CN103480278A - Preparation method and application of anti-pollution hydrophilic separating membrane - Google Patents
Preparation method and application of anti-pollution hydrophilic separating membrane Download PDFInfo
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Abstract
The invention discloses a preparation method and an application of an anti-pollution hydrophilic separating membrane. The preparation method is characterized in that a pyrocatechol derivative is used as an accelerant and a curing agent between a separating membrane material and a hydrophilic material, when blending casting film liquid of the separating membrane is prepared, the pyrocatechol derivative is added to blending liquid of the separating membrane material and the hydrophilic material, and the pyrocatechol derivative is subjected to polymerization cross-linking in a phase conversion process of the membrane preparation, so that the effect of fixing the hydrophilic material is achieved. The preparation method of the anti-pollution hydrophilic separating membrane has strong universality and is suitable for the blending of multiple hydrophilic materials and multiple membrane materials. The preparation method is simple, easy to operate, mild in conditions, economic, high-efficiency, environmentally-friendly, easy for industrialization and suitable for the preparation of multi-functional hydrophilic micro-filtration membranes, ultra-filtration membranes, nano-filtration membranes, reverse-osmosis membranes, positive-osmosis membranes, pressure-delay osmosis membranes, pervaporation membranes and the like which are used for liquid and gas separation and membrane reactors.
Description
Technical field
The present invention relates to the diffusion barrier technical field, especially a kind of preparation method of antipollution polymer separation film.The diffusion barrier that the method makes has increased the water flux of film, has improved the resistance tocrocking of film, and has improved the biocompatibility of film.Can be used to separation and purification liquid or gas, dialysis or filter blood purification, and various large molecule is as the purifies and separates of medicine and albumen, catalytic fluid and gas reaction, and purify wastewater treatment and desalinization etc. for the water of removing various inorganic salts.
Background technology
Along with extensive use and the development of diffusion barrier technology, high polymer is as main membrane material, and the research of its performance has become the focus that people pay close attention to.Organic separation membrane is that a kind of macromolecular organic is learned material, and the function of existing separation, concentrated, purification and desalination has again the features such as efficient, energy-saving and environmental protection, molecular level filtration.Yet the pollution that the current problem existed of organic film technology is mainly film and deteriorated, make film short high with use cost service life.Wherein improve the hydrophily of film, the contamination resistance that improves film has become pressing issues to be solved.The material of the most of films that use at present is polypropylene (PP), polyethylene, and Kynoar, cellulose acetate, polysulfones, polyethers are mocked with polyvinyl chloride etc.Because himself strong-hydrophobicity causes the pollutants such as protein in water, carbohydrate, natural organic matter, polysaccharide organic matter to be easy to deposition, absorption, the obstruction on the film surface, thereby forming film pollutes, make membrane flux with the prolongation of running time lower will, when special when polymeric film material is used for biomedicine field (as haemodialysis or filtration), film just the protein accelerating fibers of face absorption and antibiotic fragment in the gathering on film surface, cause a series of biological respinse, for example form thrombus and immune response.Even can ignore the impact of diffusion barrier when protein, the character such as the hydrophily of film matrix material, charge and charged density all can produce important impact to the absorption of protein.
In order to expand the application of diffusion barrier, usually need to carry out the physical and chemical performance on modification or change film surface to membrane material, give traditional diffusion barrier greater functionality, increase the water penetration of film, improve the resistance tocrocking of film, improve the biocompatibility of film.Method to the modification of membrane material has physical modification, chemical modification and surface biological modification.Current method of modifying mainly contains the hydrophiling chemical modification of coating, absorption, surface graft copolymerization and bulk material.Yet all there is certain defect in modified chemical at present.As apply and the crosslinking technology cost high, apply and the adsorption layer long-time stability poor, changed the distribution of sizes of surface apertures, often cause hole plug and permeability reduction.
Polymer blending modification is easy and simple to handle, effective and favored with it.Because single membrane material is difficult to have good hydrophily simultaneously, film forming, heat endurance, chemical stability, resistance to acids and bases, anti-microorganism property erosion, oxidative resistance and the advantage such as mechanical strength preferably, therefore adopting the blend different materials to improve the performance of film, is the key addressed this problem.The blend of macromolecular material refers to that two or more macromolecules mix, and forms a kind of new material, and it,, except the performance of comprehensive original material own, also can overcome the defect separately in original material, and produces unexistent excellent properties in original material.Polymer blended Modified Membrane is mainly improved the performance of film from following 3 aspects: 1, improve the hydrophilicity of film and the film forming of polymer; 2, improve the stain resistance of film; 3, improve the materialization stability (improving corrosion resistance, heat resistance and the mechanical strength of film) of film.
Hydrophilic polymer as being dissolved in solvent jointly with the film macromolecular material, PVP, PVA, PEG etc. is become to the homogeneous casting solution, pass through forming film with phase transformation method, can significantly improve the milipore filter surface hydrophilicity, but the water soluble such as PVP, PEG, and PVP, PEG, PVA etc. can be used as effective pore-foaming agent of milipore filter, this type of blend film is not done the fixedly processing of hydrophiling additive simultaneously, film may run off gradually along with filtering operation in long-term running, finally causes the deteriorated of the unstable and film properties of hydrophily.
How promoting the fusion of different mixture material and keeping the distribution of water wetted material on the film surface is focus and the difficult point of research at present.
(Science 2007 in Messersmith research group, 318:426-430, U.S. Patent application 20080149566) dopamine is studied to discovery, under oxygen participation condition, dopamine (dopamine) can spontaneous oxidation polymerization in weakly alkaline solution, is cross-linked into high polymer.The mechanism of crosslinking of dopamine is that its catechol group in alkaline aqueous solution is oxidized by oxygen, generation has the dopamine naphtoquinone compounds of adjacent benzene two quinone structures, then with dopamine, anti-disproportionated reaction occurs, generate Semiquinone Radicals, then coupling is crosslinked, can form at multiple substrate material surface the crosslinked composite coating of close attachment simultaneously.Research shows, adhere to catechol and the amido functional group that behavior derive from dopamine of dopamine to substrate material surface, this structure can be set up covalency and noncovalent interaction with organic and inorganic surface, thereby make poly-dopamine coating brute force be attached to any substrate material surface, comprising polytetrafluoroethylene (PTFE), the material surface that the hydrophobicitys such as Kynoar are very strong.After modification, the material surface hydrophily significantly improves; And, because but poly-dopamine has a large amount of reactive groups as catechol, amino isoreactivity group, can realize the further functionalization of material surface.As the fixing antipollution material such as polyethylene glycol and natural polysaccharide.(Polymer 2010 in Freeman research group, 51:3472-3485. patent: the water purification membrane CN102149450 A with improved polluting proofing property) this method is expanded to diffusion barrier and comprised PVDF micro-filtration membrane, PSF milipore filter and polyamide (PA) reverse osmosis membrane surface modification, grafting with amino-terminated hydrophilic PEG long-chain, reduce the absorption of film surface to bovine serum albumin (BSA) molecule, improved the contamination resistance on film surface.(the Journal of Membrane Science 2010 such as Jiang, 364:194-202.) apply a strata dopamine active layer on hydrophobic PE microporous barrier surface, then by the catechol functional group grafting heparin molecule in active layer, prepared the surperficial polymer microporous film with hydrophily and anticoagulant active.
Yet existing research and patent are all the surface modifications by diffusion barrier, after prepared by diffusion barrier, utilize poly-dopamine layer to carry out surface modification, and further little molecule or large molecule organic material are bonded in to material surface.Although this method of modifying has been obtained good surface hydrophilicity, often reduced the water flux of film.This is because utilize the formation of poly-dopamine layer to stop up the part fenestra, makes hydrone be difficult for seeing through.
Summary of the invention
The present invention mainly solves in the preparation of antipollution diffusion barrier and application process, the difficult problem that wherein aqueous favoring of blending and modifying easily washes away out and then comes off, do not changed under sex condition at the flux that keeps film, prepared the resistant to pollution polymer nanocomposite membrane of a kind of enhancement high-performance.The present invention adopts catechol derivatives to make adhesive, promote the blend of polymer solution and water wetted material to prepare the casting solution of homogeneous dispersion, and in film forming procedure by catechol derivatives in the separation membrane surface polymerization, thereby fixing water wetted material makes it be difficult for diffusing out body.The method, in the casting solution process of preparation diffusion barrier, directly will contain catechol (catechol) derivative and polymer solution and the even blend of various hydrophilic pore material.Subsequently, the pH value of adjusting coagulating bath causes alkalescent (pH:7.5-10) or adds weak oxidant in coagulating bath, promote that in casting solution inversion of phases film forming procedure, the catechol derivatives crosslinking-oxidization becomes adjacent benzene diquines polymer, thereby the dispersion of the various water wetted materials of crosslinking curing in polymeric matrix, and improve the fenestra of polymer film and the hydrophily on surface.The method is simple to operate, mild condition, and economical and efficient, and be easy to industrialization.This is because the catechol group of catechol analog derivative can form covalency and noncovalent interaction with various materials, promote the bonding of polymer and other water wetted materials, thus the various water wetted materials of homogeneous dispersion the dispersion of crosslinking curing water wetted material in polymeric matrix.Then the diffusion barrier made by test is found: the flux of doping, hydrophily, cutoff performance, hot strength, compression strength etc. all are improved largely.
Diffusion barrier matrix material of the present invention inside, separation membrane surface, fenestra surface all comprise the poly-adjacent benzene diquines compound generated after the catechol compound oxidation and be crosslinked solidifies and homodisperse water wetted material.The technical scheme of taking comprises the steps:
(1) mark takes following raw materials according by weight: the polymeric film material of 20-150 part, the water wetted material of 0-50 part, 0.1-20 the catechol analog derivative of part, the decentralized medium solvent of 10-1000 part, the inorganic additive of the organic additive of 10-50 part and 0.1-30 part;
(2) above-mentioned raw materials is added in dissolving tank, at 20-100
°condition under, stirring and dissolving 2-48 hour, standing and defoaming 1-24 hour, make casting solution;
(3) the pH value of adjustment coagulating bath causes alkalescent (pH:7.5-10) and carries out oxygen or the air bubbling, or adds oxidant in coagulating bath; After curtain coating becomes liquid film on flat board by casting solution subsequently, immerse in coagulating bath and soak 1 minute-48 hours, carry out the inversion of phases process, the preparation flat sheet membrane, or by casting solution in the spinning of hollow-fibre membrane spinning-drawing machine, and immerse coagulating bath 1 minute-48 hours, carry out the inversion of phases process, prepare hollow-fibre membrane;
Or (4) further carry out surface aggregate by the diffusion barrier made and generate and to have the aramid layer that cuts salt functional, as nanofiltration, counter-infiltration, just permeate or the pressure retarded osmosis diffusion barrier;
(5) diffusion barrier (3) or (4) made soaks 30 minutes-48 hours in protection liquid, and subsequent drying makes membrane module.
The water wetted material that common polymeric membrane for separation adds has different molecular weight (MW:40-100,000 dalton) polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, sulfonated polystyrene, SPSF, polyether sulfone, polyimides, PEI, poly N-vinyl caprolactam, poly hydroxy ethyl acrylate (HEMA), polyethyl methacrylate (EMA), nylon, starch, cellulose, shitosan and derivative thereof etc.Common hydrophilic copolymers is as polyethylene-acrylic acid, PS-b-PEG, PVDF-b-PEG, PSf-b-PEG, PS-b-PMMA, Jeffamine etc.
Described catechol analog derivative is the organic molecule that a class contains dihydroxy phenyl and derivative thereof, and its general molecular formula is:
R1 wherein, R2, R3, R4, R5 is identical or different, be selected from independently of one another hydrogen or saturated and undersaturated, straight chain and side chain, replacement and unsubstituted C1-10 alkyl, and the substituent that contains one or more groups in amino, carboxyl, sulfydryl, halogen, hydroxyl, low alkyl group, lower alkoxy, monocyclic aryl, lower acyl and their combination; Including, but not limited to DOPA (DOPA), dopamine (dopamine), 3,4-dihydroxy benzenes methylamine, 3,4-4-dihydroxy benzaldehyde, 3,4-dihydroxy benzenes acetaldehyde, 3,4-dihydroxy-benzoic acid or 3,4-dihydroxyphenyl acetic acid.
Polymeric film material is all organic polymers that can film forming, comprises hydrophobic organic polymer: silicon rubber, Kynoar, polytetrafluoroethylene (PTFE), polysulfones, polyether sulfone, poly-sulphur sulfone, polyethylene, polypropylene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylonitrile, polyimides and copolymer, modifier and their blend, hydrophilic organic polymer: polyvinyl alcohol, shitosan and copolymer thereof, modifier and blend, and Merlon, cellulose acetate, polystyrene, containing cinnamic copolymer, acrylonitrile styrene copolymer, styrene-butadiene copolymer, styrene-vinyl benzyl halide copolymer, the copolymer of styrene and acrylonitrile polyarylene oxides, cellulosic polymer, cellulose acetate butyrate, cellulose propionate, ethyl cellulose, methylcellulose, nitrocellulose, polyamide, polyimides, aromatic polyamide, the aryl polyimides, polyethers, polyarylene oxides, polyphenylene oxide, the polyxylene oxide, polyurethane, polyarylate, PETG, polyalkyl methacrylate, polyacrylate, poly terephthalic acid benzene diester, polysulfide, polyvinyl alcohol, polyvinyl ester, polyvinyl acetate, polyvinyl proprionate, polyvinylpyridine, PVP, polyvingl ether, PB Polybutene-1, poly 4-methylpene-1, polyvinyl ketone, polyvinyl aldehyde, polyvinyl formal, polyvinyl butyral resin, the polyvinyl acid amides, polyvinylamine, the polyvinyl carbamate, the polyethylene urea, polyvinyl phosphate, polyvinyl sulfate, the polyene propyl group, poly-benzo benzo imidazoles, polyhydrazide, polyoxadiazole, polytriazoles, polybenzimidazoles, polycarbodiimide, poly-phosphine piperazine and their combination.
Described solvent is water, alcohol, N, N-dimethyl formamide, dimethyl sulfoxide (DMSO) (DMSO), N-dimethylacetylamide or 1-METHYLPYRROLIDONE.
Described coagulating bath is water, ethanol, N, N-dimethyl formamide, N, the combination of one or more in N-dimethylacetylamide, 1-METHYLPYRROLIDONE and acetone; Described cushioning liquid is that concentration is the cushioning liquid of Tris, phosphate, borate, acetate, citrate or the barbiturate of 0.1 mM-1M; Described oxidant is hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sodium metaperiodate, tert-butyl hydroperoxide, organic peroxide, benzoquinones, naphthoquinones, anthraquinone, phenol, manganese dioxide, ferric oxide, cobaltic oxide or nitrobenzene.
The combination of one or more in the Tween-80 aqueous solution of the Tween-40 aqueous solution of the glycerine water solution that described protection liquid is 20-70%, the Tween-20 aqueous solution of 1-15%, 1-15%, the Tween-60 aqueous solution of 1-15%, 1-15%.
Compared with prior art, this patent of the present invention only need add the dopamine or derivatives thereof in preparation blend casting solution, the poly-dopamine layer of oxidation cross-linked one-tenth in the inversion of phases process.This method utilizes dopamine for binding agent, promote the fusion between water wetted material and polymeric film material, and be prepared according to normal masking step, carry out the modification operation without additional step, thereby simplify the masking modifying process, save cost, universality is strong, simple to operate, mild condition, economical and efficient, and be easy to industrialization.The diffusion barrier that the method makes can be used as micro-filtration, ultrafiltration, nanofiltration, counter-infiltration, forward osmosis membrane, pressure retarded osmosis film, infiltrating and vaporizing membrane and film distillation and membrane catalytic reactor, be used for separation and purification liquid or gas, comprise that various large molecules are as medicine, albumen and gas, catalytic fluid and gas reaction, and purify wastewater treatment and desalinization etc. for the water of removing various inorganic salts.
Compared with prior art, advantage of the present invention is as follows:
(1) compound of the cross linking fixative of diffusion barrier water wetted material for containing catechol (catechol) structure, utilize the characteristics of its auto polymerization under oxidation or alkali condition, in diffusion barrier inversion of phases preparation process, by monomer polymerization, consumption is less can meet the fixing needs of hydrophiling;
(2) hydrophilic fixative self has certain hydrophilic interaction, can work in coordination with the high molecular weight hydrophilic additive milipore filter is produced to anti-pollution.Can't produce and pollute and toxic and side effect water environment simultaneously;
(3) hydrophilic fixative can react with the intermingling material generation ligand complex in casting solution, is conducive to promote merge mutually and improve the stability that homogeneous phase coexists between membrane material and water wetted material, and is conducive to promote even in film of water wetted material to distribute mutually;
(4) hydrophilic fixedly occurring in nascent state basement membrane solidification process in preparation method of the present invention, having guaranteed that water-soluble water wetted material is unlikely runs off take in the precipitated phase isolating environment that water is coagulation bath, and the stability in cocoa assurance film later stage application process, can also effectively improve the film mechanical strength simultaneously.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment only are not used in and limit the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1-4
The preparation method of the hydrophilic diffusion barrier of present embodiment carries out according to the following steps:
(1) weight is divided into to the polysulfones of 15 parts, 0.1 the polyethylene glycol (molecular weight 10 of part, 000g/mol), 0.05 the dopamine of part and the N of 85 parts, the N-dimethyl formamide adds in dissolving tank, under different temperatures (25 ℃, 45 ℃, 65 ℃, 85 ℃), and stirring and dissolving 2 hours, standing and defoaming 4 hours, make casting solution;
(2) regulate the pH to 8.5 of water coagulating bath by adding phosphate buffer;
(3) casting solution curtain coating on flat board is become to liquid film, then soak 10 minutes in coagulating bath, obtain the hydrophilic polymer flat sheet membrane;
(4) diffusion barrier step (3) made soaks 50 minutes in 15% the Tween-20 aqueous solution, then it is dried, for the assembling film assembly.
Embodiment 5-9
The preparation method of the hydrophilic diffusion barrier of present embodiment carries out according to the following steps:
(1) weight is respectively to the polyvinylidene fluoride material of 20 parts, 30 parts, 40 parts, 50 parts and 60 parts, Kynoar-the polyvinyl alcohol copolymer of 3 parts, 1 part 3, the DMF of 4-4-dihydroxy benzaldehyde and 80 weight portions adds in dissolving tank, under the condition of 100 ℃, stirring and dissolving 12 hours, standing and defoaming 8 hours, make casting solution;
(2), to the N that contains 3%, add 5 parts of potassium peroxydisulfates in the water coagulating bath of N-dimethyl formamide and 1-METHYLPYRROLIDONE;
(3) by casting solution in the spinning of hollow-fibre membrane spinning-drawing machine, then in coagulating bath, soak 12 hours, make hollow-fibre membrane;
(4) diffusion barrier step (3) made soaks 3 hours in 40% glycerine water solution, then it is dried, for the assembling film assembly.
Embodiment 10-13
The preparation method of the hydrophilic polymer membrane of present embodiment carries out according to the following steps:
(1) weight is divided into to the polyacrylonitrile of 20 parts, 1 part of different hydrophilic material (polyethylene glycol, polymethyl methacrylate, polyvinylpyrrolidone, polyvinyl alcohol), 1 part 3, the DMAC of 4-dihydroxyphenyl acetic acid and 80 parts adds in dissolving tank, under the condition of 30 ℃, and stirring and dissolving 48 hours, standing and defoaming 24 hours, make casting solution;
(2) add 2 parts of phenol in the pure water coagulating bath;
(3) by casting solution in the spinning of hollow-fibre membrane spinning-drawing machine, then in coagulating bath, soak 48 hours, make hollow-fibre membrane;
(4) diffusion barrier step (3) made soaks 24 hours in 15% the Tween-80 aqueous solution, then is dried, for the assembling film assembly.
Embodiment 14-17
The preparation method of the hydrophilic diffusion barrier of present embodiment carries out according to the following steps:
(1) take by mass percentage the polyvinyl butyral resin of 15 parts, the polysulfones of 5 parts, 5 parts 3, the N of 4-dihydroxy benzenes methylamine and 50 parts, the N-dimethyl formamide adds in dissolving tank, under 20 ℃, stirring and dissolving 10 hours, standing and defoaming 15 hours, make casting solution;
(2) regulate respectively to 7.5 of pH, 8.0,8.5,9.0 of water and acetone coagulating bath by adding the Tris salt buffer;
(3) casting solution curtain coating on flat board is become to liquid film, then soak 6 hours in coagulating bath, obtain the polymer flat sheet membrane;
(4) diffusion barrier step (5) made soaks 48 hours in 5% the Tween-40 aqueous solution, then is dried, for the assembling film assembly.
Embodiment 18-25
The preparation method of the hydrophilic reverse osmosis membrane of present embodiment carries out according to the following steps:
(1) weight is divided into to the polysulfones of 18 parts, by 0.1,0.5, the dopamines of the different amounts such as 1,2 part and the N of 85 parts, the N-dimethyl formamide adds in dissolving tank, stirring and dissolving 6 hours, standing and defoaming 2 hours, make casting solution;
(2) regulate the pH to 8.5 of water coagulating bath by adding the TRIS buffer solution;
(3) casting solution curtain coating on flat board is become to liquid film, then soak 10 minutes in coagulating bath, rouse the air or oxygen bubble simultaneously in coagulating bath, promote the auto polymerization of dopamine, obtain surface-crosslinked hydrophilic polymer flat sheet membrane;
Or by casting solution in the spinning of hollow-fibre membrane spinning-drawing machine, then in coagulating bath, soak 1 hour, to drum air or oxygen bubble in coagulating bath, promote the auto polymerization of dopamine simultaneously, obtain surface-crosslinked hydrophilic hollow-fibre membrane;
(4) the polyamine separation membrane surface modification one deck aramid layer made in step (3): flat sheet membrane or hollow-fibre membrane are immersed in to the 3%(mass ratio) is (as m-phenylene diamine (MPD), o-phenylenediamine, piperazine, p-phenylenediamine (PPD), equal benzene triamine or saturated many
Unit's amine) the aqueous solution 1 minute, then remove membrane module surface excessive moisture;
(5) diffusion barrier step (4) made is immersed in the hexane solution 1 minute of 1% polynary acyl chlorides (as pyromellitic trimethylsilyl chloride, o-phthaloyl chloride, paraphthaloyl chloride, m-phthaloyl chloride etc.), then removes the unnecessary solvent in membrane module surface;
(6) 100 ° of dryings of the film that step (5) made heating 10 minutes, be immersed in 15% glycerine water solution 24 hours subsequently, and the dry hole of protecting, make membrane module;
(7) make diffusion barrier and can be used as dull and stereotyped hydridization NF membrane, doughnut hydridization NF membrane, dull and stereotyped hydridization reverse osmosis membrane or doughnut hydridization reverse osmosis membrane, dull and stereotyped hydridization forward osmosis membrane or doughnut hydridization forward osmosis membrane, and dull and stereotyped hydridization pressure retarded osmosis film or doughnut hydridization pressure retarded osmosis film.
Claims (9)
1. one kind is carried out by various water wetted materials and polymer the preparation method that blend makes hydrophilic antipollution diffusion barrier, it is characterized in that by the catechol analog derivative being joined in the casting film blend solution of water wetted material and polymer, promote the bonding of water wetted material and polymer, and in the inversion of phases film forming procedure, by oxidation catechol compounds Cheng Julin benzene diquines compound, thereby the dispersion of the various water wetted materials of crosslinking curing in polymeric matrix, mainly solve hydrophilic diffusion barrier preparation process, water wetted material disperses an inhomogeneous and caducous difficult problem in use, improve the hydrophilic and hydrophobic on separation membrane surface and fenestra surface simultaneously, roughness, contamination resistance, or the biocompatibility of reinforcing material.
2. as follows according to the concrete steps of the hydrophilic diffusion barrier of the described preparation of claim 1:
(1) mark takes following raw materials according by weight: the polymeric film material of 20-150 part, the water wetted material of 0-50 part, 0.1-20 the catechol analog derivative of part, the decentralized medium solvent of 10-1000 part, the inorganic additive of the organic additive of 10-50 part and 0.1-30 part;
(2) above-mentioned raw materials is added in dissolving tank, under the condition of 20-100 °, stirring and dissolving 2-48 hour, standing and defoaming 1-24 hour, make casting solution;
(3) the pH value of adjustment coagulating bath causes alkalescent (pH:7.5-10) and carries out oxygen or the air bubbling, or adds oxidant in coagulating bath; After curtain coating becomes liquid film on flat board by casting solution subsequently, immerse in coagulating bath and soak 1 minute-48 hours, carry out the inversion of phases process, the preparation flat sheet membrane, or by casting solution in the spinning of hollow-fibre membrane spinning-drawing machine, and immerse coagulating bath 1 minute-48 hours, carry out the inversion of phases process, prepare hollow-fibre membrane;
Or (4) further carry out surface aggregate by the diffusion barrier made and generate and to have the aramid layer that cuts salt functional, as nanofiltration, counter-infiltration, just permeate or the pressure retarded osmosis diffusion barrier;
(5) diffusion barrier (3) or (4) made soaks 30 minutes-48 hours in protection liquid, and subsequent drying makes membrane module.
3. according to the described catechol analog derivative of claim 1, be a kind of organic molecule that contains dihydroxy benzenes base section and derivative thereof, its general molecular formula is:
Include but not limited to following molecular formula:
R1 wherein, R2, R3, R4, R5 is identical or different, be selected from independently of one another hydrogen, saturated and undersaturated, straight chain and side chain, replacement and unsubstituted C1-10 alkyl, and contain amino, carboxyl, sulfydryl, one or more substituents in halogen, oh group, low-grade alkyl group, lower alkoxy groups, monocyclic aryl, lower acyl group and their combination; Including, but not limited to DOPA (DOPA), dopamine (dopamine), 3,4-dihydroxy benzenes methylamine, 3,4-4-dihydroxy benzaldehyde, 3,4-dihydroxy benzenes acetaldehyde, 3,4-dihydroxy-benzoic acid or 3,4-dihydroxyphenyl acetic acid.
4. refer to hydrophilic small molecules or macromolecular material according to the described water wetted material of claim 1, as different molecular weight (MW:40-100, 000 dalton) polyvinyl alcohol, polyethylene glycol, polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, sulfonated polystyrene, SPSF, polyether sulfone, polyimides, PEI, the poly N-vinyl caprolactam, poly hydroxy ethyl acrylate (HEMA), polyethyl methacrylate (EMA), nylon, starch, cellulose, shitosan and derivative etc. thereof, common hydrophilic copolymers is as polyethylene-acrylic acid, PS-b-PEG, PVDF-b-PEG, PSf-b-PEG, PS-b-PMMA, Jeffamine etc.
5. diffusion barrier according to claim 1, is characterized in that described basic diffusion barrier can be used as micro-filtration membrane by material, milipore filter, NF membrane, reverse osmosis membrane, forward osmosis membrane, pressure retarded osmosis film, infiltrating and vaporizing membrane or their combination; Comprise liquid separating film by purposes, gas separation membrane, and membrane reactor.
6. decentralized medium according to claim 1 is water, alcohol, dimethyl formamide, dimethyl sulfoxide (DMSO) (DMSO) dimethylacetylamide or N-methyl pyrrolidone, and two or more mixtures; Described coagulating bath is a kind of in water, ethanol, dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE and acetone or wherein several combination; Described organic additive is cationic surfactant, anion surfactant, nonionic surface active agent, acetone, ethanol, one or more mixing in glycerine; Described inorganic additive is lithium chloride, ammonium chloride, potassium chloride, lithium nitrate, ammonium nitrate, lithium perchlorate, a kind of or concentrated mixing in water; The glycerine water solution that described protection liquid is 20-70%, the polysorbas20 aqueous solution of 1-15%, the Tween-40 aqueous solution of 1-15%, the Tween-60 aqueous solution of 1-15%, the mixing of one or more in the Tween-80 aqueous solution of 1-15%.
7. the pH of adjustment coagulating bath according to claim 1 can realize by the buffer salt solution that adds pH7.5-10, and its concentration can be from 0.1 mM-1M, and its buffer salt can be but be not limited to Tris, phosphate etc.
8. oxidant according to claim 1 comprises hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, tert-butyl hydroperoxide, sodium metaperiodate, organic peroxide, quinones, nitroso compound, metal oxide, phenol, Benzazole compounds, aminobenzene; Wherein quinones comprises again benzoquinones, naphthoquinones, anthraquinone; Metal oxide comprises again valency copper, ferric iron, trivalent cobalt, manganic etc.
9. organic film material comprises all organic polymers that can film forming according to claim 1, it can be hydrophobic organic polymer, as silicon rubber, Kynoar, polytetrafluoroethylene (PTFE), polysulfones, polyether sulfone, poly-sulphur sulfone, polyethylene, polypropylene, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyacrylonitrile, polyimides and copolymer thereof, modifier and blend etc., can be also the hydrophilic organic polymer, as polyvinyl alcohol, shitosan and copolymer thereof, modifier and blend etc., organic film material also comprises Merlon, cellulose acetate, polystyrene, contains cinnamic copolymer, acrylonitrile styrene copolymer, styrene-butadiene copolymer, styrene-vinyl benzyl halide copolymer in addition, the copolymer of styrene and acrylonitrile polyarylene oxides, Merlon, cellulosic polymer, cellulose acetate butyrate, cellulose propionate, ethyl cellulose, methylcellulose, nitrocellulose, polyamide, polyimides, aromatic polyamide, aryl polyimides, polyethers, polyarylene oxides, polyphenylene oxide, polyxylene oxide, poly-(esteramides-vulcabond), polyurethane, polyester (comprising polyarylate), PETG, polyalkyl methacrylate, polyacrylate, poly terephthalic acid benzene diester, polysulfide, polyvinyl alcohol, polyvinyl ester, polyvinyl acetate, polyvinyl proprionate, polyvinylpyridine, PVP, polyvingl ether, PB Polybutene-1, poly-4-methylpentene-1, polyvinyl ketone, polyvinyl aldehyde, polyvinyl formal, polyvinyl butyral resin, the polyvinyl acid amides, polyvinylamine, the polyvinyl carbamate, the polyethylene urea, polyvinyl phosphate, polyvinyl sulfate, the polyene propyl group, poly-benzo benzo imidazoles, polyhydrazide, polyoxadiazole, polytriazoles, polybenzimidazoles, polycarbodiimide, poly-phosphine piperazine and their combination.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041721A (en) * | 2012-12-27 | 2013-04-17 | 浙江大学 | Surface modification method for polymer separation membrane |
| CN103183340A (en) * | 2013-03-27 | 2013-07-03 | 复旦大学 | Ultra-high-modulus and high-strength oxidized graphene film and preparation method thereof |
| CN103212315A (en) * | 2013-04-27 | 2013-07-24 | 中材科技股份有限公司 | Preparation method of graft modified polytetrafluoroethylene (PTFE) microporous membrane with lasting hydrophilism |
-
2013
- 2013-09-06 CN CN201310401281.7A patent/CN103480278B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041721A (en) * | 2012-12-27 | 2013-04-17 | 浙江大学 | Surface modification method for polymer separation membrane |
| CN103183340A (en) * | 2013-03-27 | 2013-07-03 | 复旦大学 | Ultra-high-modulus and high-strength oxidized graphene film and preparation method thereof |
| CN103212315A (en) * | 2013-04-27 | 2013-07-24 | 中材科技股份有限公司 | Preparation method of graft modified polytetrafluoroethylene (PTFE) microporous membrane with lasting hydrophilism |
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