CN1468649A

CN1468649A - Method for producing selective diffusion barrier with excellent pollution resistibility

Info

Publication number: CN1468649A
Application number: CNA021261067A
Authority: CN
Inventors: 具滋永; 金淳植; 洪成杓; 尹圣老
Original assignee: SEAHAN INDUSTRY Co Ltd
Current assignee: SEAHAN INDUSTRY Co Ltd
Priority date: 2002-07-16
Filing date: 2002-07-16
Publication date: 2004-01-21
Anticipated expiration: 2022-07-16
Also published as: CN100427189C

Abstract

The present invention provides the manufacture process of selective separating film with excellent anti-fouling performance. On porous support, polyamide film is formed, and on the polyamide film hydrophilic coating is formed. When the composite reverse osmosis polyamide film is manufactured, epoxy compound containing at least two epoxy radicals is coated onto the polyamide film and crosslinked to form the hydrophilic coating of water insoluble polymer.

Description

The manufacture method of the selective diffusion barrier that stain resistance is good

Technical field

The present invention relates to have the selective diffusion barrier and the manufacture method thereof of good anti-pollution characteristic.

Prior art

The material that is dissociated can separate from solvent with various selective membranes.As such film, can enumerate the secondary filter film, super diffusion barrier, nanometer diffusion barrier and reverse osmosis membrane.In the half brine desalination operation and desalinization operation that adopt reverse osmosis separating membrane, lower-molecular substance and salt do not see through the reverse side of diffusion barrier, and have only refined water to see through, yet, at this moment, for the water that obtains seeing through, must apply the above pressure of former water osmotic pressure.

In the salt solution and desalinization operation that adopt reverse osmosis membrane, when making salt solution contact reverse osmosis membrane, salinity and the ion that dissociates and particle do not see through film, have only pure water to pass through, thereby can remove salt ion and particle.At this moment, when influent density increases, because osmotic pressure increases,, require at least 97% salt rejection rate in order to be suitable for salt solution and desalinization, so, must improve the salt rejection rate coefficient of reverse osmosis membrane, and, even at lower pressure, must have handling capacity, promptly must possess the high flow capacity characteristic by the more relatively water of film.The circulation of the film of desalinization conditional request generally speaking, is at 800Psi (pound/inch ²) time reaches 10 and add human relations/foot ². day (gfa) requires pressure at 225Psi to be issued to 15 in half brine desalination operation and adds human relations/foot ². day (gfa) according to the difference of purposes, also has two kinds of important events of the lower flow of salt rejection rate higher flows and salt rejection rate in contrast.

The general type of reverse osmosis membrane is to be made of the polyamide-based film on porous supporting course and the supporting course.Typical polyamides film is that multi-functional amine and multi-functional halo acyl group obtain by interfacial polymerization.

In the past; United States Patent (USP) 4 in the Cadotte application; disclose in 277,344 that the aromatic halo acyl compounds that will contain 2 multi-functional amine of the substituent aromatic series of primary amine and have a halo acyl group functional group more than 3 carries out interfacial polymerization and the technology that obtains aromatic polyamide thin-film.Here, the method for making of reverse osmosis membrane is, on trickle porous polysulfones supporting mass, after the m-phenylene diamine (MPD) coating, remove residual m-phenylene diamine (MPD) solution, make with trimesic acid chlorine (TMC) (the トリメゾイ Le Network ロライ De) reaction that is dissolved in the freon (trichorotrifluoroethane).At this moment, be 10 seconds the time of contact of interfacial polymerization, is reflected in 1 second and carries out.Even the Cadotte film shows that good flow and salt rejection rate are true, yet, for more perfect film is provided, various researchs have been carried out in the flow increase of polyamide reverse osmosis composite film and the raising of salt rejection rate.On the other hand, the chemical-resistant that has also carried out film improves research, but nearly all research, and its main flow is the method for the various additives of use in the solutions employed during toward interfacial polymerization.

As an example, disclosed reverse osmosis membrane manufacture method comprises in the United States Patent (USP) 4872894 (in October, 1989 registration) of Tomashke, (a) in order on trickle porous supporting course, to form liquid level, the aromatic series polyamine reactants of the basic monomer that contains at least 2 above amine functional groups and the aqueous solution that contains the monomer amine salt, be coated on the step on the trickle porous supporting mass; (b) amine reactive reactant, by on average having 2.2 halo acyl groups in each reaction molecular at least, multi-functional halo acyl compounds or its mixture constitute, in the organic solvent solution of the aromatic amine reactive reactant of basic monomer, and the step of contact aforesaid liquid layer; (c) in order to form above-mentioned water penetration permeable membrane, go on foot poly-product to above-mentioned 2 in 60～110 ℃ 1～10 minute step of temperature drying.

In solutions employed, add additive during as interfacial polymerization and make the patent of film, can enumerate the United States Patent (USP) 6063278 and 6015495 etc. of United States Patent (USP) 4830885, the Koo of United States Patent (USP) 5576057 and 5614099, the Tran of United States Patent (USP) 4983291, the Hirose of Chau.

Other example as the United States Patent (USP) 5178766 according to Ikeda, in order to improve the separating property of reverse osmosis separating membrane, on the surface of the polyamide by interfacial polymerization system film, makes its covalent bond quaternary ammonium.Used quaternary ammonium has epoxy radicals, '-aziridino, episulfide, haloalkyl, amino, carboxyl, halo carbonyl, hydroxyl etc. as reactive group in the site with surface reaction.

, even above-mentioned polyamide laminated film has good separating property and through performance, but can not avoid current membrane pollution problem.Example as the film pollution, can enumerate owing to suspended material or dissolved substance in the absorption of film surface or adhere to the decline that causes through flow, still, generally speaking, because hydrophobicity combination and electrostatic attraction combine suspension, dissolved substance and film surface in the filtered solution.Owing to polluting the through performance that makes diffusion barrier, reduces this film, so, in order to obtain the permeate water of certain flow, must adjust pressure continually, in serious pollution occasion, need wash continually, this all is a problem.

As reducing the test that film pollutes, electroneutral hydrophilic macromolecules such as pva coating are proposed in the United States Patent (USP) 6177011 of Hachisuka on the laminated film surface of polyamide once more, improve stain resistance, list with as list of references of the present invention.

The problem that the invention quasi-solution is determined

The objective of the invention is to make diffusion barrier to have the anti-pollution characteristic, particularly selective diffusion barriers such as polyamide reverse osmosis composite film are carried out the hydrophily coating, make the good diffusion barrier of stain resistance.

Be used to solve the way of problem

In order to achieve the above object, the present invention is after forming polyamide film on the porous supporting mass, on above-mentioned polyamide film, form hydrophilic coating, when making polyamide reverse osmosis composite film, above-mentioned hydrophily coating is after being coated on the epoxide with at least 2 above epoxy radicals on the polyamide film, form water-insoluble macromolecule and constitute by crosslinked, this is the characteristics that the polyamide reverse osmosis composite film that the present invention relates to is made.

In addition, the manufacture method of the porous diffusion barrier that the present invention relates to, it is characterized in that, on porous separation membrane surfaces such as milipore filter or secondary filter film, when carrying out the manufacturing porous diffusion barrier of hydrophily coating, above-mentioned hydrophily rubbing method is to make back, surface that the compound with at least 2 above epoxy radicals is coated on diffusion barrier form water-insoluble high molecular method by crosslinked.

The coating of above-mentioned hydrophily, applicable without limits and all to the material behavior and the purposes of the polyamide-based laminated film by interfacial polymerization on the porous supporting mass, simultaneously, the material and the kind of porous supporting mass are also done to limit and all can use.So-called trickle porous supporting mass has the microporosity structure, particularly must have the fully aperture of permeate water, plays the effect as supporting mass when film forms, so, must have the aperture of 1～500nm.The aperture that surpasses 500nm when film forms, produces defective owing to depression makes final composite membrane.Material as the spendable microporosity supporting mass of the present invention can use the high molecular materials of various halogenations such as polysulfones, polyether sulfone, polyimides, polyamide, PEI, polyacrylonitrile, polymethyl methacrylate, polyethylene, polypropylene and Kynoar.

In addition, the thickness of porous supporting mass does not limit in the present invention, is preferred (more preferably 40～75 μ m) in the scope of about 25～125 μ m.

The polyamide-based laminated film that the present invention is used, the material that generally uses polyamine and react with polyamine is by interfacial polymerization system film.At this moment, so-called polyamine means that each monomer has the material of 2～3 amine functional groups, for example primary amine or secondary amine class.As the example of polyamine, can use m-phenylene diamine (MPD), p-phenylenediamine (PPD) and as the aromatic series primary diamines of substituent.As other example, can use annular aliphatic secondary amine, aromatic amines etc. such as cyclic aliphatic primary diamines, piperazine such as aliphatic primary amine, cyclohexanediamine.Other suitable materials can be found from list of references of the present invention.

The present invention limits the kind of polyamine, yet, particularly preferably be the m-phenylene diamine (MPD) of aromatic series primary diamines or the made film of piperazine of cyclic aliphatic secondary diamine is suitable for use as diffusion barrier as polyamine.When using piperazine, can form the aperture polyamide composite film that be in nanofiltration scope big than reverse osmosis separating membrane as polyamine.Nano-filtration membrane, compare with reverse osmosis separating membrane, the salt rejection rate of its 1 valency ion is low, yet, organic substance removal more than 300 is effective for divalent ion and molecular weight, being applicable in the demineralized water operation and drinking water operation of hardness components such as removing calcium and magnesium, is effective for the humin of the parent of removing carcinogen such as haloform.

The polyamine aqueous solution mainly uses with the concentration of 0.1～20 weight %, yet, the preferred polyamine aqueous solution that is to use 0.5～8 weight %.The pH of the polyamine aqueous solution is 7～13, can regulate by the acid, the alkali that add 0.001～5 weight %.As the example of this acid, alkali, can enumerate phosphate, three alginate amine of hydroxide, carboxylate, carbonate, borate, metal alkyl etc.In addition, in the polyamine aqueous solution, can add in the energy and the alkaline acid acceptor of the acid (HCl) that produces during interfacial polymerization, perhaps, also can add polar solvent, amine salt, poly-tertiary amine etc. as other additive.

As with the material of polyamine reaction, can use polyacyl halide, poly-sulfonic acid halide, PIC etc., preferredly be to use trimesic acid chlorine (Trimesoyl chloride) (TMC) and isophthaloyl chloride aromatic series polyamides halogen such as (IPC).With the material of amine reaction, generally with in the organic solvent that water mixes do not dissolving the use of 0.005～5 weight % (more preferably 0.01～0.5 weight %) back.As representative examples of organic, can use the alkane of 8～12 of halogenated hydrocarbons, hexane, cyclohexane, heptane, the carbon numbers of freon class, consider that freon destroys environmental problem such as ozone and owing to the low fire etc. that causes of its boiling point, the ISO PAR (Exxon Covp.) of the alkane mixture of use carbon number 8～12 is preferred.

The general manufacturing process of the reverse osmosis membrane that is suitable among the present invention is, at first, by with after removing superfluous polyamine solution with roll extrusion, sponge absorption, air knife and suitable method on the surface of the porous supporting mass of polyamine (polyfunctional group amine) aqueous solution coating, by contain can and the organic solvent of the material that reacts of polyamine in to flood or method such as sprayer contacts 5 seconds～10 minutes (more preferably 20 seconds～4 minutes).The diffusion barrier that adopts such method to obtain,, in the alkaline aqueous solutions such as sodium carbonate of 0.2 weight %, after flooding 1～30 minute under the suitable water temperature of normal temperature～95 ℃,, obtain reverse osmosis membrane with the distilled water washing in below 50 ℃ approximately after dry 1 minute.After the reverse osmosis membrane made from said method fully washed,, carry out the hydrophily coating with suitable epoxide on resulting polyamide film surface.At this moment, employed epoxide is the epoxy radicals that has at least more than 2, is formed on and forms cancellated non-soluble polymer in the coating process.Here, the network structure of formation is a very important part in the hydrophily coating, and as not forming network structure, then the actual separation film in use can be washed hydrophilic coating off from the surface of diffusion barrier.

The epoxide that uses among the present invention, at least has the epoxy reaction base more than 2, the generally polymerization that forms from 2 reactive groups has linear structure, is water miscible, yet, even each monomer only has 2 reactive groups, when using primary diamines, secondary diamine, form network structure by crosslinking agent as crosslinking agent, thereby generate water-insoluble macromolecule, can elution in the service condition of general diffusion barrier.In addition, in the occasion with 3 above epoxy reaction bases, needn't carry out crosslinkedly with above-mentioned crosslinking agent, the polymerization by epoxide itself also can form network structure, forms water-insoluble macromolecule.

In general open loop of epoxy compound polymerization, by reaction, when the epoxide ring open loop, oxygen atom is converted into ether or alcohol.The catalyst that uses in the ring-opening polymerisation can roughly be divided into base catalyst, acidic catalyst and heat.As the base catalyst that ring-opening polymerisation is used, can enumerate the carboxylate such as borates such as phenates, Boratex, sodium acetates such as phosphate such as carbonate such as hydroxide, potash, tertiary sodium phosphate, phenol sodium such as alkoxide, NaOH, potassium hydroxide of caustic alcohol etc. or primary amine, secondary amine, tertiary amine etc.The acidic catalyst that is used for ring-opening polymerisation can be enumerated inorganic acid, organic acid and lewis acid etc.The concrete hydrochlorate that can use four halogen tartaric acid such as boron trihalides such as fluorocarboxylic acid, phenol or phenol derivatives such as sulfuric acid, hydrochloric acid, nitric acid, aromatic sulphonic acid, aliphatic sulfonic, ring sulfonic acid, carboxylic acid, trifluoracetic acid, boric acid, tetrafluoro boric acid, aluminum trihalide, three aluminium alkoxides, boron trifluoride, tetrafluoro boric acid zinc, tetrachloro tartaric acid, quaternary ammonium salt, ammonia or primary amine, secondary amine, tertiary amine etc.In addition, can carry out ring-opening reaction with heat, yet at this moment, the temperature that may be suitable for is 10～200 ℃ (more preferably 20～150 ℃), the scope of reaction time 1 second～7 days (more preferably 5 seconds～3 days) is preferred.

Spendable epoxide among the present invention, each monomer accurately has can enumerating of 2 epoxide rings, ethylene glycol diglycidylether, 1, the ammediol diglycidyl ether, 1, the 3-butanediol diglycidyl ether, 1, the 4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,2-pentanediol diglycidyl ether, 2,4-pentanediol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, 1, the 2-hexanediol diglycidyl ether, 1, the 5-hexanediol diglycidyl ether, 2, the 5-hexanediol diglycidyl ether, 2-ethyl-1, the 3-hexanediol diglycidyl ether, 1,7-heptandiol diglycidyl ether, 1,2-ethohexadiol diglycidyl ether, 1,8-ethohexadiol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,2-decanediol diglycidyl ether, 1,12-12 carbon glycol diglycidyl ethers, 1,2-12 carbon glycol diglycidyl ethers, the glycerine diglycidyl ether, the trimethylolpropane diglycidyl ether, 1,1,1-three (methylol) ethane diglycidyl ether, the pentaerythrite diglycidyl ether, the sorbierite diglycidyl ether, neopentylglycol diglycidyl ether, the dibromoneopentyl glycol diglycidyl ether, the quinhydrones diglycidyl ether, resorcinolformaldehyde resin, bisphenol A diglycidyl ether, the hydrogenated bisphenol A diglycidyl ether, polyethyleneglycol diglycidylether ((CH ₂CH ₂O) _n, n=2～400), polypropylene glycol diglycidyl ether ((CH ₃) CH ₂CH ₂O) _n, n=2～100) etc.

The epoxide that uses among the present invention, each monomer accurately has 3 epoxide rings, can enumerate the glycerine triglycidyl ether, two glycerine triglycidyl ether, the pentaerythrite triglycidyl ether, the sorbierite triglycidyl ether, glycerine propoxylate triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 1,1,1-three (methylol) ethane triglycidyl ether, 1,1,1-three (hydroxyphenyl) ethane triglycidyl ether, the trishydroxymethylnitromethane triglycidyl ether, three (2, the 3-glycidyl) isocyanuric acid ester, fluoro sugar alcohol (グ Le シノ one Le) triglycidyl ether, N, N-diglycidyl-4-glycidyl oxo aniline, chloropropylene oxide and 1,3, the reactant of 5-three (2-ethoxy) cyanogen urea acid, the reactant of chloropropylene oxide and three (methylol) aminomethane.

The epoxide that may use among the present invention, each monomer has having of 4 epoxide rings accurately: sorbierite four glycidol ethers, pentaerythrite four glycidol ethers, polyglycereol four glycidol ethers, 4,4-di-2-ethylhexylphosphine oxide (N, N-diglycidylaniline) etc.

The epoxide that may use among the present invention, each monomer accurately has having of 4 above epoxide rings, the reactant of cellulosic substituent such as the reactant of reactant, cellulose and the chloropropylene oxide of reactant, polyacrylamide and the chloropropylene oxide of reactant, polyethylene phenol and the chloropropylene oxide of sorbierite five glycidol ethers, sorbierite six glycidol ethers, polyglycerol polyglycidyl ether, epoxy cresol novolac resin, polyvinyl alcohol and epichlorhydrin and hydroxyethylcellulose and hydroxypropyl cellulose and chloropropylene oxide.

Above-mentioned epoxide can make the reaction of chloropropylene oxide and polyhydroxy, amino or amide compound and makes in the presence of NaOH.As polyhydroxy, the example of amino or amide compound, can enumerate ethylene glycol, propane diols, 1, ammediol, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 2-pentanediol, 2,4 pentanediols, 1, the 6-hexylene glycol, 1, the 2-hexylene glycol, 1, the 5-hexylene glycol, 2, the 5-hexylene glycol, 2-ethyl-1, the 3-hexylene glycol, 1, the 7-heptandiol, 1, the 2-ethohexadiol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1, the 10-decanediol, 1, the 2-decanediol, 1,12-12 carbon glycol, 1,2-12 carbon glycol, glycerine, trimethylolpropane, 1,1,1-three (methylol) ethane, three (methylol) aminomethane, 1,3, the acid of 4-three (2-methylol) cyanogen urea, pentaerythrite, sorbierite, neopentyl glycol, dibromoneopentyl glycol, quinhydrones, resorcinol, bisphenol-A, hydrogenated bisphenol A, isocyanuric acid, fluoro sugar alcohol (グ Le シノ one Le), methylene dianiline, phenolic resins, polyvinyl alcohol, polyvinyl phenol, polyacrylamide, cellulose and cellulose replace body, chitosan, polyethylene glycol ((CH ₂CH ₂O) _n, n=2～400), polypropylene glycol ((CH ₃) CH ₂CH ₂O) _n, n=2～100 etc.

Among the present invention, when using epoxide as diffusion barrier, at first, after making reactions such as chloropropylene oxide and above-mentioned polyhydroxy, amino or amide compound, employing is different from the method that the epoxide that makes the reaction product that obtains is suitable for diffusion barrier, on the film surface, directly make 2 kinds of compound reactions, can form epoxide on the spot with suitable catalyst.

In the present invention, in order in polymerization process, to generate network structure, crosslinking agent, in occasion with 2 epoxide rings, must have can with the site of 3 above epoxy reactions, and with the compound reaction with 3 above epoxide rings, must have can with the reactive group of 2 above epoxy reactions.As mentioned above, the compound with 2 epoxide rings also can use the crosslinking agent with 2 above primary amine, secondary amine, forms network structure.Being suitable for crosslinking agent of the present invention, is the compound with reactive groups such as hydroxyl, primary amino radical, secondary amino group, uncle's amino, carboxyl, acid anhydride, amide groups, aldehyde radical, urea groups, thiol bases.Crosslinking agent reaction site with 2 above reactive groups is similar or inhomogeneous reaction site.

As the above-mentioned crosslinking agent that the present invention may use, can enumerate ethylene glycol with 2 hydroxyls, propane diols, 1, ammediol, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 2-pentanediol, 2, the 4-pentanediol, 1, the 6-hexylene glycol, 1, the 2-hexylene glycol, 1, the 5-hexylene glycol, 2, the 5-hexylene glycol, 2-ethyl-1, the 3-hexylene glycol, 1, the 7-heptandiol, 1, the 2-ethohexadiol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1, the 10-decanediol, 1, the 2-decanediol, 1,12-12 carbon glycol, 1,2-12 carbon glycol, neopentyl glycol, dibromoneopentyl glycol, quinhydrones, resorcinol, bisphenol-A, hydrogenated bisphenol A, polyethylene glycol ((CH ₂CH ₂O) _n, n=2～400), polypropylene glycol ((CH ₃) CH ₂CH ₂O) _n, n=2～100 etc.

Example as the crosslinking agent with 3 above hydroxyls that may use among the present invention, can enumerate glycerine, trimethylolpropane, 1,1,1-three (methylol) ethane, 1,1,1-three (hydroxyphenyl) ethane, three (methylol) aminomethane, three (methylol) nitromethane, 1,3, the acid of 5-three (2-ethoxy) cyanogen urea, pentaerythrite, sorbierite, glucose, fructose, maltose, mannose, aminoglucose, mannosamine, polysaccharide, different three cyanogen urea acid, the fluoro sugar alcohol, methylene dianiline, phenolic resins, polyethylene glycol, polyvinyl phenol, polyacrylamide, chitosan, cellulose and hydroxyethylcellulose, hydroxypropyl cellulose, ethyl cellulose, methylcellulose etc. replace body.

In addition, the crosslinking agent that may use among the present invention, as contain can with the examples of substances of 2 amino of epoxy reaction (primary, secondary, uncle or their combination), can enumerate H ₂N (CH ₂) _nNH ₂(n=2～12), H ₂N (CH ₂CH ₂O) _nCH ₂CH ₂NH ₂(n=1～400), R ₁R ₂N (CH ₂) _nNR ₃R ₄(n=2～12; R ₁, R ₂, R ₃, R ₄The combination of=hydrogen, methyl, ethyl, propyl group, butyl, cyclohexyl, phenyl etc.), as concrete example N is arranged, N, N ', N '-tetramethyl-1,4-butanediamine, N, N, N ', N '-tetramethyl-1,6-hexamethylene diamine, N, N, N ', N '-tetramethyl-1,3-propane diamine, N, N, N ', N '-tetramethylethylenediamine etc.

H ₂N-((R ₅) CH ₂) _nNH ₂, R ₁R ₂N ((R ₅) CH ₂) _nNR ₃R ₄(n=2～12; R ₁, R ₂, R ₃, R ₄, R ₅The combination of=hydrogen, methyl, ethyl, propyl group, butyl, cyclohexyl, hydroxyl, phenyl etc.), N is arranged, N, N ', N '-tetramethyl-1,3-butanediamine, N, N, N ', N '-tetramethyl-1,3-diaminourea-2-propyl alcohol etc. as concrete example.

In addition, DACH, 1,3-cyclohexane two (methylamine), 4,4-trimethylene two piperazines, piperazine, 1, the 4-lupetazin, 1,4-diazabicyclo (2.2.2) octane, 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene, 1,5-diazabicyclo (4.3.0) ninth of the ten Heavenly Stems-alicyclic diamine and m-phenylene diamine (MPD)s such as 5-alkene, m-xylene diamine, two (4-aminophenyl) sulfone etc. also can be made crosslinking agent and use, in addition, remove N, N, N ', N '-tetramethyl-2-fourth-1,4-diamines main chain has beyond the compound of two keys, has and N N, N ', N '-tetramethyl-1, the compound of 4-butanediamine same structure also can be used as crosslinking agent in the present invention.

The crosslinking agent that may use among the present invention, as have more than 3 can with the examples of materials of the amino of epoxy reaction (primary, secondary, uncle or their combination), can enumerate N, N '-two (2-aminoethyl)-1,3-propane diamine, diethyl triamine, triethyl group tetramine, three (2-aminoethyl) amine, N, N ', N ', N " pentamethyl diethyl triamine, triaminobenzene, 1; 1,3,3-TMG, polymine, chitosan, poly-(allylamine), polyvinyl pyridine.

Use occasion among the present invention with amino crosslinking agent, according to the consumption or the extent of reaction, the separation membrane surface electric charge can improve in positive electricity (+) side, when handling the cationic material of former water band, by the electrostatic repulsion forces effect, not only improve removal efficiency but also have anti-fouling performance.Otherwise, employing has tartaric acid, the gluconic acid, 3 of band negative charge (-) effect groups such as hydroxyl and acidic group, 5-dihydroxy benzoic acid, 2,5-dihydroxy benzenes sulfonic acid, sylvite, 2,5-dihydroxy-1,4-benzenedisulfonic acid etc. are during as crosslinking agent, because surperficial negative charge is low, to removing the anionic material of being with of handling former water is effectively, and, have stain resistance.In addition,, when having the material of neutral groups such as hydroxyl, amide groups, carbonyl when use, neutral surface charge can be obtained, when separating belt cation or anionic material, effect widely can be got as crosslinking agent.At last; when employing has zwitterionic compound; can realize having cation; the separation membrane surface of two kinds of ions of anion; example as this compounds; can enumerate; 3; 5-diaminourea benzoic acid; 2-tarine (taurine); 2-[three (methylol) methyl] amino-1-ethyl sulfonic acid; 3-[three (methylol) methyl] amino-1-propane sulfonic acid; 2-hydroxyl-3-[three (methylol) methyl] amino-1-propane sulfonic acid; beta-hydroxy-4-(2-ethoxy)-1-piperazine propane sulfonic acid; β; β '-dihydroxy-1; 4-piperazine two (propane sulfonic acid); 2,5-diamino benzene sulfonic acid etc.

Epoxide coating diffusion barrier the time, can adopt the solution state of water, alcohols or their appropriate solvent that mixture constituted.At this moment, the content of epoxide is that 0.00001～20 weight % (more preferably 0.0001～5 weight %) is preferred.

On the other hand, add suitable crosslinking agent as required, adopt the sprayer method, T-die methods, meniscus (メニスカス) method, the rubbing method that intersects are in 1 second～10 minutes (more preferably 5 seconds～5 minutes) of contact, polyamide laminated film surface.Crosslinked for heating applied diffusion barrier to promote, in 10～200 ℃ (more preferably 20～150 ℃) dry 1 second～7 days (more preferably 5 seconds～3 days).

As mentioned above, the hydrophilic coating that the present invention relates to, not only can be used as the polyamide reverse osmosis diffusion barrier, and can directly be used as porous diffusion barriers such as secondary filter film, super filter membrane, in various operations such as surface water processing, Separation of Proteins, food and drink be refining, be effective for reducing the pollution that protein, big molecule and colloid cause.Above-mentioned secondary filter film has the aperture of 0.1～10 μ m, and above-mentioned super filter membrane has the aperture of 0.001～0.05 μ m, and is generally well known as diffusion barrier.

Embodiment

By the following example and the present invention of comparative example more specific description, but scope of the present invention is not limited to by it.

Embodiment 1

The porous polysulfones supporting mass of the thickness 140 μ m of casting on the nonwoven, in the meta-aminotoluene of 2 weight % and the 2-ethyl-1 of 0.3 weight %, dipping is 40 seconds in the 3-hexylene glycol solution, remove supporting mass surplus between behind the aniline solution, dipping is after 1 minute in as the organic solution of 0.1 weight % trimesic acid chlorine of the Isopar solvent of solvent.Remove superfluous organic solvent, then,, in 0.2% aqueous sodium carbonate of normal temperature, after the dipping washing in 30 minutes, fully wash with pure water more again, make the polyamide reverse osmosis diffusion barrier in air drying 1 minute.

On the polyamide reverse osmosis separation membrane surface made from said method, with containing sorbierite four glycidol ethers 0.1 weight %, N, N, N ', N '-tetramethyl-1, the aqueous solution of 6-hexamethylene diamine (TMHD) 0.04 weight % and glycerine (wetting agent) 3 weight %, spray after 20 seconds, remove superfluous solution, then, in 50 ℃ carry out 4 minutes dryings after, keeping is 1 day in the air of normal temperature.

The diffusion barrier made from said method is carried out performance evaluation, adopt the sodium-chloride water solution of 200ppm, under 25 ℃, the pressure condition of 225psi, adopt the type of flow of reporting to the leadship after accomplishing a task, measure and see through flow and salt rejection rate, confirm the initial stage basic physical properties.The result obtains 99% salt rejection rate and the through performance of 22gfd.Then, under identical conditions, add 30ppm milk powder (contained protein in the milk powder, under aqueous solution state, exist with the colloid form of twining between protein molecule form or protein molecule, can infer them and be easy to be adsorbed on the film surface), make circulation after 4 hours, measuring separating property and diactinic result is, can obtain 99.4% and the value of 17.6gfd.

Comparative example 1

Except not forming hydrophilic coating, carry out equally with embodiment, make the polyamide reverse osmosis diffusion barrier.

The diffusion barrier performance evaluation that the foregoing description 1 and comparative example 1 are made the results are shown in table 1.

Table 1

Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)
Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)	Comparative example 1	????99	????29	????15.7	????46
Embodiment 1	????99	????22.3	????17.4	????22	Comparative example 1	????99	????29	????15.7	????46

In above-mentioned table 1, can see that embodiment's 1 is little than comparative example 1 through the flow slip.This just means can obtain the stable flow that sees through, owing to the trouble of change service conditions such as the washing that can save the cycle or pressure adjusting, so can think that this is economic operation architecture.In addition, when washing contaminated film after the stain resistance evaluation, the initial stage rerum natura of embodiment 1 can be recovered fully, and the initial stage rerum natura of comparative example 1 only recovers 80%, this shows, what polluter was stronger in the comparative example 1 adheres to.

Embodiment 2

Except with 2 of 0.05 weight %, beyond the 5-dihydroxy benzenes sulfonic acid sylvite replacement TMHD, adopt method similarly to Example 1 to make polyamide reverse osmose membrane.

Comparative example 2

Except not forming hydrophilic coating, adopt method similarly to Example 2 to make polyamide reverse osmose membrane.

The diffusion barrier performance that the foregoing description 2 and comparative example 2 obtain is estimated, be the results are shown in table 2.

Table 2

Diffusion barrier

The initial stage desalination

Initial stage sees through

After stain resistance is estimated

See through flow

	Rate (%)	Flow (gfd)	See through flow (gfd)	Slip (%)
	Rate (%)	Flow (gfd)	See through flow (gfd)	Slip (%)	Comparative example 2	????99	????27.3	????22.5	????17.6
Embodiment 2	????99.4	????23.2	????20.9	????9.9	Comparative example 2	????99	????27.3	????22.5	????17.6

As shown in Table 2, the film of possess hydrophilic property coating, it is less that it sees through the flow slip.

Embodiment 3

Except with 2 of the glycerine triglycidyl ether of 0.2 weight %, 0.04 weight, 2-(ethylidene dioxy base) two (ethylamine) replaces adopting method similarly to Example 1 beyond sorbierite four glycidol ethers, the TMHD, makes polyamide reverse osmose membrane.

Comparative example 3

Except not forming hydrophilic coating, adopt method similarly to Example 3 to make polyamide reverse osmose membrane.

The diffusion barrier performance that the foregoing description 3 and comparative example 3 obtain is estimated, be the results are shown in table 3.

Table 3

Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)
Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)	Comparative example 3	????97	????51.7	????25.8	????46.8
Embodiment 3	????97.7	????39.2	????23.5	????32.6	Comparative example 3	????97	????51.7	????25.8	????46.8

As shown in Table 3, carried out the film of hydrophily coating, it is less that it sees through the flow slip.

Embodiment 4

Except the polymine of the ethylene glycol diglycidylether of adopting 0.25 weight %, 0.025 weight % replaces sorbierite four glycidol ethers, TMHD, adopt method similarly to Example 1, make polyamide reverse osmose membrane.

Comparative example 4

Except not forming hydrophilic coating, adopt method similarly to Example 4, make polyamide reverse osmose membrane.

The performance of the diffusion barrier that the foregoing description 4 and comparative example 4 are obtained is estimated, and the results are shown in table 4.

Table 4

Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)
Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)	Comparative example 4	????97	????51.7	????25.8	????46.8
Embodiment 4	????97	????31.7	????23.6	????22.6	Comparative example 4	????97	????51.7	????25.8	????46.8

As shown in Table 4, carry out the film of hydrophily coating, it is less that it sees through the flow slip.

Embodiment 5

Except polyethyleneglycol diglycidylether, 0.05 weight % trifluoracetic acid with 1.1 weight % replace sorbierite four glycidol ethers, TMHD, adopt method similarly to Example 1, make polyamide reverse osmose membrane.

Comparative example 5

Except not forming hydrophilic coating, adopt method similarly to Example 5, make polyamide reverse osmose membrane.

The performance of the diffusion barrier that the foregoing description 5 and comparative example 5 are obtained is estimated, and the results are shown in table 5.

Table 5

Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)
Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)	Comparative example 5	??97.2	????40.9	????29.8	????25.5
Embodiment 5	??98.3	????21.7	????21.5	????4.4	Comparative example 5	??97.2	????40.9	????29.8	????25.5

By table 5 as seen, carried out the film of hydrophily coating, it is less that it sees through the flow slip.

Embodiment 6

Adopt method similarly to Example 1, and with the content of the change of the glycerine of TMHD, the 2 weight % of sorbierite four glycidol ethers of 0.15 weight %, 0.06 weight %, after polyamide reverse osmose membrane carried out hydrophily coating, compare with the reverse osmosis membrane (comparative example 6) that does not carry out the hydrophily coating, its basic physical properties evaluation and stain resistance evaluation result are summarized in table 6.In addition, the milk powder that the DTAB (DTAB) of interpolation 50ppm replaces embodiment 1 carries out the stain resistance evaluation as polluter.(DTAB is a cationic surfactant, have by hydrophobicity in conjunction with and electrostatic attraction and strong adsorption in the character of separation membrane surface).

Table 6

Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)
Diffusion barrier	Initial stage salt rejection rate (%)	Initial stage sees through flow (gfd)	After estimating, stain resistance sees through flow (gfd)	See through flow slip (%)	Comparative example 6	????97	????55.2	????28.5	????48.3
Embodiment 6	????97.6	????33.6	????27.9	????17.1	Comparative example 6	????97	????55.2	????28.5	????48.3

As shown in Table 6, carried out the film of hydrophily coating, it is less that it sees through the flow slip.

Embodiment 7

To adopting method similarly to Example 1 to carry out the diffusion barrier of hydrophily coating and the diffusion barrier that did not carry out the hydrophily coating, each 10 drips, and the result of mensuration contact angle is that mean value is 48.8 ° and 54.6 °.This result proves, the more hydrophiling of the separation membrane surface that adopts the hydrophily coating.

The effect of invention

Confirm as the foregoing description and comparative example, polyamide reverse osmose membrane by hydrophily coating of the present invention, owing to have good especially anti-fouling performance, can solve because the shortcoming of existing diffusion barriers such as diactinic decline of diffusion barrier that the film pollution causes and frequent washing.

Claims

1. the manufacture method of a polyamide reverse osmosis composite film, it is characterized in that, after forming polyamide film on the porous supporting mass, on this polyamide film, carry out the hydrophily coating, and manufacturing hydrophilic polyamide reverse osmosis composite membrane, wherein, the coating of described hydrophily is to make behind the epoxide coating polyamide composite film that contains at least 2 above epoxy radicals and be cross-linked to form water-insoluble macromolecule.

2. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 1; it is characterized in that polyamide film is that the amine reaction compounds that will be selected from from polyamine, multi-functional halo acyl group, multi-functional halosulfonyl groups and multi-functional isocyanates makes by interfacial polymerization.

3. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 2, it is characterized in that polyamine is the amines that is selected from fragrant primary diamines or its substituent, alkane primary diamines, cyclic aliphatic primary diamines, cyclic aliphatic secondary diamine, aromatic series secondary diamine, the benzene dimethylamine a kind or 2 kinds or above mixing.

4. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 3 is characterized in that the aromatic series primary diamines is a m-phenylene diamine (MPD).

5. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 3 is characterized in that the cyclic aliphatic secondary diamine is a piperazine.

6. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 1, it is characterized in that, epoxide is selected from: the glycerine triglycidyl ether, two glycerine triglycidyl ether, the pentaerythrite triglycidyl ether, the sorbierite triglycidyl ether, glycerine propoxylate triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 1,1,1-three (methylol) ethane triglycidyl ether, 1,1,1-three (hydroxyphenyl) ethane triglycidyl ether, the trishydroxymethylnitromethane triglycidyl ether, three (2, the 3-ethoxycarbonyl propyl) isocyanuric acid ester, fluoro sugar alcohol triglycidyl ether, N, N-diglycidyl-4-glycidyl oxo aniline, epichlorhydrin and 1,3, the product of 5-three (2-ethoxy) cyanogen urea acid, the product of chloropropylene oxide and three (methylol) aminomethane, sorbierite four glycidol ethers, pentaerythrite four glycidol ethers, polyglycerol four glycidol ethers, 4,4 '-di-2-ethylhexylphosphine oxide (N, the N-diglycidylaniline), sorbierite five glycidol ethers, sorbierite six glycidol ethers, the polyglycerol polyglycidyl ether, the epoxy radicals cresol novolac resin, the product of polyvinyl alcohol and chloropropylene oxide, the product of polyethylene phenol and chloropropylene oxide, the product of polyacrylamide and chloropropylene oxide, cellulose and table chlorine chlorohydrin reaction product, and the product of cellulosic substituent such as hydroxyethylcellulose and hydroxypropyl cellulose and chloropropylene oxide.

7. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 1 is characterized in that, the crosslinked of epoxides undertaken by self-polymerization and/or crosslinking agent.

8. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 7, it is characterized in that, crosslinking agent has the functional group that can obtain with 2 above epoxy reactions, and functional group's form can be selected from single functional group or 2 or the above functional group in hydroxyl, amino, carboxyl, acid anhydride, amide groups, carbonyl, the sulfydryl (thiol base).

9. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 8, it is characterized in that, can be selected from ethylene glycol as crosslinking agent with hydroxyl, propane diols, 1, ammediol, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 2-pentanediol, 2, the 4-pentanediol, 1, the 6-hexylene glycol, 1, the 2-hexylene glycol, 1, the 5-hexylene glycol, 2, the 5--hexylene glycol, 2-ethyl-1, the 3-hexylene glycol, 1, the 7-heptandiol, 1, the 2-ethohexadiol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1.10-decanediol, 1, the 2-decanediol, 1,12-12 carbon glycol, 1,2-12 carbon glycol, glycerine, trimethylolpropane, 1,1,1-three (methylol) ethane, three (methylol) aminomethane, 1,3, the acid of 5-three (2-ethoxy) cyanogen urea, pentaerythrite, sorbierite, neopentyl glycol, dibromoneopentyl glycol, quinhydrones, resorcinol, bisphenol-A, hydrogenated bisphenol A, isocyanuric acid, the fluoro sugar alcohol, methylene dianiline, phenolic resins, polyvinyl alcohol, polyethylene phenol, polyacrylamide, chitosan, polyethylene glycol ((CH ₂CH ₂O) _n, n=2～400), polypropylene glycol ((CH ₃CH ₂CH ₂O) _nN=2～100), 1,1,1-three (hydroxyphenyl) ethane, three (methylol) nitromethane, glucose, fructose, maltose, mannose, grapes glucosamine, mannosamine, polysaccharide, cellulose, hydroxyethylcellulose, hydroxypropyl cellulose, ethyl cellulose, methylcellulose.

10. the good reverse osmosis composite membrane manufacture method of the stain resistance described in the claim 8 is characterized in that crosslinking agent is selected from H ₂N (CH ₂) _nNH ₂(n=2～12), H ₂N (CH ₂CH ₂O) _nCH ₂CH ₂NH ₂(n=2～400), R ₁R ₂N (CH ₂) _nNR ₃R ₄(n=2～12; R ₁, R ₂, R ₃, R ₄The combination of=hydrogen, methyl, ethyl, propyl group, butyl, cyclohexyl, phenyl etc.), H ₂N ((R ₅) CH ₂) _nNH ₂, R ₁R ₂N ((R ₅) CH ₂) _nNR ₃R ₄(n=2～12; R ₁, R ₂, R ₃, R ₄, R ₅The combination of=hydrogen, methyl, ethyl, propyl group, butyl, cyclohexyl, hydroxyl, phenyl etc.), ester ring type amine (DACH, 1,3-cyclohexane two (methylamine)), 4,4 '-trimethylene, two piperazines, piperazine, 1,4-lupetazin, 1,4-diazabicyclo (2.2.2) octane, 1,8-diazabicyclo (5.4.0) 11 carbon-7-alkene, 1,5-diazabicyclo (4.3.0) ninth of the ten Heavenly Stems-5-alkene, aromatic diamine (m-phenylene diamine (MPD)), m-xylene diamine, two (4-aminophenyl) sulfone, 2, the compound in 2 '-(vinyl dioxy) two (ethamine).

11. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 8 is good, it is characterized in that, crosslinking agent is to be selected from N, N, N ', N '-tetramethyl-2-fourth-1,4-diamines, N, N,-two (2-amino-ethyls)-1,3-propane diamine, diethylenetriamines, trien, three (2-amino-ethyl) amine, N, N, N ', N ', N " five methyl diethylentriamine, triaminobenzene, 1,1; 3, the compound in 3-TMG, polymine, chitosan, poly-(allylamine), the polyvinylpyridine.

12. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 8 is good is characterized in that, crosslinking agent is to be selected from tartaric acid, gluconic acid, 3,5-dihydroxy benzoic acid, 2,5-dihydroxy benzenes sulfonic acid, sylvite, 2,5-dihydroxy-1, the compound in the 4-benzenedisulfonic acid di-potassium.

13. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 8 is good; it is characterized in that; crosslinking agent is to be selected from 3; 5-diaminourea benzoic acid, 2-aminoethane sulphonic acid (taurine), 2-[three (methylol) methyl] amino-1-ethyl sulfonic acid, 3-[three (methylol) methyl] amino-1-propane sulfonic acid, 2-hydroxyl-3[three (methylol) methyl] amino-1-propane sulfonic acid, beta-hydroxy-4-(2-ethoxy)-1-piperazine propane sulfonic acid; β; β '-dihydroxy-1; 4-piperazine two (propane sulfonic acid), 2, the compound in the 5-diamino benzene sulfonic acid.

14. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good, it is characterized in that, epoxide is to be selected from ethylene glycol diglycidylether, 1, the ammediol diglycidyl ether, 1, the 3-butanediol diglycidyl ether, 1, the 4-butanediol diglycidyl ether, 1,5-pentanediol diglycidyl ether, 1,2-pentanediol diglycidyl ether, 2,4-pentanediol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, 1, the 2-hexanediol diglycidyl ether, 1, the 5-hexanediol diglycidyl ether, 2, the 5-hexanediol diglycidyl ether, 2-ethyl-1, the 3-hexanediol diglycidyl ether, 1,7-heptandiol diglycidyl ether, 1,2-ethohexadiol diglycidyl ether, 1,8-ethohexadiol diglycidyl ether, 1,9-nonanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 1,2-decanediol diglycidyl ether, 1,12-12 carbon glycol diglycidyl ethers, 1,2-12 carbon glycol diglycidyl ethers, the glycerine diglycidyl ether, the trimethylolpropane diglycidyl ether, 1,1,1-three (methylol) ethane diglycidyl ether, the pentaerythrite diglycidyl ether, the sorbierite diglycidyl ether, neopentylglycol diglycidyl ether, the dibromoneopentyl glycol diglycidyl ether, the quinhydrones diglycidyl ether, benzene xylenol diglycidyl ether, bisphenol A diglycidyl ether, the hydrogenated bisphenol A diglycidyl ether, polyethyleneglycol diglycidylether, ((CH ₂CH ₂O) _n, n=2～400), polypropylene glycol diglycidyl ether, ((CH ₃) CH ₂CH ₂O) _n, n=2～100) in.

15. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 14 is good is characterized in that, epoxide is to use the compound with 3 above epoxide-reactive functional groups as crosslinking agent.

16. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 15 is good, it is characterized in that, crosslinking agent is to have 3 above epoxide-reactive functional groups, and functional group's form is selected from 1 functional group in hydroxyl, carboxyl, acid anhydride, amide groups, carbonyl, the sulfydryl (thiol base) or 2 or above functional group generates.

17. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 7 is good is characterized in that, crosslinking agent is to be selected from tartaric acid, gluconic acid, 3,5-dihydroxy benzoic acid, 2, the sylvite of 5-dihydroxy benzenes sulfonic acid, 2,5-dihydroxy-1, the compound in the 4-benzenedisulfonic acid disodium salt.

18. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 7 is good, it is characterized in that crosslinking agent is to be selected from N, N '-two (2-amino-ethyl)-1,3-propane diamine, diethylenetriamines, trien, three (2-amino-ethyl) amine, N, N, N ', N ', N " five methyl diethylentriamine, triaminobenzene, 1; 1,3, the compound in 3-TMG, polyethylene imine based, chitosan, poly-(allylamine), the polyvinyl pyridine.

19. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good, it is characterized in that, epoxide can use the diamine compound crosslinking agent crosslinked to carry out, and diamine compound has the structure of primary amine+primary amine, secondary amine+secondary amine, primary amine+secondary amine.

20. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good, it is characterized in that, form the back at polyamide film, before hydrophily coating, this polyamide composite film after the alkaline aqueous solution washing, the washing step of washing with pure water again.

21. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good, it is characterized in that, during with epoxide coating polyamide film, adopt 0.00001～20 weight % solution of pure water, ethanol or its combination, polyamide composite film is coated with.

22. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good is characterized in that, the crosslinked of epoxide is with behind the epoxide parent coating polyamide composite film, makes the surface go up the epoxy product that generates and carries out crosslinked.

23. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good, it is characterized in that the base catalyst that the crosslinked employing of epoxide is selected from alkoxide, hydroxide, carbonate (カ one ボネイト), phenolate, carboxylate, ammonia, primary amine, secondary amine, the tertiary amine carries out crosslinked.

24. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good is characterized in that, the crosslinked employing of epoxide is selected from that the acid catalyst selected in inorganic acid, organic acid, the lewis acid carries out.

25. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good is characterized in that, the crosslinked of epoxide is to be undertaken by dry 1 second～7 days in 10～200 ℃ scope.

26. the reverse osmosis composite membrane manufacture method that the stain resistance described in the claim 1 is good is characterized in that, the crosslinked of epoxide is in the presence of acid catalyst or base catalyst, in 10～150 ℃ scope, by drying handle 1 second～carry out over 2 days.

27. porous diffusion barrier manufacture method that stain resistance is good, it is characterized in that, employing is selected from polysulfones, polyether sulfone, polyimides, polyamide, PEI, polyacrylonitrile, poly-(methacrylate), polyethylene, polypropylene, hydrophily coating is carried out and when making hydrophilic porous property diffusion barrier in the surface of the porous diffusion barrier that the material in the halogenated polymer is made, after adopting the epoxide that has 2 above epoxy radicals at least that the porous diffusion barrier is carried out above-mentioned hydrophily coating, make this epoxide be cross-linked to form water-insoluble high molecular method.

28. the porous diffusion barrier manufacture method that the stain resistance described in the claim 27 is good is characterized in that, the porous diffusion barrier is super filter membrane or secondary filter film.

29. the porous diffusion barrier manufacture method that the stain resistance described in the claim 27 is good is characterized in that, the crosslinked of epoxide undertaken by self-polymerization or crosslinking agent.

30. the porous diffusion barrier manufacture method that the stain resistance described in the claim 27 is good is characterized in that crosslinking agent is the diamine compound with structure of primary amine+primary amine, secondary amine+secondary amine, primary amine+secondary amine.