic, thereby it can provide a hydrophobic binding site as enzyme in water.Big quantity research confirms, through Van der Waals force, hydrogen bond, hydrophobic interaction and intermolecular space matching effect, cyclodextrin can organicly carry out molecular recognition with inorganic molecule to many, forms Subjective and Objective inclusion complex and molecular assembly system.Therefore, in fields such as environmental protection, catalysis, separation, food and medicine, cyclodextrin has received great attention and extensive use.Discover that chemicals mass-energy such as cyclodextrin and phenolic compound and phenyl boric acid effectively form the Subjective and Objective inclusion complex.
At present the interactional basic principle and the rule of cyclodextrin and phenolic compound have been carried out furtheing investigate (referring to H.Endo through means such as gold surface self assemblies; Et al.; Orientational effectof surface-confined cyclodextrin on the inclusion of bisphenols, Langmuir, 2005; 21,1314-1321).Simultaneously, existing patent also discloses method and the technology of utilizing phenolic compound in the cyclodextrin absorption sewage.Like publication number the selective reinforcement processing method that discloses a kind of bisphenol waste water in the Chinese invention patent application of CN 1778704A: directly add predetermined amount of beta-cyclodextrin in the waste water and discern bisphenol wherein, utilize uviol lamp directly to carry out light degradation then.But water-soluble in view of cyclodextrin for the cyclodextrin that prevents to add causes secondary pollution, and is beneficial to recovery, regeneration and the repeated use of cyclodextrin, generally directly cyclodextrin is not used for the absorption of water body phenolic compound.Disclose a kind of preparation method of lignin-Based cyclodextrin ester multi-purpose sorbent among the Chinese invention patent ZL200610010395.9, used immobilized cyclodextrin to come materials such as adsorbing phenol.Publication number is the preparation method who discloses a kind of water purifying adsorbent polycyclodextrin in the Chinese invention patent application of CN 1352199A: carry out polymerization with cyclodextrin and crosslinking agent etc. and obtain crosslinked cyclodextrin, this crosslinked cyclodextrin is multiple organic pollution in the adsorbed water body effectively.
In sum, prior art all is directly to handle with cyclodextrin or its polymer powder foot couple sewage, exists adsorbent to reclaim and the repeated use difficulty, even causes secondary pollution problem, and still lack effective regeneration means at present; In addition, in the prior art cyclodextrin just as a kind of adsorbent, not with sewage disposal in separation process combine, and actual sewage often contains complicated multiple pollutant, needs the introducing of water treatment means such as film separation.This shows that technology and technology that the existing recognition reaction that utilizes cyclodextrin is removed phenolic comp ' ds pollution in the water body remain in obvious deficiency, have hindered practical application.
Summary of the invention
The invention provides a kind of preparation method of molecular-recognition separation membrane, this method is simple to operate, is suitable for suitability for industrialized production.
The present invention also provides a kind of phenolic compound has been had remarkable adsorption capacity and the convenient molecular-recognition separation membrane of regenerating, reclaiming.
A kind of preparation method of molecular-recognition separation membrane comprises the steps:
(1) adopt polymer separation film that surface or body have carboxyl as basement membrane;
(2) basement membrane is first at 1-ethyl-3-(N; The N-dimethyl aminopropyl) activation is carried out in immersion in the carbodiimide and the N-maloyl imines aqueous solution, and washing is immersed in the basement membrane after the activation in the phenyl boric acid solution then and reacts; Washing obtains the fixedly diffusion barrier of phenyl boric acid;
The solvent of described phenyl boric acid solution is an ethanol water;
(3) fixedly the diffusion barrier of phenyl boric acid is immersed in the Tris-HCl cushioning liquid of pH=7 of cyclodextrin and reacts, and promptly makes molecular-recognition separation membrane after the washing.
The present invention finds: can be at the fixing phenyl boric acid of membrane surface through epilamellar carboxyl; And then the recognition reaction of cyclodextrin is fixed cyclodextrin through phenyl boric acid; Owing to have very strong adhesion between phenyl boric acid and the cyclodextrin; Even regenerate the cyclodextrin of absorbing phenolic compound, can not destroy combining of cyclodextrin and phenyl boric acid yet, thereby develop a kind of molecular-recognition separation membrane that has remarkable adsorption capacity and convenient regeneration, reclaims.
In the step (1), described surface has the polymer separation film of carboxyl can select the film of introducing carboxyl through existing methods such as plasma treatment, glycerol polymerization or coatings at surface of separating film of polymer for use.
The polymer separation film that described surface has in the polymer separation film of carboxyl can be selected this area polymer separation film commonly used, optimization polypropylene diffusion barrier, polyethylene diffusion barrier, polysulfones diffusion barrier, polyethersulfone separating membrane, polyacrylonitrile diffusion barrier, polyether-ether-ketone diffusion barrier, cellulose acetate diffusion barrier or polyvinylidene fluoride separation membrane for use.
Described body has the preferred acrylonitrile of the polymer separation film-acrylic copolymer diffusion barrier of carboxyl; Further preferred acrylic acid molar content is acrylonitrile-acrylic copolymer diffusion barrier of 1%～15%.
In the step (2), the mol ratio of 1-ethyl-3-(N, N-dimethyl aminopropyl) carbodiimide and N-maloyl imines is preferably 1: 1 in described 1-ethyl-3-(N, the N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution;
The concentration of described 1-ethyl-3-(N, N-dimethyl aminopropyl) carbodiimide is preferably 0.1mg/mL～10mg/mL;
Described soak time is preferably 0.5 hour～and 3 hours;
The concentration of described phenyl boric acid solution is preferably 1mmol/L～50mmol/L; The concentration expressed in percentage by volume of ethanol water is preferably 20%～80%; Basement membrane after the activation be immersed in the time of reacting in the phenyl boric acid solution be preferably 0.5 hour～3 hours.
In the preferred aminobenzene boric acid of described phenyl boric acid, the aminobenzene boronic acid derivatives one or more; Further preferred aminobenzene boric acid.
In the step (3), the concentration of cyclodextrin is preferably 1mmol/L～50mmol/L in the Tris-HCl cushioning liquid of described cyclodextrin;
The described reaction time is preferably 5 minutes～and 3 hours.
Described Tris-HCl buffer solution is a tris-HCI buffer; Its compound method is according to this area method in common; Be generally: the trishydroxymethylaminomethane of 12.114g is dissolved in about 0.9L water, adds the concentrated hydrochloric acid of 46mL 11.6N, water adjustment final volume is to 1L; Wherein N is an equivalent concentration, the gram-equivalent number/liquor capacity of equivalent concentration=solute (liter).
Described cyclodextrin is selected one or more in alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin, alpha-cyclodextrin derivative, beta-cyclodextrin derivative, the gamma-cyclodextrin derivative for use, one or more in preferred alpha-cyclodextrin, beta-schardinger dextrin-, the gamma-cyclodextrin.
The molecular-recognition separation membrane that the present invention is based on phenyl boric acid and cyclodextrin recognition reaction can be used for removing phenolic compound in the water body.
The method that adopts molecular-recognition separation membrane of the present invention to remove phenolic compound in the water body is generally: described molecular-recognition separation membrane is immersed in the aqueous solution of phenolic compound vibration absorption 1～6 hour.
The investigation of molecular-recognition separation membrane absorption property of the present invention: the change in concentration that detects absorption front and back phenolic compound through ultraviolet spectra; Calculate adsorption rate, the concentration of phenolic compound before adsorption rate=(concentration of the concentration of phenolic compound before the absorption-absorption back phenolic compound)/absorption.
The concentration of the aqueous solution of described phenolic compound is generally 0.5mmol/L～20mmol/L.After if the excessive concentration of the aqueous solution of phenolic compound can be regenerated to the molecular recognition film; Repeat multiple adsorb; Can handle the molecular-recognition separation membrane that is adsorbed with phenolic compound through polyphenol oxidase; Molecular-recognition separation membrane is regenerated: the molecular-recognition separation membrane that will be adsorbed with phenolic compound is immersed in the phosphate buffer solution that concentration is the polyphenol oxidase of 0.1mg/mL～10mg/L (pH=7.0); Reacted 10 minutes～3 hours, promptly reusable after molecular-recognition separation membrane is regenerated.
Described phenolic compound includes but not limited to phenol, nitrophenol, methylphenol, catechol, resorcinol, hydroquinones, bisphenol-A (promptly 2; Two (4-hydroxy phenyl) propane of 2-), one or more in the Bisphenol F (promptly two (4-hydroxy phenyl) methane), bisphenol b (promptly 2,2-pair of (4-hydroxy phenyl) butane) etc.
The present invention has following advantage and beneficial effect:
(1) with the polymer separation film is base material immobilization cyclodextrin; Can be with the removal and the film separation process coupling of phenols micromolecular compound; Polymer separation film has higher specific surface area as porous material simultaneously, and immobilization cyclodextrin density is higher, can improve the adsorption capacity of phenolic compound.
(2) the fixing of cyclodextrin carries out through cyclodextrin-phenyl boric acid recognition reaction, and adhesion is strong, and immobilization process is simple, convenient, and the cyclodextrin after fixing has enough site efficient identification phenolic compounds.
(3) can be through the polyphenol oxidase cyclodextrin of absorbing phenolic compound of regenerating simply, easily, and can not destroy combining of cyclodextrin and phenyl boric acid, can not reduce the absorption property of molecular-recognition separation membrane significantly, significantly improve the reusability of cyclodextrin.
(4) the immobilization cyclodextrin reclaims easily, can not cause secondary pollution.
(5) preparation method of molecular-recognition separation membrane is simple to operate, is suitable for suitability for industrialized production, and the molecular-recognition separation membrane that makes has significant adsorption capacity to phenolic compound.
The specific embodiment
Through following examples the present invention is done more detailed description, but said embodiment is not construed as limiting the invention.
Embodiment 1
With the surperficial carboxylic polypropylene separation membrane that makes as follows as basement membrane: polypropylene separation membrane is immersed in the n-heptane solution of light trigger benzophenone that concentration is 1mmol/L; Naturally dry after 1 hour; Again film being immersed the monomer volumetric concentration is in 10% the acrylic acid aqueous solution; Ultraviolet light irradiation took out after 20 minutes, and it is dry to clean the back, promptly makes surperficial carboxylic polypropylene separation membrane.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) (1-ethyl-3-(N in the carbodiimide and the N-maloyl imines aqueous solution; The N-dimethyl aminopropyl) concentration of carbodiimide is 1mg/mL); Soak and carried out activation in 0.5 hour, washing, then the basement membrane after the activation being immersed in concentration is that 50mmol/L, solvent are that concentration expressed in percentage by volume is reaction 3 hours in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that alpha-cyclodextrin concentration is 50mmol/L; Reacted 3 hours, washing is removed and is made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 1
The surface that embodiment 1 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the phenol solution that concentration is 20mmol/L, vibration absorption 1 hour, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with phenol is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 10mg/mL, reacted 10 minutes, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 2
With the surperficial carboxylic polyethylene diffusion barrier that makes as follows as basement membrane: the polyacrylic acid aqueous solution of preparation 5g/L; Then the polyethylene diffusion barrier is immersed in this solution; Took out after at room temperature vibrating 3 hours and dry; Handled 30 seconds in the atmospheric plasma appearance, the washing back is dry, promptly makes surperficial carboxylic polyethylene diffusion barrier again.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) (1-ethyl-3-(N in the carbodiimide and the N-maloyl imines aqueous solution; The N-dimethyl aminopropyl) concentration of carbodiimide is 10mg/mL); Soak and carried out activation in 1 hour, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 1 hour in the aminobenzene BAS of 20% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of beta-schardinger dextrin-that beta-schardinger dextrin-concentration is 20mmol/L; Reacted 1 hour, washing is removed and is made the surface behind the unconjugated beta-schardinger dextrin-to combine the diffusion barrier of beta-schardinger dextrin-be molecular-recognition separation membrane.
Application examples 2
The surface that embodiment 2 is made combines the diffusion barrier of beta-schardinger dextrin-to be immersed in the nitrophenol aqueous solution that concentration is 10mmol/L, vibration absorption 3 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with nitrophenol is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 2mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 3
With the surperficial carboxylic polysulfones diffusion barrier that makes as follows as basement membrane: the polysulfones diffusion barrier is immersed in the n-heptane solution of light trigger benzophenone that concentration is 1mmol/L; Naturally dry after 1 hour; Again film being immersed the monomer volumetric concentration is in 10% the acrylic acid aqueous solution; Ultraviolet light irradiation took out after 20 minutes, and it is dry to clean the back, promptly makes surperficial carboxylic polysulfones diffusion barrier.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 0.1mg/mL) in; Soak and carried out activation in 3 hours, washing, then the basement membrane after the activation being immersed in concentration is that 1mmol/L, solvent are that concentration expressed in percentage by volume is reaction 0.5 hour in the aminobenzene BAS of 80% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of gamma-cyclodextrin that gamma-cyclodextrin concentration is 1mmol/L; Reacted 5 minutes, washing is removed and is made the surface behind the unconjugated gamma-cyclodextrin to combine the diffusion barrier of gamma-cyclodextrin be molecular-recognition separation membrane.
Application examples 3
The surface that embodiment 3 is made combines the diffusion barrier of gamma-cyclodextrin to be immersed in the methylphenol aqueous solution that concentration is 0.5mmol/L, vibration absorption 6 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with cresols is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 0.1mg/mL, reacted 3 hours, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 4
With the surperficial carboxylic polyethersulfone separating membrane that makes as follows as basement membrane: polyethersulfone separating membrane is immersed in the n-heptane solution of light trigger benzophenone that concentration is 1mmol/L; Naturally dry after 1 hour; Again film being immersed the monomer volumetric concentration is in 10% the acrylic acid aqueous solution; Ultraviolet light irradiation took out after 20 minutes, and it is dry to clean the back, promptly makes surperficial carboxylic polyethersulfone separating membrane.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 10mg/mL) in; Soak and carried out activation in 2 hours, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 1 hour in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid immersed in the Tris-HCl cushioning liquid (pH=7.0) that alpha-cyclodextrin and gamma-cyclodextrin total concentration are 20mmol/L alpha-cyclodextrin/gamma-cyclodextrin reacted 2 hours; The weight ratio of alpha-cyclodextrin and gamma-cyclodextrin is 1: 1, and it is molecular-recognition separation membrane that the diffusion barrier that makes surperficial coupling collar dextrin behind the unconjugated cyclodextrin is removed in washing.
Application examples 4
The diffusion barrier of the surperficial coupling collar dextrin that embodiment 4 is made is immersed in the catechol aqueous solution that concentration is 10mmol/L, and vibration absorption 3 hours detects the variation of phenolic compound concentration before and after the absorption through ultraviolet spectra, calculates adsorption rate 1; The diffusion barrier that is adsorbed with catechol is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 5mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 5
With the surperficial carboxylic polyacrylonitrile diffusion barrier that makes as follows as basement membrane: the polyacrylonitrile diffusion barrier is immersed in the n-heptane solution of light trigger benzophenone that concentration is 1mmol/L; Naturally dry after 1 hour; Again film being immersed the monomer volumetric concentration is in 10% the acrylic acid aqueous solution; Ultraviolet light irradiation took out after 20 minutes, and it is dry to clean the back, promptly makes surperficial carboxylic polyacrylonitrile diffusion barrier.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 2mg/mL) in; Soak and carried out activation in 1 hour, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 1 hour in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that alpha-cyclodextrin concentration is 30mmol/L; Reacted 1 hour, washing is removed and is promptly made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 5
The surface that embodiment 5 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the resorcinol aqueous solution that concentration is 10mmol/L, vibration absorption 3 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with resorcinol is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 2mg/mL, reacted 2 hours, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 6
With the surperficial carboxylic polyether-ether-ketone diffusion barrier that makes as follows as basement membrane: the polyether-ether-ketone diffusion barrier is immersed in the n-heptane solution of light trigger benzophenone that concentration is 1mmol/L; Naturally dry after 1 hour; Again film being immersed the monomer volumetric concentration is in 10% the acrylic acid aqueous solution; Ultraviolet light irradiation took out after 20 minutes, and it is dry to clean the back, promptly makes surperficial carboxylic polyether-ether-ketone diffusion barrier.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 2mg/mL) in; Soak and carried out activation in 1 hour, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 1 hour in the aminobenzene BAS of 60% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid immersed in the Tris-HCl cushioning liquid (pH=7.0) that alpha-cyclodextrin and beta-schardinger dextrin-total concentration are 20mmol/L alpha-cyclodextrin/beta-schardinger dextrin-reacted 1 hour; The weight ratio of alpha-cyclodextrin and beta-schardinger dextrin-is 1: 1, and it is molecular-recognition separation membrane that the diffusion barrier that makes surperficial coupling collar dextrin behind the unconjugated cyclodextrin is removed in washing.
Application examples 6
The diffusion barrier of the surperficial coupling collar dextrin that embodiment 6 is made is immersed in the hydroquinones aqueous solution that concentration is 10mmol/L, and vibration absorption 3 hours detects the variation of phenolic compound concentration before and after the absorption through ultraviolet spectra, calculates adsorption rate 1; The diffusion barrier that is adsorbed with hydroquinones is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 5mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 7
With the surperficial carboxylic separation membrane made from cellulose that makes as follows as basement membrane: separation membrane made from cellulose is immersed in the n-heptane solution of light trigger benzophenone that concentration is 1mmol/L; Naturally dry after 1 hour; Again film being immersed the monomer volumetric concentration is in 10% the acrylic acid aqueous solution; Ultraviolet light irradiation took out after 20 minutes, and it is dry to clean the back, promptly makes surperficial carboxylic separation membrane made from cellulose.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 2mg/mL) in; Soak and carried out activation in 1 hour, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 1 hour in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that alpha-cyclodextrin concentration is 20mmol/L; Reacted 1 hour, washing is removed and is promptly made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 7
The surface that embodiment 7 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the bisphenol-A aqueous solution that concentration is 10mmol/L, vibration absorption 3 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with bisphenol-A is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 4mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 8
With the surperficial carboxylic polyvinylidene fluoride separation membrane that makes as follows as basement membrane: the polyacrylic acid aqueous solution of preparation 5g/L; Then polyvinylidene fluoride separation membrane is immersed in this solution; Took out after at room temperature vibrating 3 hours and dry; Handled 30 seconds in the atmospheric plasma appearance, the washing back is dry, promptly makes surperficial carboxylic polyvinylidene fluoride separation membrane again.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 2mg/mL) in; Soak and carried out activation in 1 hour, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 2 hours in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that alpha-cyclodextrin concentration is 20mmol/L; Reacted 1 hour, washing is removed and is promptly made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 8
The surface that embodiment 8 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the Bisphenol F aqueous solution that concentration is 10mmol/L, vibration absorption 3 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with Bisphenol F is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 5mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 9
With the carboxylic acrylonitrile of body-acrylic copolymer diffusion barrier (the acrylic acid molar content is 1%) as basement membrane.Basement membrane makes according to following method: be that acrylonitrile-acrylic copolymer of 1% is dissolved in the dimethylacetylamide under 80 ℃ with the acrylic acid molar content; Be mixed with mass percentage concentration and be 14% solution; Leave standstill after 6 hours blade coating on glass plate; In air, place in the water-bath that changes 25 ℃ after 1 minute over to, take out after 1 hour, clean and promptly get basement membrane.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 0.1mg/mL) in; Soak and carried out activation in 3 hours, washing, then the basement membrane after the activation being immersed in concentration is that 50mmol/L, solvent are that concentration expressed in percentage by volume is reaction 3 hours in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that alpha-cyclodextrin concentration is 50mmol/L; Reacted 3 hours, washing is removed and is promptly made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 9
The surface that embodiment 9 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the bisphenol b aqueous solution that concentration is 20mmol/L, vibration absorption 6 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with bisphenol b is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 5mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 10
With the carboxylic acrylonitrile of body-acrylic copolymer diffusion barrier (the acrylic acid molar content is 15%) as basement membrane.Basement membrane makes according to following method: be that acrylonitrile-acrylic copolymer of 15% is dissolved in the dimethylacetylamide under 80 ℃ with the acrylic acid molar content; Be mixed with mass percentage concentration and be 18% solution; Leave standstill after 6 hours blade coating on glass plate; In air, place in the water-bath that changes 25 ℃ after 1 minute over to, take out after 1 hour, clean and promptly get basement membrane.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 2mg/mL) in; Soak and carried out activation in 0.5 hour, washing, then the basement membrane after the activation being immersed in concentration is that 1mmol/L, solvent are that concentration expressed in percentage by volume is reaction 0.5 hour in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that concentration is alpha-cyclodextrin 1mmol/L; Reacted 5 minutes, washing is removed and is promptly made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 10
The surface that embodiment 10 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the bisphenol-A aqueous solution that concentration is 10mmol/L, vibration absorption 3 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with bisphenol-A is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 2mg/mL, reacted 30 minutes, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 11
With the carboxylic acrylonitrile of body-acrylic copolymer diffusion barrier (the acrylic acid molar content is 8%) as basement membrane.Basement membrane makes according to following method: be that acrylonitrile-acrylic copolymer of 8% is dissolved in the dimethylacetylamide under 80 ℃ with the acrylic acid molar content; Be mixed with mass percentage concentration and be 15% solution; Leave standstill after 6 hours blade coating on glass plate; In air, place in the water-bath that changes 25 ℃ after 1 minute over to, take out after 1 hour, clean and promptly get basement membrane.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 0.1mg/mL) in; Soak and carried out activation in 1 hour, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 1 hour in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that alpha-cyclodextrin concentration is 20mmol/L; Reacted 1 hour, washing is removed and is promptly made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 11
The surface that embodiment 11 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the bisphenol-A aqueous solution that concentration is 10mmol/L, vibration absorption 3 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with bisphenol-A is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 50mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Embodiment 12
With the carboxylic polypropylene separation membrane in surface as basement membrane.Basement membrane makes as follows: compound concentration is about the polyacrylic acid aqueous solution of 5g/L, then polypropylene separation membrane is immersed in this polymer solution, takes out after at room temperature vibrating 3 hours and dries, and promptly makes surperficial carboxylic polypropylene separation membrane.
It is 1-ethyl-3-(N of 1: 1 that basement membrane is immersed mol ratio; The N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution (1-ethyl-3-(N; The N-dimethyl aminopropyl) concentration of carbodiimide is 2mg/mL) in; Soak and carried out activation in 1 hour, washing, then the basement membrane after the activation being immersed in concentration is that 20mmol/L, solvent are that concentration expressed in percentage by volume is reaction 1 hour in the aminobenzene BAS of 50% ethanol water; Fix amino phenyl boric acid on the film surface, obtain the diffusion barrier of fixing amino phenyl boric acid.
The diffusion barrier of fixing amino phenyl boric acid is immersed in the Tris-HCl cushioning liquid (pH=7.0) of alpha-cyclodextrin that alpha-cyclodextrin concentration is 20mmol/L; Reacted 1 hour, washing is removed and is promptly made the surface behind the unconjugated alpha-cyclodextrin to combine the diffusion barrier of alpha-cyclodextrin be molecular-recognition separation membrane.
Application examples 12
The surface that embodiment 12 is made combines the diffusion barrier of alpha-cyclodextrin to be immersed in the nitrophenol aqueous solution that concentration is 10mmol/L, vibration absorption 3 hours, and the variation through phenolic compound concentration before and after the ultraviolet spectra detection absorption calculates adsorption rate 1; The diffusion barrier that is adsorbed with nitrophenol is immersed in the phosphate buffer solution (pH=7.0) of the polyphenol oxidase of 50mg/mL, reacted 1 hour, promptly reusable after film is regenerated.Reuse 2 times according to above-mentioned steps, obtain adsorption rate 2 and adsorption rate 3 respectively.The result sees table 1.
Each diffusion barrier is to the adsorption rate of phenolic compound among table 1 embodiment
Claims (8)
1. the preparation method of a molecular-recognition separation membrane comprises the steps:
(1) adopt polymer separation film that surface or body have carboxyl as basement membrane;
(2) basement membrane is first at 1-ethyl-3-(N; The N-dimethyl aminopropyl) activation is carried out in immersion in the carbodiimide and the N-maloyl imines aqueous solution, and washing is immersed in the basement membrane after the activation in the phenyl boric acid solution then and reacts; Washing obtains the fixedly diffusion barrier of phenyl boric acid;
The solvent of described phenyl boric acid solution is an ethanol water;
(3) fixedly the diffusion barrier of phenyl boric acid is immersed in the Tris-HCl cushioning liquid of the pH=7 that contains cyclodextrin and reacts, and promptly makes molecular-recognition separation membrane after the washing;
The polymer separation film that the surface has in the polymer separation film of carboxyl is polypropylene separation membrane, polyethylene diffusion barrier, polysulfones diffusion barrier, polyethersulfone separating membrane, polyacrylonitrile diffusion barrier, polyether-ether-ketone diffusion barrier, cellulose acetate diffusion barrier or polyvinylidene fluoride separation membrane;
The polymer separation film that body has carboxyl is acrylonitrile-acrylic copolymer diffusion barrier;
Described phenyl boric acid is an aminobenzene boric acid.
2. the preparation method of molecular-recognition separation membrane according to claim 1; It is characterized in that; In the step (1), described surface has the polymer separation film of carboxyl for introduce the film of carboxyl at surface of separating film of polymer through the method for plasma treatment, glycerol polymerization or coating.
3. the preparation method of molecular-recognition separation membrane according to claim 1 is characterized in that, acrylic acid molar content is 1%～15% in described acrylonitrile-acrylic copolymer diffusion barrier.
4. the preparation method of molecular-recognition separation membrane according to claim 1; It is characterized in that; In the step (2); The mol ratio of 1-ethyl-3-(N, N-dimethyl aminopropyl) carbodiimide and N-maloyl imines is 1: 1 in described 1-ethyl-3-(N, the N-dimethyl aminopropyl) carbodiimide and the N-maloyl imines aqueous solution;
The concentration of described 1-ethyl-3-(N, N-dimethyl aminopropyl) carbodiimide is 0.1mg/mL～10mg/mL;
Described soak time is 0.5 hour～3 hours;
The concentration of described phenyl boric acid solution is 1mmol/L～50mmol/L; The concentration expressed in percentage by volume of ethanol water is 20%～80%; It is 0.5 hour～3 hours that basement membrane after the activation is immersed in the time of reacting in the phenyl boric acid solution.
5. the preparation method of molecular-recognition separation membrane according to claim 1 is characterized in that, in the step (3), the concentration of cyclodextrin is 1mmol/L～50mmol/L in the described Tris-HCl cushioning liquid that contains cyclodextrin;
The described reaction time is 5 minutes～3 hours.
6. the preparation method of molecular-recognition separation membrane according to claim 1 is characterized in that, described phenyl boric acid is an aminobenzene boric acid;
Described cyclodextrin is one or more in alpha-cyclodextrin, beta-schardinger dextrin-, the gamma-cyclodextrin.
7. molecular-recognition separation membrane according to the preparation method of each described molecular-recognition separation membrane of claim 1～6 preparation.
8. molecular-recognition separation membrane according to claim 7 is the application in the phenolic compound in removing water body; It is characterized in that described phenolic compound is one or more in phenol, nitrophenol, methylphenol, catechol, resorcinol, hydroquinones, bisphenol-A, Bisphenol F, the bisphenol b.
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