CN103464013A - High-performance hybrid separation membrane and preparation method thereof - Google Patents
High-performance hybrid separation membrane and preparation method thereof Download PDFInfo
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- CN103464013A CN103464013A CN2013103147395A CN201310314739A CN103464013A CN 103464013 A CN103464013 A CN 103464013A CN 2013103147395 A CN2013103147395 A CN 2013103147395A CN 201310314739 A CN201310314739 A CN 201310314739A CN 103464013 A CN103464013 A CN 103464013A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000926 separation method Methods 0.000 title claims abstract description 17
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Abstract
The invention provides a high-performance hybrid separation membrane and a preparation method thereof. The interior of the separation membrane matrix material, the surface of the separation membrane and the surface of the membrane pores all contain poly-o-phenylendiquinone compounds generated after oxidation of the catechol compounds and nano materials which are cross-linked, cured and uniformly dispersed. The preparation method adopts the technical route that the catechol derivative is added into a casting film blending solution of the nano material and the polymer to promote the adhesion of the nano material and the polymer, and the catechol compound is oxidized into the poly-catechol compound in the phase inversion film forming process, so that the dispersion of various nano materials in a polymer matrix is crosslinked and cured, and the preparation method specifically comprises the steps of preparation of a casting film solution, modulation of a coagulation bath, film forming, curing and/or modification.
Description
Technical field
The present invention relates to the diffusion barrier technical field, especially high-performance hydridization diffusion barrier and preparation method thereof.
Background technology
There is a serious shortage in the supply for freshwater resources, and energy breach enlarges rapidly and environmental pollution is on the rise is the important bottleneck that restricts now human civilization health and sustainable development.As a kind of emerging high efficient separation technology, membrane separation technique is regarded as 21st century one of the most potential rising industry, has been widely used in the every field such as chemical industry, environmental protection, electronics, light industry, weaving, oil, food, medicine, biotechnology and energy project.Diffusion barrier, because of its unique structure, is a dark horse aspect environmental protection and resource regeneration, and in environmental project, particularly water treatment aspect has a wide range of applications.
The diffusion barrier technology refers on molecular level, with the pellicle barrier layer that elects, the compounding substances of different-grain diameter, when the semipermeable membrane, is realized the technology that machinery separates, popular say exactly to solute in mixture with solvent, separated, classification, purification and enrichment.The separation method traditional with other compared, and film separates and to have that process is simple, better economy, there is no that phase transformation, separation are larger, energy-conservation, efficient, non-secondary pollution, continued operation at normal temperatures, can directly amplify, can single-mindedly join the advantage such as film.
According to the size in diffusion barrier aperture, generally can be divided into four classes such as micro-filtration membrane (MF), milipore filter (UF), NF membrane (NF), reverse osmosis membrane (RO), its filtering accuracy is more and more higher by above order.According to different operator schemes, traditional counter-infiltration (RO), ultrafiltration (UF), micro-filtration (MF) etc. need move under certain impressed pressure; And emerging just infiltration (FO) only need overcome lower fluid flow resistance, without moving, therefore have that energy consumption is low, the salt rejection is high and film pollutes the advantages such as little under the impressed pressure environment.
According to source and the character of membrane material, diffusion barrier divides again organic film and inoranic membrane.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.Because it is organic material, even also can degrade after discarded, can be to environment.The organic film material of extensive use now comprises the polymer such as Kynoar, polyether sulfone, polysulfones, 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 form that film pollutes and deteriorated, make that film service life is short and use cost is high.Current method of modifying mainly contains the hydrophiling chemical modification of coating, absorption, surface graft copolymerization, bulk material.Although above method has improved resistance tocrocking and water flux, improved some kinds, also there is certain defect.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.
The inorganic nano material blending and modifying becomes one of focus of domestic and international academia and engineering circles research.The inorganic nano material related to comprises that various inorganic nanoparticles are as various metals, metal oxide, quantum dot and alloy nano-material; Monodimension nanometer material comprises various inorganic nano-tubes, nano wire, as CNT, titanium nanotube, titanium nano wire; The two-dimensional nano material is as imvite with low cost, rectorite etc.Chinese patent 201210096520.8(Kynoar-CNT composite separating film and preparation method thereof) utilize and ultrasonicly add churned mechanically method even carbon nanotube is distributed in Kynoar, finally by the wet method phase inversion, made the poly-vinylidene-fluoride composite film of doped carbon nanometer pipe, because the surface that can finely improve Kynoar that adds of CNT can, strengthen the hydrophily of film, improve the resistance tocrocking of film, therefore make the pure water flux of film be greatly improved.This nano composite membrane mainly contains following characteristics: (1) nano material can effectively be improved the section pore structure of polymer film, effectively improves composite membrane water permeation performance and separative efficiency; (2) nano material can effectively be improved polymer film surface current potential, physicochemical characteristic, microscopic appearance, and the interface behavior on pollutant and film surface in the reduction water body, alleviate film and pollute; (3) nano material can effectively be improved the mechanical behavior of polymer film, strengthens the close characteristic of resistance to compression of composite membrane, thereby extends the cycle of operation in the engineering application.But hybridized film prepared by this method need to be by nano particle and organic film material or monomer material blend, and this easily makes nanoparticle reunite and coagulation, disperses unevenly, and then causes membrane structure inhomogeneous, affects its performance.And in use, nano material easily comes off, make film lose excellent properties.Therefore need to before blend, carry out modification by nanoparticle or the film itself to doping.
Chinese patent 201210099764.1(nanofiltration separation membrane and preparation method thereof) DOPA and/or dopamine are stablized to auto polymerization in membrane surface, again with long-chain molecule in amino or sulfydryl react, carry out the nanofiltration separation membrane that grafting and crosslinked rear preparation hydrophily strengthen.
This method of utilizing dopamine modified Nano material to prepare the hydridization diffusion barrier is to carry out the poly-dopamine layer of oxidation polymerization generation at the separation membrane surface prepared to carry out, need step various, cost is higher, and the poly-dopamine layer generated easily stops up fenestra, causes water flux to descend.
Summary of the invention
The object of the invention is to solve nano material in prior art and disperse an inhomogeneous and caducous difficult problem, provide a kind of nano material to be uniformly dispersed and the high-performance hydridization diffusion barrier of difficult drop-off, can improve by the kind that changes nano material the performance such as the biocompatibility of hydrophilic and hydrophobic, roughness, contamination resistance or reinforcing material on separation membrane surface and fenestra surface and antibiotic, catalysis simultaneously or give performance and the enhance mechanical strength such as conduction that material is new, optics, thermodynamics.
Another purpose of purpose of the present invention is to provide the method for this high-performance hydridization diffusion barrier of preparation.
For achieving the above object, the technology path that the present invention takes is: the catechol analog derivative is joined in the casting film blend solution of nano material and polymer, promote the bonding of nano material and polymer, and in the inversion of phases film forming procedure, by oxidation catechol compounds Cheng Julin benzene diquines compound, thus the dispersion of the various nano materials of crosslinking curing in polymeric matrix.
For realizing first purpose of the present invention, 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 nano material.
For realizing second purpose of the present invention, the technical scheme of taking comprises the steps:
(1) preparation of casting solution: weight is divided into the catechol analog derivative of nano material, 0.1-30 part of polymeric film material, 0.1-30 part of 1-60 part and 10-100 part the solvent out-of-order join in dissolving tank, under the condition of 20-100 ℃, stirring and dissolving 1-48 hour, standing and defoaming 1-24 hour, make casting solution;
(2) modulation of coagulating bath: the pH value of regulating coagulating bath by adding cushioning liquid is 7.5-10; Perhaps in coagulating bath, add oxidant;
(3) film forming: casting solution curtain coating on flat board is become to liquid film, then soak 1 minute-48 hours in coagulating bath, make dull and stereotyped hydridization diffusion barrier; Perhaps casting solution is passed through to the spinning of hollow-fibre membrane spinning-drawing machine, then soak 1 minute-48 hours in coagulating bath, make doughnut hydridization diffusion barrier;
(4) solidify: the hydridization diffusion barrier that step (3) is made soaks 30 minutes-48 hours in protection liquid, then is dried.
The diffusion barrier made in step (3) can also be modified to one deck aramid layer according to traditional surface aggregate method, then solidify and make 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 according to the method for step (4), and dull and stereotyped hydridization pressure retarded osmosis film or doughnut hydridization pressure retarded osmosis film.
Described nano material according to chemical composition can be divided into metal nano material, inorganic nonmetallic nanometer material, organic and high molecule nano material and nano composite material, described metal material includes but not limited to nano particle, nanometer rods, nano wire or the Nano sol of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi and alloy thereof, described Inorganic Non-metallic Materials comprises the CNT of CNT and various finishinges, organic clay if you would take off soil and tired de-soil etc., Graphene and Graphene derivative are (as the free oxidation Graphene, the sulfuration Graphene, the hydroxide Graphene, the carbonating Graphene, the group that nitrogenize Graphene and sulfonated Graphene form), the zeolite of zeolite and modification, Nano diamond, cadmiumsulfide quantum dot, cadmium telluride quantum dot and nano ceramic material, and contain the metallic compound that one or more are selected from the component in following group: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi.
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.
Described polymeric film material is all organic polymers that can film forming, comprise 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, nylon and copolymer thereof, 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, dimethyl sulfone, N, N-dimethyl formamide, N, N-dimethylacetylamide or N-methyl pyrrolidone.
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 mix in casting solution and add the dopamine or derivatives thereof in preparation, 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 nano 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.
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 nano composite polymer film of present embodiment carries out according to the following steps:
(1) weight is divided into to the polyether sulfone of 5 parts, the nano titanium oxide of 0.1 part, the N of the dopamine of 0.5 part and 20 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 8.0 of water and isopropyl alcohol coagulating bath by adding phosphate buffer;
(3) casting solution curtain coating on flat board is become to liquid film, then soak 30 minutes in coagulating bath, obtain nano material doped 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 nano composite polymer film of present embodiment carries out according to the following steps:
(1) weight fraction is respectively to the polythene material of 20 parts, 30 parts, 40 parts, 50 parts and 60 parts, the CNT of 3 parts, 10 parts 3, the ethanol 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 containing 3%N, add 5 parts of hydrogen peroxide 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 nano composite polymer film of present embodiment carries out according to the following steps:
(1) weight is divided into to the shitosan of 10 parts, the different nano materials of 30 minutes (imvite, tired de-soil, Nano silver grain, titanium nanometer rods), 1 part 3, the pure water of 4-dihydroxyphenyl acetic acid and 60 parts adds in dissolving tank, under the condition of 30 ℃, 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 nano composite polymer film of present embodiment carries out according to the following steps:
(1) take by mass percentage the polyvinyl butyral resin of 15 parts, the cadmiumsulfide quantum dot 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 95 ℃, 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 nano material doped polymer flat sheet membrane;
(4) diffusion barrier step (3) made soaks 48 hours in 5% the Tween-40 aqueous solution, then is dried, for the assembling film assembly.
Claims (9)
1. a high-performance hydridization diffusion barrier, the poly-adjacent benzene diquines compound that it is characterized in that in this diffusion barrier matrix material inside, separation membrane surface, fenestra surface generates after all comprising the catechol compound oxidation and being crosslinked solidifies and homodisperse nano material.
2. the preparation method of a high-performance hydridization diffusion barrier comprises following steps:
(1) preparation of casting solution: weight is divided into the catechol analog derivative of nano material, 0.1-30 part of polymeric film material, 0.1-30 part of 1-60 part and 10-100 part the solvent out-of-order join in dissolving tank, under the condition of 20-100 ℃, stirring and dissolving 1-48 hour, standing and defoaming 2-24 hour, make casting solution;
(2) modulation of coagulating bath: the PH that regulates coagulating bath by adding cushioning liquid is 7.5-10; Perhaps in coagulating bath, add oxidant;
(3) film forming: casting solution curtain coating on flat board is become to liquid film, then soak 1 minute-48 hours in coagulating bath, make dull and stereotyped hydridization diffusion barrier; Perhaps casting solution is passed through to the spinning of hollow-fibre membrane spinning-drawing machine, then soak 1 minute-48 hours in coagulating bath, make doughnut hydridization diffusion barrier;
(4) solidify: the hydridization diffusion barrier that step (3) is made soaks 30 minutes-48 hours in protection liquid, then is dried.
3. the preparation method of a kind of high-performance hydridization diffusion barrier according to claim 2, it is characterized in that the diffusion barrier that will make in step (3), according to traditional surface aggregate method modification one deck aramid layer, then solidifies and makes dull and stereotyped hydridization NF membrane, doughnut hydridization NF membrane, dull and stereotyped hydridization reverse osmosis membrane or doughnut hydridization reverse osmosis membrane according to the method for step (4).
4. the preparation method of a kind of high-performance hydridization diffusion barrier according to claim 1 or the described a kind of high-performance hydridization diffusion barrier of claim 2, is characterized in that described nano material according to chemical composition can be divided into metal nano material, inorganic nonmetallic nanometer material, organic and high molecule nano material and nano composite material, described metal material includes but not limited to nano particle, nanometer rods, nano wire or the Nano sol of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi and alloy thereof, described Inorganic Non-metallic Materials comprises the CNT of CNT and various finishinges, organic clay if you would take off soil and tired de-soil etc., Graphene and Graphene derivative are (as the free oxidation Graphene, the sulfuration Graphene, the hydroxide Graphene, the carbonating Graphene, the group that nitrogenize Graphene and sulfonated Graphene form), the zeolite of zeolite and modification, Nano diamond, cadmiumsulfide quantum dot, cadmium telluride quantum dot and nano ceramic material, and contain the metallic compound that one or more are selected from the component in following group: Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi.
5. the preparation method of a kind of high-performance hydridization diffusion barrier according to claim 1 or the described a kind of high-performance hydridization diffusion barrier of claim 2, it is characterized in that described catechol analog derivative is the organic molecule that a class contains dihydroxy phenyl and derivative thereof, 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.
6. the preparation method of a kind of high-performance hydridization diffusion barrier according to claim 2, it is characterized in that the polymeric film material described in step (1) is all organic polymers that can film forming, comprises hydrophobic organic polymer: silicon rubber, Kynoar, polytetrafluoroethylene (PTFE), polysulfones, polyether sulfone, poly-sulphur sulfone, polyethylene, nylon, 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, polyvinyl phosphate, polyvinyl sulfate, polybenzimidazoles, polyhydrazide, polyoxadiazole, polytriazoles, polybenzimidazoles, polycarbodiimide, poly-phosphine piperazine and their combination.
7. the preparation method of a kind of high-performance hydridization diffusion barrier according to claim 2, is characterized in that the solvent described in step (1) is water, alcohol, N, N-dimethyl formamide, N, N-dimethylacetylamide or N-methyl pyrrolidone.
8. the preparation method of a kind of high-performance hydridization diffusion barrier according to claim 2, it is characterized in that the coagulating bath described in step (2) 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.
9. the preparation method of a kind of high-performance hydridization diffusion barrier according to claim 2, is characterized in that in the Tween-80 aqueous solution of the Tween-60 aqueous solution, 1-15% of the Tween-40 aqueous solution, the 1-15% of the Tween-20 aqueous solution, the 1-15% of glycerine water solution that the protection liquid described in step (4) is 20-70%, 1-15% the combination of one or more.
Priority Applications (1)
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