CN100387320C - Chelation type hollow fiber affinity membrane chromatogram, its manufacturing method and use - Google Patents
Chelation type hollow fiber affinity membrane chromatogram, its manufacturing method and use Download PDFInfo
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- CN100387320C CN100387320C CNB2005100153510A CN200510015351A CN100387320C CN 100387320 C CN100387320 C CN 100387320C CN B2005100153510 A CNB2005100153510 A CN B2005100153510A CN 200510015351 A CN200510015351 A CN 200510015351A CN 100387320 C CN100387320 C CN 100387320C
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Abstract
The present invention relates to a hollow fiber affinity membrane chromatogram in a chelation type and a preparation method and an application thereof. A plurality of thiourea base groups or mercapto chelation base groups which can form a chelation object with a noble metal ions or a heavy metal ions are arranged on the surface of a membrane micropore of the affinity membrane chromatogram. The preparation method of the fiber affinity membrane chromatogram comprises: 1, using polysulfone as a raw material to synthesize a modified polysulfone membrane forming material provided with an active reaction base group through a Fu's reaction; 2, designing a proper technological parameter and using dry spray-wet spinning technique to spin a hollow fiber substrate membrane; 3, immersing the substrate membrane into a saturation thiourea solution of 200 to 500 ml at the temperature of 15 to 45 DEG C; taking the substrate membrane out after a reaction is carried out for 24 to 30 hours, and thoroughly washing the substrate membrane by distilled water; obtaining the hollow fiber affinity membrane chromatogram in a polysulfone benzylthiourea chelation type. The affinity membrane chromatogram is especially used for the high-selectivity separation of the noble metal ions or the heavy metal ions, and has the advantages of good selectivity, high adsorption rate, simple and convenient use and convenient implementation.
Description
Technical field
The present invention relates to a kind of affinity film chromatography technology, be specially a kind of chelating type hollow fiber affinity membrane chromatogram and manufacture method and purposes, international Patent classificating number intends being Int.Cl
7B01D15/08.
Background technology
Along with life science and bionic developing rapidly, more and more higher to the requirement that biological macromolecule purifying separates, will utilize high selectivity that affinity media has and specificity that one or both can be separated from the mixture of tens of even hundreds of materials with the required component that it produces specific bond to the very little big molecule of number molecular weight difference.The affinity film chromatography isolation technics has appearred in late 1980s.Affinity film chromatography is meant and is connecting the functional group that can react or " spacerarm " (generally should be the compound greater than three carbon atoms) of certain-length as the film surface of carrier, select a suitable affinity ligand again for use, allow itself and the lip-deep active group of film " spacerarm " produce covalent bond under certain condition, generate the film separating medium that has affinity ligand.Film separating medium (as flat sheet membrane, hollow-fibre membrane etc.) is assemblied in certain assembly, promptly can be used to carry out the separation and the purifying of large biological molecule system.
At present, thus the affinity film chromatography preparation process generally be earlier with connect spacerarm after membrane material activation, the modification, aglucon is made affinity film chromatography.The feature that desirable affinity film chromatography matrix has is: high porosity, big surfaces externally and internally is long-pending, high chemistry, biology, mechanical stability, certain hydrophily, low non-specific adsorption, existence can chemically reactive group, high binding capacity, anti-solvent washing, cost is low, good reproducibility (Shang Zhenhua etc. membrane science and technology, 1995,15 (2): 1).Affinity film chromatography separates to be based on and (is generally ultrafiltration or micro-filtration membrane) on the film separating medium and utilizes the functional group that is had in its surface and the hole, with its activation, connect spacerarm with a certain size, select a suitable affinity ligand again for use, under appropraite condition, make itself and spacerarm molecule produce covalent bond, generate the film that has affinity ligand.Sample mixture is passed through film lentamente, make in the sample and can produce the interactional molecule of specificity (complex) with affinity ligand and produce coupling or combine, generate corresponding complex compound, then by the change condition, as eluent composition, pH value, ionic strength, temperature etc., to dissociate with the complex molecule generation of aglucon generation affinity interaction, it is received, again film is washed, regeneration and balance, in order to separating next time with (zymetology principle, Strove S.Methods inEnzymolgy, 1990,182:357-379).Cellulose is the affinity film chromatography host material of using the most extensively at present.3-chloro-1 such as Shang Zhenhua, connect p-phenylenediamine (PPD) behind the 2 propylene oxide activation celluloses and do spacerarm, connect bovine serum albumin, reactive dye K2BP and F3GA then and do aglucon, prepared a series of dish formula affinity film chromatography is applied to the separation and purification of alpha-interferon, albumin and alkaline phosphatase etc., respond well (Shang Zhenhua etc., membrane science and technology, 1995,15 (2): 1).Then they are again that host material has made well behaved affinity film chromatography with filter paper: use 3-chloro-1 under alkali condition, connect hexamethylene diamine behind the 2 propylene oxide activation filter paper and do spacerarm, be used for the endotoxic removal (Shang Zhenhua etc. of multicomponent solution with glutaraldehyde cross-linking method immobilized upward histidine, PB then, analytical chemistry, 1997,25:1010-1015).Polyamide, polycaprolactam (nylon) film owing to have favorable mechanical performance and chemical stability, have obtained to use widely.Klein etc. (European patent EP 0441660A1,1991) with hydrochloric acid with the nylon membrane hydrolysis after, number of amino groups can increase by 4 times on the film.(Shang Zhenhua etc. such as Shang Zhenhua, analytical chemistry, 1997,25:1010-1015) 66 microporous barriers of the nylon after the hydrolysis are activated with dibromopropane, connect hexamethylene diamine and do spacerarm, with the immobilized histidine of going up of glutaraldehyde method, the affinity film chromatography that makes can successfully be removed the endotoxin in the pharmaceutical preparations such as amino acid injection, bovine serum albumin, lysozyme again.(chromatogram such as Pestch, Petsch D, Beeskow T C, Anspach F B, DeckwerW D.J.Chromator., 1995,715:49-65) with being that aglucon makes the endotoxin that a series of affinity film chromatographies are used for removing buffer solution and protein solution with polylysine, PB, histidine etc. behind glucan, polyvinyl alcohol, the HEC modification of nylon film.Polysulfones is a kind of good filmogen, but its intrinsic hydrophobicity makes it directly not be used as affine separating medium, must carry out chemical modification, becomes to have certain hydrophilic film and could use.(membrane science such as Klein, Klein E, Eichhole E, YeagerD H.J.Membr.Sci., 1994,90:69-80) HEC in the coupling behind spent glycol diglycidyl ether (EGDGE) the activation PS membrane, hexamethylene diamine is done spacerarm on bonding after the EGDGE activation again, the recombinant protein rPrA that activates in the coupling again does aglucon, thereby makes a series of affinity film chromatographies.Polyolefin also can be used as host material after chemical modification.(membrane science, Kiyohara S, SasakiM, Staito K, Sugita K, Sugo T.J.Member.Sci., 1996,109:87-92 such as Kiyohara; Chromatogram, Kiyohara S, Kim M, Toida Y, Saito K, Sugita K.J.Chromatogr., 1997,785:209-215) graft acrylic acid and GMA on the porous polyethylene hollow fiber film do aglucon with L-amino acid and make affinity film chromatography, and the result shows that the performance of GMA caudacoria in the grafting is better than graft acrylic acid.(chromatogram Kim M, Satio K, Furusaki S, Sato T, Sugo T, IshigakiI.J.Chromatogr., 1991,585:45-51 such as Kim; 1991,585:27-33) GMA on radiation induced grafting on the polypropylene hollow membrane does aglucon with phenylalanine, tryptophan, absorption gamma globulin (BGG).(chromatogram such as Legallais, Legallais c, Anspach F B, Bueno S M A, HauptK, Vijayalshmi M A.J.Chromatogr., 1997, thus 691:33-41) adopt the copolymerization of ethene and vinyl alcohol to make excellent mechanical intensity and certain hydrophilic hollow-fibre membrane, with 1, histidine is done aglucon in the 4-butanediol diglycidyl ether activation back coupling, can be used for removing endotoxin from 1gG solution.(biotechnology progress such as Iwata, Iwata H., Saito K., FurusakiS..Biotechnol.Prog., 1991,7:412) graft glycidyl methacrylate on polypropylene screen makes the copper ion affinity film chromatography and is used to adsorb polypeptide (M=28) and the bovine serum albumin that contains HIS-LEU; (biotechnology and engineering such as Ruckenstein, Ruckenstein E., ZengX..Biotechnology and Bioengineering, 1997,56 (6): 6) carried out the research that separates lysozyme with chitin (chitin) affinity film chromatography; On this basis; (Li Jing etc. such as Li Jing; SCI; 1999; 20 (8) 1322-1327) adopt cryogenic oxygen or ammonia plasma treatment method modified polypropene microporous barrier; mechanism based on activation, coupling and the chelating process of plasma modification film has prepared the metal ion-chelant affinity film chromatography, and the purifying that is used for lysozyme with separate.Bao Shixiang etc. (1995,46 (1): 15-19) adopting novel hollow-fibre membrane is the aglucon carrier, is aglucon with the staphylococcal protein A for Bao Shixiang etc., chemical industry journal, prepare can be from human serum the A albumen affinity film chromatography of adsorbing separation γ-immunoglobulin (Ig).Remove cellulose membrane, nylon membrane, PS membrane, outside the polyethylene hollow membrane, can be used as the affinity film chromatography host material and reduce poly-hydroxyethyl first acrylate (PHEEMA) (chromatogram in addition, Denizlz A, Salih B, Arica M Y, Kesenci K, Hasirci V, PiskinE.J.Chromatogr., 1997,758:217-226), chitin (membrane science, RuckensteinE, Zeng X F.J.Membr Sci., 1998,142:13-26), glyceryl methacrylate and ethylene glycol dimethacrylate copolymer (chromatogram, Kasper C, Meringova L, FreitagR, Tennikova T.J.Chromatogr., 1998,798:65-72), polyvinyl alcohol (membrane science, Li R H, Barbari T A.J.Membr Sci., 1994,88:115-125), polyethers urea alkanes polymer (chromatogram, Bamford C H, Al-Lamee K G.J.Chromatogr., 1992,606:19), inoranic membrane such as glass hollow-fibre membrane (biotechnology and engineering, Serafica G C, Pimbley J, BelfortG.Biotechnol.Bioeng., 1994,43:21-36) etc.
By above-mentioned document as can be known, the affinity film chromatography preparation process generally be earlier with connect spacerarm after membrane material activation, the modification, thereby aglucon is made affinity film chromatography, prepared affinity film chromatography is after through complicated chemical modification, and some important performances can be affected.Row as above-mentioned dish formula affinity film chromatography (Shang Zhenhua etc. membrane science and technology, 1995,15 (2): in the preparation process 1), at process 3-chloro-1,2 propylene oxide activations, connect p-phenylenediamine (PPD) and do spacerarm, connect bovine serum albumin, reactive dye K2BP and F3GA then and do after the chemical modification of complexity such as aglucon, the cellulosic filming performance of matrix filmogen becomes relatively poor; The filmogen of polysulfones, polyamide, polycaprolactam function admirables such as (nylon) that has favorable mechanical performance and a chemical stability in above-mentioned usefulness is during as base film, base film is activated, connect again after the modification behind the multistep chemical reactions such as spacerarm, aglucon resulting affinity film chromatography become at aspects such as mechanical performances relatively poor (as European patent EP 0441660A1,1991; Chromatogram, Kiyohara S, KimM, Toida Y, Saito K, Sugita K.J.Chromatogr., 1997,785:209-215).Therefore the major defect that this manufacture method exists is: membrane material is activated, connect multistep chemical reactions such as spacerarm, aglucon again after the modification after, the filming performance of membrane material and aspects such as spinning property and mechanical performance can be subjected to very big influence.At present, because the limitation of product structure and its preparation method makes most of affinity film chromatographies also only limit to the separation and purification of large biological molecule, the high selectivity that is not applied to metal ion is as yet separated.
Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined provides a kind of chelating type hollow fiber affinity membrane chromatogram and manufacture method and purposes.This affinity film chromatography has special adsorptive selectivity to expensive, heavy metal ion, and good fluid breathability and stable mechanical performance have boundless application prospect in fields such as water treatments; Compare with classical production process, it is simple that this affinity film chromatography manufacture method has technology, and flow process is short, and is with low cost, and be easy to engineering amplification enforcement; Compare with traditional affinity film chromatography purposes, this affinity film chromatography is specially adapted to, and high selectivity expensive, heavy metal ion is separated.
The technical scheme that the present invention solves described product technology problem is: design a kind of chelating type hollow fiber affinity membrane chromatogram, this affinity film chromatography has the thiocarbamide or the sulfydryl chelation group that can form chelate in a large number with precious metal ion or heavy metal ion on the membrane micropore surface.
The technical scheme that the present invention solves described manufacture method technical problem is: design a kind of chelating type hollow fiber affinity membrane chromatogram manufacture method, this manufacture method comprises
1. modification polysulfones filmogen is synthetic
With the polysulfones is parent material, by Fu Shi (Friedel-Crafts) reaction, synthesizes the modification polysulfones filmogen that has active reactive group, and synthetic technological condition is:
Polysulfones consumption: 40-60% (disregarding the weight of organic solvent, surplus same);
Chloromethyl ether consumption: 60-40%;
Zinc chloride consumption: 2-6%;
Reaction temperature: 30-50 ℃;
Reaction time: 6-10 hour;
2. the spinning of doughnut matrix membrane
Adopt and do spray-wet spinning technology spinning doughnut matrix membrane, with modification polysulfones filmogen, additive and the organic solvent of described drying in 10-20: 2-8: after the 78-88 ratio is evenly mixed, under 20-35 ℃, be stirred to dissolving fully, make spinning solution; Described additive is meant polyethylene glycol (number-average molecular weight is respectively 400,600,10000), ethylene glycol or ammonium chloride; Described organic solvent is meant N, dinethylformamide or N, and the N-dimethylacetylamide, its spinning technique is:
Spinning solution temperature: 20-70 ℃;
Extrude volume flow: 30-50mL/min;
Dry-spinning path length: 5-40cm;
Core flow quantity: 0.2-0.8L.h
-1
Spinning winding speed: 20-40m/min, the aftertreatment technology parameter is:
Hot drawing-off: 1-3 doubly;
Heat treatment temperature: 30-60 ℃;
Preservation state: hygrometric state;
3. the manufacturing of chelating type hollow fiber affinity membrane chromatogram
Described 10-30 gram modification polysulfone hollow fibre matrix membrane is immersed in 15-45 ℃ the saturated thiourea solution of 200-500 milliliter, react taking-up after 24-30 hour, fully wash, can prepare polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram with distilled water.
If the polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram of preparing is further carried out basic hydrolysis, can prepare sulfydryl chelating type hollow fiber affinity membrane chromatogram.Be specially the polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram that to prepare and be immersed in 70-90 ℃, 0.5-1.5M NaOH or potassium hydroxide alkalescence solution in take out after hydrolysis 6-10 hour, fully wash with distilled water, use 0.5-1.5M acid solution example hydrochloric acid rinsing twice again, promptly make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
The technical scheme that the present invention solves described chelating type hollow fiber affinity membrane chromatogram purposes technical problem is: design a kind of chelating type hollow fiber affinity membrane chromatogram purposes, this affinity film chromatography is exclusively used in the high selectivity of expensive or heavy metal ion to be separated.
Compared with prior art, chelating type hollow fiber affinity membrane chromatogram of the present invention has have a large amount of thiocarbamides or mercapto groups on the membrane micropore surface, and thiocarbamide or mercapto groups and some expensive, heavy metal ion such as Ag+, Hg2+ etc. can form chelate, therefore this affinity film chromatography is called the chelating type hollow fiber affinity membrane chromatogram, also therefore this affinity film chromatography has the new purposes of the high selectivity separation that is applied to expensive or heavy metal ion, and the affinity film chromatography of prior art is mainly used in the separation and purification of large biological molecule.Chelating type hollow fiber affinity membrane chromatogram manufacture method of the present invention is that filmogen is carried out after the chemical modification, thereby going on foot three step chemical reactions through two again can connect chelation group and make affinity film chromatography on the membrane micropore surface, with long flow path, the prior art of technology complexity is compared, it is simple to have technology, flow process is shorter, and is with low cost, and is easy to the characteristics that engineering is amplified enforcement and promoted.Chelating type hollow fiber affinity membrane chromatogram of the present invention can be exclusively used in need be to occasion expensive, that heavy metal ion is carried out selective absorption, and it is good to have selectivity, the unique applications that adsorption rate is high.Experimental result shows that polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram is to Hg
2+Maximum dynamically chelating capacity can reach 326 μ g/cm
2, maximum rejection is up to 95.5%; Sulfydryl chelating type hollow fiber affinity membrane chromatogram is to Hg
2+Maximum dynamically chelating capacity can reach 350 μ g/cm
2, maximum rejection is up to 97.1%.
Description of drawings
(resolution ratio is 1cm to Fig. 1 for the VECTOR22 Fourier infrared spectrum figure of conventional PS membrane
-1);
(resolution ratio is 1cm to Fig. 2 for the VECTOR22 Fourier infrared spectrum figure of polysulfones benzyl thiocarbamide chelating type affinity film chromatography of the present invention
-1);
(resolution ratio is 1cm to Fig. 3 for the VECTOR22 Fourier infrared spectrum figure of sulfydryl chelating type affinity film chromatography of the present invention
-1).
The specific embodiment
Further narrate the present invention below in conjunction with embodiment:
Manufacture method of the present invention is to adopt the macromolecule design philosophy, and chelating affinity chromatography technology and membrane separation technique are organically combined, and preparation has concurrently and filters and the bifunctional hollow fiber affinity membrane chromatogram of ion chelating.Manufacture method of the present invention is specific as follows:
1, modification polysulfones filmogen is synthetic
The present invention is parent material with the polysulfones, by Fu Shi (Friedel-Crafts) reaction, synthesize have active reactive group modification polysulfones filmogen.Be specially the 10-30 gram polysulfones filmogen that drying is crossed and be dissolved in 200-300 milliliter organic solvent dichloromethane or the dichloroethanes, add 0.5-2.5 gram zinc chloride down at 15-25 ℃, 10-30 restrains chloromethyl ether; After dropwising, slowly be warming up to 30-50 ℃, reacted 6-10 hour.Reaction is cooled to room temperature with solution after finishing; Slowly pour in 200-500 ml methanol or the distilled water solution in the bottle and vigorous stirring, modification polysulfones filmogen is separated out into block; With this block hot distilled water cyclic washing, till no bubble is overflowed, then it is dried down at 60-70 ℃, promptly obtain rough modification polysulfones filmogen.Rough modification polysulfones filmogen is cut into small pieces, is dissolved in 200-300 milliliter organic solvent dichloromethane or the dichloroethanes, then solution is poured in 500 milliliters of 70-90 ℃ of distilled water, stir, adularescent bar or floccule are separated out.Sediment is filtered, dry under 60-70 ℃ at last again with distilled water washing three times, promptly obtain the modification polysulfones filmogen made from extra care.The active reactive group chlorinity of the modification polysulfones filmogen that is synthesized reaches 10-14%.Chlorinity is crossed when hanging down, and active group is few on the film surface micropore, is unfavorable for connecting more chelation group; And chlorinity is when too high, and then the spinnability of modification polysulfones filmogen can obviously reduce.
Synthetic technological condition is:
Polysulfones consumption: 40-60% (disregarding the weight of organic solvent, surplus same);
Chloromethyl ether consumption: 60-40%;
Zinc chloride consumption: 2-6%;
Reaction temperature: 30-50 ℃;
Reaction time: 6-10 hour.
After the process chemical modification, obvious deterioration can take place in the physicochemical properties of most filmogens, and especially the filming performance of material and spinning property can be destroyed, to such an extent as to can not film forming and spinning.Therefore, from numerous filmogens, filter out the parent material that meets target call, determine best synthetic technological condition, make it after chemical reaction, can connect active reactive group smoothly, reach 10-14% to prepare active reactive group (chlorinity), and the active filmogen with good filming performance and spinning property is one of key problem in technology point of the present invention.
2, the spinning of doughnut matrix membrane
Adopt existing dried spray-wet spinning technology spinning doughnut matrix membrane.With modification polysulfones filmogen, additive and the organic solvent of described drying in 10-20: 2-8: the 78-88 ratio is evenly mixed, and preferred mixed proportion is 15: 5: 80; Under 20-35 ℃, be stirred to dissolving fully then, make spinning solution, solution is static stand-by; Described additive is meant polyethylene glycol (number-average molecular weight is respectively 400,600,10000), ethylene glycol or ammonium chloride, preferred polyethylene glycol; Described organic solvent is meant N, dinethylformamide or N, N-dimethylacetylamide; To put into storage vat, deaeration after the spinning casting solution filtration that prepare.High pressure nitrogen will be extruded from spinning head through the modification polysulfones filmogen solution after the metering as pressure source; Core liquid hole, center from spinning head under head tank pressure enters the cavity of doughnut as supporter and interior setting medium simultaneously; After modification polysulfones filmogen dynamic analysis of spinning left spinning head, the air gap between spinning head and coagulating tank entered coagulating tank; In coagulating tank, behind the abundant coagulation forming, handle through hot-stretch and thermal finalization again, promptly obtain the doughnut matrix membrane.The doughnut matrix membrane of spinning function admirable is the key of preparation chelating hollow fiber affinity membrane chromatogram.In spinning modification polysulfone hollow fibre matrix membrane process, can utilize the variation of winding speed to control the thickness of tunica fibrosa or the thin and thick of tunica fibrosa.Under the constant situation of other condition, improve winding speed and can obtain thinner doughnut matrix membrane, and membranous wall to be thinner, the surface forms little close cortex; Reduce winding speed, the result is then opposite.The winding speed of controlling well in the spinning process is necessary technical process.Through experiment repeatedly, the result shows that control spinning winding speed is comparatively suitable between 20-40m/min.Modification polysulfone hollow fibre matrix membrane is preserved under hygrometric state.
Described dried spray-wet spinning technology parameter is:
Spinning solution temperature: 20-70 ℃;
Extrude volume flow: 30-50mL/min;
Dry-spinning path length: 5-40cm;
Core flow quantity: 0.2-0.8L.h
-1
Spinning winding speed: 20-40m/min, the aftertreatment technology parameter is:
Hot drawing-off: 1-3 doubly;
Heat treatment temperature: 30-60 ℃.
Compare with initial filmogen, the active filmogen that is synthesized all has been subjected to very big influence at aspects such as filming performance and spinning properties, especially adopts traditional dried spray-wet method spinning doughnut matrix membrane, has very big difficulty at the spinning manufacture view.Therefore, optimization is suitable and determine best spinning process condition, with the actual doughnut matrix membrane that spins out function admirable, also is one of the technology of the present invention key point.
3, the preparation of chelating type hollow fiber affinity membrane chromatogram
The present invention carries out the thiocarbamide reaction with modification polysulfone hollow fibre matrix membrane, can prepare polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram.On this basis, further carry out basic hydrolysis, can prepare sulfydryl chelating type hollow fiber affinity membrane chromatogram.The former concrete technology is, prepared 10-30 gram modification polysulfone hollow fibre matrix membrane is immersed in 15-45 ℃ the saturated thiourea solution of 200-500 milliliter, react after 24-30 hour and take out, fully wash with distilled water, promptly make polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram (referring to Fig. 2).As can be seen from Figure 2, the absworption peak at 1640cm-1 place is the thiocarbamide peak, illustrates that Cl has been converted into thiocarbamide; 1402.06cm-1 locate to occur the N-C=S characteristic absorption peak, when the reaction of modification polysulfones and thiocarbamide is described, also generated isothiourea, that is to say, examination of infrared spectrum is the result prove, contrasts conventional PS membrane (referring to Fig. 1), has the thiocarbamide chelation group on the polysulfones benzyl thiocarbamide chelating type affinity membrane of the present invention.And the latter's concrete technology is, prepared polysulfones benzyl thiocarbamide chelating type doughnut chelating type affinity film chromatography is immersed in 70-90 ℃, 0.5-1.5M 300 milliliters of NaOH or potassium hydroxide alkalescence solution in, constantly stir, take out the doughnut membrane chromatography after hydrolysis 6-10 hour, fully wash with distilled water earlier, and then, promptly make sulfydryl chelating type hollow fiber affinity membrane chromatogram (referring to Fig. 3) with 300-500 milliliter 0.5-1.5M acid solution example hydrochloric acid rinsing twice.As can be seen from Figure 3, at 2500cm
-1Weak absworption peak appears in the place, and this peak promptly is the characteristic peak of sulfydryl, that is to say that the examination of infrared spectrum result proves, contrasts conventional PS membrane (referring to Fig. 1), has a large amount of sulfydryl chelation groups on the sulfydryl chelating type affinity film chromatography of the present invention.In a word, the Fourier infrared spectrum experiment shows, has the thiocarbamide or the mercapto groups that can form chelate in a large number with expensive or heavy metal ion on the hollow fiber affinity membrane chromatogram of the present invention.These two kinds of chelating type hollow fiber affinity membrane chromatograms all will be preserved under hygrometric state.
From numerous chelating reagents, filter out and to combine with doughnut matrix membrane with active reactive group, again can be with expensive, heavy metal ion is carried out the suitable chelating reagent thiocarbamide of chelating absorption, adopt appropriate chemical methods, make and have the thiocarbamide or the sulfydryl chelation group that can form chelate in a large number on the doughnut matrix membrane micropore surface with expensive or heavy metal ion, and the preferable preparation process condition of optimization (being described technological parameter), to produce chelating type hollow fiber affinity membrane chromatogram one of key problem in technology point of the present invention especially that expensive or heavy metal ion are had big adsorption capacity and a high selectivity.
The present invention does not address part and is applicable to prior art.
Introduce specific embodiments of the invention below, but the present invention is not limited by the examples:
Embodiment 1:
Make polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram.
20 gram polysulfones are dissolved in 200 milliliters of organic solvent dichloromethane, add 1 gram zinc chloride respectively, 20 gram chloromethyl ethers; Be warming up to 30 ℃, reacted 6 hours.Reaction is cooled to room temperature after finishing; Pour in 200 ml methanol solution in the bottle and vigorous stirring, separate out into block; With this block cyclic washing, oven dry; It is dissolved in 200 milliliters of organic solvent dichloromethane, obtains solution, pour in 300 milliliters of 80 ℃ of distilled water, stir, the adularescent bar is separated out, and sediment is filtered, and washing is also dry, promptly obtains the modification polysulfones filmogen made from extra care.With refining modification polysulfones filmogen and polyethylene glycol (number-average molecular weight 400) and N, dinethylformamide mixes by 15: 4: 81 (weight ratio), is mixed with casting solution.Put into storage vat after the filtration, deaeration.High pressure nitrogen is as pressure source, to filter through the casting solution after the metering, enter dried spray-wet-spinning frame then and carry out spinning, obtain modification polysulfone hollow fibre matrix membrane, spinning technology parameter is designed to: modification polysulfones filmogen concentration is 15%, and additives polyethylene glycol (number-average molecular weight 400) concentration is 4%, the spinning solution temperature is 25 ℃, extruding volume flow is 40mL/min, and dry-spinning path length is 10cm, and the core flow quantity is 0.4L.h
-1, winding speed is 25m/min, and hot drawing-off is 2 times, and heat treatment temperature is 40 ℃.With the 12 gram matrix membranes that obtain 30 ℃ down with 350 milliliters of saturated thiocarbamides reactions after 24 hours, take out washing, promptly obtain polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram of the present invention.
Embodiment 2
Make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
20 gram polysulfones are dissolved in 250 milliliters of organic solvent dichloroethanes, add 2 gram zinc chloride respectively, 30 gram chloromethyl ethers; Be warming up to 36 ℃, reacted 8 hours.Reaction is cooled to room temperature after finishing; Pour in 250 ml methanol solution in the bottle and vigorous stirring, separate out into block; With this block cyclic washing, oven dry; It is dissolved in 250 milliliters of organic solvent dichloroethanes, obtains solution, pour in 400 milliliters of 80 ℃ of distilled water, stir, the adularescent bar is separated out.Sediment is filtered, and washing is also dry, promptly obtains the modification polysulfones filmogen made from extra care.With refining modification polysulfones filmogen and additives polyethylene glycol (number-average molecular weight 10000) and organic solvent N, N-dimethylacetylamide 15: 2: 83 by a certain percentage (weight ratio) mixes, and is mixed with casting solution.Put into storage vat after the filtration, deaeration.High pressure nitrogen is as pressure source, to filter through the casting solution after the metering, enter dried spray-wet-spinning frame then and carry out spinning, obtain modification polysulfone hollow fibre matrix membrane, spinning technology parameter is designed to: modification polysulfones filmogen concentration is 15%, and additive concentration is 2%, the spinning solution temperature is 27 ℃, extruding volume flow is 42mL/min, and dry-spinning path length is 13cm, and the core flow quantity is 0.5L.h
-1, winding speed is 27m/min, and hot drawing-off is 2.5 times, and heat treatment temperature is 40 ℃.With the 10 gram matrix membranes that obtain 25 ℃ down with 300 milliliters of saturated thiocarbamides reactions after 28 hours, take out washing, and then immerse in 300 milliliters of 1NNaOH solution 82 ℃ under hydrolysis 10h, constantly stirring; Take out, fully wash with distilled water earlier, use 300 milliliters of 0.5N HCl solution rinsing twice then, promptly make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
Embodiment 3
Make polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram.
25 gram polysulfones are dissolved in 300 milliliters of organic solvent dichloroethanes, drip 25 gram zinc chloride/chloromethyl ether (1: 10) compounds, be warming up to 32 ℃, reacted 10 hours.Reaction is cooled to room temperature after finishing; Pour in 500 ml distilled waters solution in the bottle and vigorous stirring, separate out into block; With this block cyclic washing, oven dry; It is dissolved in 300 milliliters of organic solvent dichloroethanes, obtains solution, pour in 350 milliliters of 90 ℃ of distilled water, stir, the adularescent bar is separated out.Sediment is filtered, and washing is also dry, promptly obtains the modification filmogen made from extra care.With refining modification filmogen and additive ethylene glycol and organic solvent N, N-dimethylacetylamide 16: 4: 80 by a certain percentage (weight ratio) mixes, and is mixed with casting solution.Put into storage vat after the filtration, deaeration.High pressure nitrogen is as pressure source, to filter through the casting solution after the metering, enter dried spray-wet-spinning frame then and carry out spinning, obtain modification polysulfone hollow fibre matrix membrane, spinning technology parameter is designed to: modification filmogen concentration is 16%, and the additive glycol concentration is 4%, the spinning solution temperature is 25 ℃, extruding volume flow is 40mL/min, and dry-spinning path length is 12cm, and the core flow quantity is 0.6L.h
-1, winding speed is 30m/min, and hot drawing-off is 1.5 times, and heat treatment temperature is 50 ℃.With the 15 gram matrix membranes that obtain 35 ℃ down with 500 milliliters of saturated thiocarbamides reactions after 28 hours, take out washing, promptly obtain polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram of the present invention.
Embodiment 4
Make chelating type polysulfones benzyl thiocarbamide hollow fiber affinity membrane chromatogram.
15 gram polysulfones are dissolved in 300 milliliters of organic solvent dichloromethane, are warming up to 40 ℃, drip 15 gram zinc chloride/chloromethyl ether (1: 10) compounds, reacted 7 hours.Reaction is cooled to room temperature after finishing; Pour in 400 milliliters of absolute methanols solution in the bottle and vigorous stirring, separate out into block; With this block cyclic washing, oven dry; It is dissolved in 300 milliliters of organic solvent dichloromethane, obtains solution, pour in 500 milliliters of 85 ℃ of distilled water, stir, the adularescent bar is separated out.Sediment is filtered, and washing is also dry, promptly obtains the modification filmogen made from extra care.With refining modification filmogen and inorganic additive ammonium chloride and organic solvent N, N-dimethylacetylamide 16: 2: 82 by a certain percentage (weight ratio) mixes, and is mixed with casting solution.Put into storage vat after the filtration, deaeration.High pressure nitrogen is as pressure source, to filter through the casting solution after the metering, enter dried spray-wet-spinning frame then and carry out spinning, obtain modification polysulfone hollow fibre matrix membrane, spinning technology parameter is designed to: modification filmogen concentration is 16%, and the additive ammonium chloride concentration is 2%, the spinning solution temperature is 35 ℃, extruding volume flow is 42mL/min, and dry-spinning path length is 10cm, and the core flow quantity is 0.5L.h
-1, winding speed is 28m/min, and hot drawing-off is 2 times, and heat treatment temperature is 45 ℃.With the 10 gram matrix membranes that obtain 40 ℃ down with 300 milliliters of saturated thiourea solutions reactions after 26 hours, take out washing, promptly obtain polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram of the present invention.
Embodiment 5
Make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
20 gram polysulfones are dissolved in 350 milliliters of organic solvent dichloromethane, are warming up to 36 ℃, drip 30 gram zinc chloride/chloromethyl ether (1: 20) compounds, reacted 10 hours.Reaction is cooled to room temperature after finishing; Pour in 500 ml distilled waters solution in the bottle and vigorous stirring, separate out into block; With this block cyclic washing, oven dry; It is dissolved in 350 milliliters of organic solvent dichloromethane, obtains solution, pour in 500 milliliters of 90 ℃ of distilled water, stir, the adularescent bar is separated out.Sediment is filtered, and washing is also dry, promptly obtains the modification filmogen made from extra care.With refining modification filmogen and organic additive ethylene glycol and organic solvent N, N-dimethylacetylamide 18: 2: 80 by a certain percentage (weight ratio) mixes, and is mixed with casting solution.Put into storage vat after the filtration, the negative pressure deaeration.High pressure nitrogen is as pressure source, to filter through the casting solution after the metering, enter dried spray-wet-spinning frame then and carry out spinning, obtain modification polysulfone hollow fibre matrix membrane, spinning technology parameter is designed to: modification filmogen concentration is 18%, and additive concentration is 2%, the spinning solution temperature is 30 ℃, extruding volume flow is 40mL/min, and dry-spinning path length is 12cm, and the core flow quantity is 0.4L.h
-1, winding speed is 25m/min, and hot drawing-off is 2.5 times, and heat treatment temperature is 42 ℃.With the 12 gram matrix membranes that obtain 38 ℃ down with 400 milliliters of saturated thiourea solutions reactions after 28 hours, take out washing, and then immerse in 350 milliliters of 1.0N KOH solution 85 ℃ under hydrolysis 10h, constantly stirring; Take out, fully wash with distilled water earlier, use 400 milliliters of 0.6N HCl solution rinsing twice then, promptly make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
Embodiment 6
Make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
28 gram polysulfones are dissolved in 500 milliliters of organic solvent dichloroethanes, are warming up to 32 ℃, drip 30 gram zinc chloride/chloromethyl ether (1: 20) compounds, reacted 10 hours.Reaction is cooled to room temperature after finishing; Pour in 500 milliliters of absolute methanols solution in the bottle and vigorous stirring, separate out into block; With this block cyclic washing, oven dry; It is dissolved in 500 milliliters of organic solvent dichloroethanes, obtains solution, pour in 500 milliliters of 95 ℃ of distilled water, stir, the adularescent bar is separated out.Sediment is filtered, and washing is also dry, promptly obtains the modification filmogen made from extra care.With refining modification filmogen and polymeric additive polyethylene glycol (number-average molecular weight 600) and organic solvent N, N-dimethylacetylamide 19: 2: 79 by a certain percentage (weight ratio) mixes, and is mixed with casting solution.Put into storage vat after the filtration, deaeration.High pressure nitrogen is as pressure source, to filter through the casting solution after the metering, enter dried spray-wet-spinning frame then and carry out spinning, obtain modification polysulfone hollow fibre matrix membrane, spinning technology parameter is designed to: modification filmogen concentration is 19%, and additives polyethylene glycol (number-average molecular weight 600) concentration is 2%, the spinning solution temperature is 42 ℃, extruding volume flow is 45mL/min, and dry-spinning path length is 14cm, and the core flow quantity is 0.6L.h
-1, winding speed is 30m/min, and hot drawing-off is 3 times, and heat treatment temperature is 45 ℃.With the 23 gram matrix membranes that obtain 40 ℃ down with 500 milliliters of saturated thiourea solutions reactions after 30 hours, take out washing, and then immerse in the 1.0N KOH solution 500 milliliters 90 ℃ under hydrolysis 10h, constantly stirring; Take out, fully wash with distilled water earlier, use 400 milliliters of 1.0N HCl solution rinsing twice then, promptly make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
Embodiment 7
Polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram is to Hg
2+Removal.
Polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram of the present invention processing is made chelating type hollow fiber affinity membrane chromatogram assembly, and be placed in and carry out removal of mercury experiment on the homemade hollow-fibre membrane chromatography experiment device.The result is that this membrane chromatography is to Hg
2+Maximum dynamically chelating capacity can reach 326 μ g/cm
2, maximum rejection is up to 95.5%.
Embodiment 8
Sulfydryl chelating type hollow fiber affinity membrane chromatogram is to Hg
2+Removal.
Sulfydryl chelating type hollow fiber affinity membrane chromatogram of the present invention processing is made chelating type hollow fiber affinity membrane chromatogram assembly, and be placed in and carry out removal of mercury experiment on the homemade hollow-fibre membrane chromatography experiment device.The result shows that this sulfydryl chelating type hollow fiber affinity membrane chromatogram is to Hg
2+Maximum dynamically chelating capacity can reach 350 μ g/cm
2, maximum rejection is up to 97.1%.
Claims (4)
1. a chelating type hollow fiber affinity membrane chromatogram is characterized in that this affinity film chromatography has the thiocarbamide or the mercapto groups that can form chelate in a large number with expensive or heavy metal ion on the membrane micropore surface.
2. the manufacture method of a chelating type hollow fiber affinity membrane chromatogram according to claim 1, this manufacture method comprises
(1). synthesizing of modification polysulfones filmogen
With the polysulfones is parent material, by the Fu Shi reaction, synthesizes the modification polysulfones filmogen that has active reactive group, and synthetic technological condition is:
Polysulfones consumption: 40-60% (disregarding the weight of organic solvent, surplus same);
Chloromethyl ether consumption: 60-40%;
Zinc chloride consumption: 2-6%;
Reaction temperature: 30-50 ℃;
Reaction time: 6-10 hour;
(2). the spinning of doughnut matrix membrane
Adopt and do spray-wet spinning technology spinning doughnut matrix membrane, with modification polysulfones filmogen, additive and the organic solvent of described drying in 10-20: 2-8: after the 78-88 ratio is evenly mixed, under 20-35 ℃, be stirred to dissolving fully, make spinning solution; Described additive is meant polyethylene glycol (number-average molecular weight is respectively 400,600,10000), ethylene glycol or ammonium chloride; Described organic solvent is meant N, dinethylformamide or N, and the N-dimethylacetylamide, its spinning technique is:
Spinning solution temperature: 20-70 ℃;
Extrude volume flow: 30-50mL/min;
Dry-spinning path length: 5-40cm;
Core flow quantity: 0.2-0.8L.h
-1
Spinning winding speed: 20-40m/min, the aftertreatment technology parameter is:
Hot drawing-off: 1-3 doubly;
Heat treatment temperature: 30-60 ℃;
Preservation state: hygrometric state;
(3). the manufacturing of chelating type hollow fiber affinity membrane chromatogram
Described modification 10-30 gram polysulfone hollow fibre matrix membrane is immersed in 15-45 ℃ the saturated thiourea solution of 200-500 milliliter, react taking-up after 24-30 hour, fully wash, can prepare polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram with distilled water.
3. the manufacture method of chelating type hollow fiber affinity membrane chromatogram according to claim 2 is characterized in that modification polysulfones filmogen, additive and the organic solvent of described drying evenly mixes in 15: 5: 80 ratio; Described additive is a polyethylene glycol; The active reactive group chlorinity of the modification polysulfones filmogen that is synthesized reaches 10-14%.
4. according to the manufacture method of claim 2 or 3 described chelating type hollow fiber affinity membrane chromatograms, it is characterized in that the prepared polysulfones benzyl thiocarbamide chelating type hollow fiber affinity membrane chromatogram that goes out is immersed in 70-90 ℃, 0.5-1.5M NaOH or potassium hydroxide alkalescence solution in further take out after hydrolysis 6-10 hour, fully wash with distilled water, use 0.5-1.5M acid solution example hydrochloric acid rinsing twice again, promptly make sulfydryl chelating type hollow fiber affinity membrane chromatogram.
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