CN104069749B - A kind of dissaving polymer polyamide composite reverse osmosis membrane and preparation method thereof - Google Patents
A kind of dissaving polymer polyamide composite reverse osmosis membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 62
- 229920000642 polymer Polymers 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000004952 Polyamide Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 229920002647 polyamide Polymers 0.000 title claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 127
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 44
- 125000003368 amide group Chemical group 0.000 claims abstract description 42
- 150000001412 amines Chemical class 0.000 claims abstract description 29
- -1 aromatic series acyl chlorides Chemical class 0.000 claims abstract description 22
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 10
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 44
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 43
- 239000007864 aqueous solution Substances 0.000 claims description 31
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 25
- 239000004332 silver Substances 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 22
- 239000004310 lactic acid Substances 0.000 claims description 22
- 235000014655 lactic acid Nutrition 0.000 claims description 22
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 20
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 18
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 17
- 230000001476 alcoholic effect Effects 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 16
- 239000004760 aramid Substances 0.000 claims description 13
- 229920003235 aromatic polyamide Polymers 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000010612 desalination reaction Methods 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 6
- 238000003618 dip coating Methods 0.000 claims description 4
- 229920000768 polyamine Chemical group 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 claims description 3
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 3
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 claims description 3
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 claims description 3
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 3
- OABYVIYXWMZFFJ-ZUHYDKSRSA-M sodium glycocholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(=O)NCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 OABYVIYXWMZFFJ-ZUHYDKSRSA-M 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000001471 micro-filtration Methods 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 230000004907 flux Effects 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 15
- 238000002791 soaking Methods 0.000 description 14
- 210000004379 membrane Anatomy 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004288 Sodium dehydroacetate Substances 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 239000000149 chemical water pollutant Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940079839 sodium dehydroacetate Drugs 0.000 description 1
- 235000019259 sodium dehydroacetate Nutrition 0.000 description 1
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Abstract
The invention discloses a kind of dissaving polymer polyamide composite reverse osmosis membrane and preparation method thereof, this complex reverse osmosis membrane carries out interfacial polymerization with Hyperbranched Polymer with Terminal Amido and linear multiple amine mixed solution with aromatic series acyl chlorides organic solution on porous support layer and makes。The stable chemical performance of dissaving polymer complex reverse osmosis membrane of the present invention, mechanical performance are excellent, flux is big, salt rejection rate is high, can be widely applied to the field such as environmental protection, food。
Description
Technical field
The invention belongs to technical field of membrane separation, be specifically related to a kind of Hyperbranched Polymer with Terminal Amido complex reverse osmosis membrane and preparation method thereof。
Background technology
Reverse osmosis membrane is a kind of pressure drive membrane, its energy all dissolving salts of effectively catching and molecular weight Organic substance more than 100, allow hydrone to pass through simultaneously, be widely used in pure water and preparation of high-purity water, the field such as prepared by drinking water, Treated sewage reusing, landfill leachate treatment, desalinization。At present, commercialization reverse osmosis membrane is composite membrane mostly, is usually and adopts interfacial polymerization techniques to obtain at the ultra-thin compacted zone of porous support layer surface recombination。Porous support layer, also known as basement membrane, acts the effect increasing mechanical strength；Compacted zone, also referred to as epidermal area, plays desalination, therefore also known as desalination layer。Aromatic polyamide composite membrane, fatty polyamide composite membrane etc. is had disclosed in being currently known。But but the problem that current the studied reverse osmosis membrane higher flux of ubiquity salt rejection rate is relatively low。
Dissaving polymer (hyperbranchedpolymer) is a kind of polymer with special macromolecular structure, there is the three dimensions pore passage structure of novelty, unique performance and potential application prospect, make this base polymer be subject to attention and the favor of vast researcher, be considered the important directions of 21 century polymer science development。Hyperbranched polymer molecule chain not easy entanglement, containing a large amount of active function groups, there is unique advantages such as viscosity is low, dissolubility is good, be widely used in the fields such as agricultural, medicine, liquid crystal, functional material, life sciences, cosmetics, coatings industry, paint industry。Dissaving polymer has special space structure, can be used for preparing the reverse osmosis composite membrane of high flux, equipment with high desalinization, but currently available technology does not openly utilize dissaving polymer to prepare technique and the method for complex reverse osmosis membrane。
Summary of the invention
The present invention seeks to overcome the deficiencies in the prior art, utilizes dissaving polymer to have the characteristic of special space structure, it is provided that dissaving polymer polyamide composite reverse osmosis membrane that a kind of flux is big and salt rejection rate is high and preparation method thereof。
First, the present invention provides the technical scheme of a kind of dissaving polymer polyamide composite reverse osmosis membrane: its polyamide desalination layer formed by interfacial polymerization by porous support layer and its surface, described polyamide desalination layer is dissaving polymer aramid layer, and described dissaving polymer aramid layer is formed by interfacial polymerization by Hyperbranched Polymer with Terminal Amido, polyamine and aromatic series acyl chlorides。
Such scheme can be more preferably:
Described dissaving polymer is molecular weight is 2000 ~ 5000 Hyperbranched Polymer with Terminal Amidos；Described dissaving polymer aramid layer thickness is 30nm ~ 200nm。
Described porous support layer is any one in polyacrylonitrile, polyether sulfone, modified polyvinilidene fluoride and polysulfones micro-filtration membrane or ultrafilter membrane, and described open support layer thickness is 60 μm ~ 120 μm。Porous support layer can oneself prepare or market is buied。
Described complex reverse osmosis membrane is Flat Membrane, hollow-fibre membrane or tubular membrane；The pore-size distribution of described complex reverse osmosis membrane is 0.5 ~ 10nm。
Then, it is provided that a kind of preparation method of above-mentioned dissaving polymer polyamide composite reverse osmosis membrane, it comprises the following steps:
(1), at the mixed aqueous solution of the hygrometric state porous support layer surface dip-coating dissaving polymer cleaned up Yu linear multiple amine, then removing surface liquid, the time of described dip-coating is 3s ~ 300s；The total mass fraction of described dissaving polymer and linear multiple amine mixed aqueous solution is 2% ~ 10%；Described dissaving polymer is molecular weight is 2000 ~ 5000 Hyperbranched Polymer with Terminal Amidos；Described linear multiple amine is at least one in diethylamine, triethylamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, piperazine, 4-aminomethylpiperazine, m-diaminobenzene., o-phenylenediamine and p-phenylenediamine；
(2), contact scribbling Hyperbranched Polymer with Terminal Amido with the organic solution of aromatic series acyl chlorides with the porous support layer surface of linear multiple amine mixed aqueous solution, obtain aramid layer after carrying out interfacial polymerization on the surface of porous support layer, the time of described interfacial polymerization is 3s ~ 120s；The mass fraction of described aromatic series acyl chlorides organic solution is 0.05% ~ 2%, described aromatic series acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, at least one faced in phthalyl chloride, paraphthaloyl chloride and benzene-disulfo-chloride, and the solvent of described organic solution is at least one in the aliphatic hydrocarbon containing 4 ~ 10 carbon atoms；Then drop is except the residual reaction solution on surface, and at room temperature dries in the shade, described in time of drying in the shade be 4s ~ 300s；
(3) porous support layer with aramid layer desalination layer prepared by step (2), adopt following four solution rinse last drying successively to complex reverse osmosis membrane；Described solution is followed successively by: mass fraction is a solution of 3% ~ 15%, and described a is any one in maleic acid, maleic anhydride, citric acid, oxalic acid, lactic acid；Mass fraction is the b solution of 3% ~ 15%, and described b is methanol or ethanol；Mass fraction is the c solution of 0.05% ~ 5%, and described c is any one in nano TiO 2 carrying silver, nano zine oxide, nanometer silver, nano titanium oxide；Mass fraction is the d solution of 5% ~ 10%, and described d is at least one in glycerol, camphorsulfonic acid, sodium sulfite。
Such scheme can be more preferably:
The total mass fraction of described Hyperbranched Polymer with Terminal Amido and linear multiple amine mixed aqueous solution is 3% ~ 5%；The mass fraction of described aromatic series acyl chlorides organic solution is 0.1% ~ 0.3%；Described aromatic series acyl chlorides is preferably pyromellitic trimethylsilyl chloride；The solvent of described organic solution is preferably normal hexane。
Described a is preferably lactic acid, and the mass fraction of lactic acid solution is 5% ~ 7%；Described b is preferably ethanol, and the mass fraction of alcoholic solution is 5% ~ 7%；Described c is preferably nano TiO 2 carrying silver, and the mass fraction of nano TiO 2 carrying silver solution is 0.6% ~ 1%。
Also including the surfactant that mass fraction is 0.05% ~ 0.8% in described mixed aqueous solution, described surfactant is at least one in dodecylbenzene sodium sulfonate, sodium glycocholate, dioctyl succinate disulfonate acid, sodium lauryl sulphate, sodium laurylsulfate；Described surfactant more preferably dodecylbenzene sodium sulfonate, and its mass fraction is preferably 0.15%。
The temperature of described drying is 75 ~ 100 DEG C, the time is 2min ~ 40min；The temperature of described drying more preferably 85 DEG C, time more preferably 3min。
The rinsing time of four kinds of described solution is 60s。
Compared with prior art, the stable chemical performance of dissaving polymer complex reverse osmosis membrane in the present invention, mechanical performance is excellent, flux is big, salt rejection rate is high, can be widely applied to the field such as environmental protection, food。
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but not as a limitation of the invention。
First a kind of preparation method of dissaving polymer polyamide composite reverse osmosis membrane is provided, comprises the following steps:
(1) one side of the porous support layer of hygrometric state is immersed into Hyperbranched Polymer with Terminal Amido and in linear multiple amine mixed aqueous solution, after continuing 20s, removes the liquid on surface with rubber roll-in；
(2) continuing to be immersed in the organic solution containing aromatic series acyl chlorides by this surface, dry in the shade under room temperature after continuing 20s 30s, forms dissaving polymer aramid layer；
(3) then carry out substep rinsing, be soaking a solution 1min, the b solution 1min of 3% ~ 15%, the c solution 1min of 0.05% ~ 5%, the d solution 1min of 5% ~ 10% that mass fraction is 3% ~ 15% successively, finally dry and obtain reverse osmosis membrane。
The configuration process of several solns in said method is then provided:
1, the process for preparation of Hyperbranched Polymer with Terminal Amido and linear multiple amine mixed aqueous solution is: by Hyperbranched Polymer with Terminal Amido (HBP ~ NH2) add in 18 DEG C ~ 65 DEG C aqueous solutions containing surfactant with linear multiple amine blends, stirring 20min ~ 90min forms required aqueous solution to solution complete miscibility。
Wherein polyamine is at least one in diethylamine, triethylamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, piperazine, 4 ~ aminomethylpiperazine, m-diaminobenzene., o-phenylenediamine, p-phenylenediamine。
Wherein Hyperbranched Polymer with Terminal Amido molecular weight is 2000 to 5000, and polymer ends is amino group；The total mass fraction of Hyperbranched Polymer with Terminal Amido and linear multiple amine mixed aqueous solution is 2% ~ 10%, it is preferable that 3% ~ 5%, and wherein Hyperbranched Polymer with Terminal Amido can regulate and control voluntarily with the ratio of linear multiple amine。
Wherein surfactant sodium dodecyl base benzene sulfonic acid sodium salt, sodium glycocholate, dioctyl succinate disulfonate acid, sodium lauryl sulphate, at least one in sodium laurylsulfate, it is preferable that dodecylbenzene sodium sulfonate, mass fraction is 0.05% ~ 0.8%, it is preferable that 0.15%。
、The process for preparation of aromatic series acyl chlorides organic solution is: added by aromatic series acyl chlorides in organic solvent, stirs 20min ~ 90min to solution complete miscibility at 18 DEG C ~ 65 DEG C, forms required organic solution。
Wherein aromatic series acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, at least one faced in phthalyl chloride, paraphthaloyl chloride, benzene-disulfo-chloride, it is preferable that pyromellitic trimethylsilyl chloride。
Wherein organic solvent is at least one in the aliphatic hydrocarbon containing 4 ~ 10 carbon atoms, it is preferable that normal hexane。
Wherein the mass fraction of aromatic series acyl chlorides organic solution is 0.05% ~ 2%, it is preferable that 0.1% ~ 0.3%。
、The preparation of solution needed for four step rinse step: preparation mass fraction is a solution of 3% ~ 15% respectively, the b solution of 3% ~ 15%, the c solution of 0.05% ~ 5%, the d solution of 5% ~ 10%。
Wherein a solution be in maleic acid, maleic anhydride, citric acid, oxalic acid, lactic acid any one, it is preferable that lactic acid, mass fraction preferably 5% ~ 7%。
Wherein b solution is at least one in methanol, alcoholic solution, it is preferable that ethanol, mass fraction preferably 5% ~ 7%。
Wherein c solution be in nano TiO 2 carrying silver, nano zine oxide, sodium dehydroacetate, sodium sulfite, nanometer silver, nanometer titanium dioxide titanium solution any one, it is preferable that nano TiO 2 carrying silver solution, mass fraction preferably 0.6% ~ 1%。
Wherein d solution is at least one in glycerite, camphorsulfonic acid solution, sodium sulfite solution, and mass fraction is 5% ~ 15%。
Drying steps after rinsing is: the polymeric film after rinsing is dried in an oven and obtained reverse osmosis membrane。Drying temperature is 75 ~ 100 DEG C, it is preferable that 85 DEG C, drying time is 2min ~ 40min, it is preferable that 3min, blower fan wind speed 2m/s ~ 20m/s, it is preferable that 4m/s。
The composite membrane pore-size distribution finally prepared is 0.5nm ~ 10nm, and aramid layer thickness is 30nm ~ 200nm。
The complex reverse osmosis membrane performance that said method is prepared by following method is adopted to be tested:
On diaphragm monitor station, flux and salt rejection rate to complex reverse osmosis membrane are tested, and test condition is: self-control 250ppmNaCl aqueous solution, test temperature are 25 DEG C, monitor station operating pressure is 0.45Mpa, monitor station Validity Test area 5.2 square feet。Open detection platform, 12min is run under test pressure, start to measure (the product water collection prepared by every sample film, collect 8min altogether, sample film test quantity at least 3 prepared by every kind of preparation method, test result is averaged), record strong brine electrical conductivity (i.e. NaCl aqueous solution electrical conductivity), product water volume (ml) and product water conductivity (μ s/cm), calculate permeant flux (gfd, i.e. gallon/square feet sky), calculating salt rejection rate (%), salt rejection rate computing formula is 1 ~ (producing water conductivity/strong brine electrical conductivity) × 100%。
On the basis of preparation method disclosed above, various raw materials respectively according to chosen below for example come the present invention is described further；Namely Hyperbranched Polymer with Terminal Amido is chosen as the Hyperbranched Polymer with Terminal Amido that molecular weight is 2000,3000 and 5000, polyamine is chosen as m-diaminobenzene., aromatic series acyl chlorides is chosen as pyromellitic trimethylsilyl chloride, organic solvent is chosen as normal hexane, a solution is chosen as lactic acid solution, b solution is chosen as alcoholic solution, and c solution is chosen as nano TiO 2 carrying silver solution, and d solution is chosen as glycerite。
Embodiment 1
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state is immersed into Hyperbranched Polymer with Terminal Amido that molecular weight is 2000 with in linear multiple amine mixed aqueous solution (total mass fraction 3.5%), surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1%, m-diaminobenzene. mass fraction 2.5%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 2
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 3.5%) that the one side of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1.5%, m-diaminobenzene. mass fraction 2%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 3
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 3.5%) that the one side face of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 2%, m-diaminobenzene. mass fraction 1.5%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 4
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 3.5%) that the one side of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 2.5%, m-diaminobenzene. mass fraction 1%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 5
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 3.5%) that the one side of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 3%, m-diaminobenzene. mass fraction 0.5%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 6
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 4%) that the one side face of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1%, m-diaminobenzene. mass fraction 3%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Comparative example 1
The preparation method of a kind of complex reverse osmosis membrane, comprises the following steps:
(1) being immersed in linear multiple amine aqueous solution by the one side of the porous support layer of hygrometric state, remove surface liquid, wherein m-diaminobenzene. mass fraction 3.5% with rubber roll-in after continuing 20s, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 7
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 3.5%) that the one side of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1.5%, m-diaminobenzene. mass fraction 2%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 6% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 8
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 3.5%) that the one side of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1.5%, m-diaminobenzene. mass fraction 2%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 7% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 9
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) it is in 2000 Hyperbranched Polymer with Terminal Amidos and linear multiple amine mixed aqueous solution (mass fraction 3.5%) that the one side of the porous support layer of hygrometric state is immersed into molecular weight, surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1.5%, m-diaminobenzene. mass fraction 2%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.3% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 6%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Comparative example 2
The preparation method of a kind of complex reverse osmosis membrane, comprises the following steps:
(1) being immersed in linear multiple amine aqueous solution by the porous support layer one side of hygrometric state, remove surface liquid, wherein m-diaminobenzene. mass fraction 3.5% with rubber roll-in after continuing 20s, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 6% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 10
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state is immersed into Hyperbranched Polymer with Terminal Amido that molecular weight is 3000 with in linear multiple amine mixed aqueous solution (total mass fraction 3.5%), surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1%, m-diaminobenzene. mass fraction 2.5%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
Embodiment 11
The preparation method of a kind of dissaving polymer polyamide composite reverse osmosis membrane, comprises the following steps:
(1) one side of the porous support layer of hygrometric state is immersed into Hyperbranched Polymer with Terminal Amido that molecular weight is 5000 with in linear multiple amine mixed aqueous solution (total mass fraction 3.5%), surface liquid is removed with rubber roll-in after continuing 20s, wherein Hyperbranched Polymer with Terminal Amido mass fraction in the solution is 1%, m-diaminobenzene. mass fraction 2.5%, dodecylbenzene sodium sulfonate mass fraction is 0.15%；
(2) continuing one side and be immersed in containing, in the hexane solution that mass fraction is 0.1% pyromellitic trimethylsilyl chloride, continuing 20s, dry in the shade under room temperature after wherein 30s；
(3) four step rinsings are then carried out, it is at the nano TiO 2 carrying silver solution 1min soaking lactic acid solution 1min, the alcoholic solution 1min of 5%, 0.6% that mass fraction is 5% successively, the glycerite 1min of 12%, finally at 85 DEG C, dry 3min drying obtains reverse osmosis membrane。
The performance test results of the sample film prepared by above-described embodiment and reference examples is as shown in the table:
| Classification | Flux (GFD) | Salt rejection rate (%) |
| Embodiment 1 | 30.5 | 97.6 |
| Embodiment 2 | 34.8 | 97.4 |
| Embodiment 3 | 39.4 | 96.8 |
| Embodiment 4 | 42.3 | 95.3 |
| Embodiment 5 | 47.4 | 94.0 |
| Embodiment 6 | 28.3 | 97.2 |
| Comparative example 1 | 20.1 | 97.4 |
| Embodiment 7 | 36 | 96.2 |
| Embodiment 8 | 37.2 | 95.3 |
| Embodiment 9 | 36.2 | 95.8 |
| Comparative example 2 | 24.8 | 95.6 |
| Embodiment 10 | 30.4 | 96.8 |
| Embodiment 11 | 27.8 | 97.1 |
Contrast by above example and technical specification, the present invention (embodiment 1-11) is under the premise keeping salt rejection rate and prior art (comparative example 1 and 2) to be basically unchanged, by introducing Hyperbranched Polymer with Terminal Amido in desalination layer, utilize its three dimensions pore passage structure can increase substantially flux, thus improving the efficiency of reverse osmosis；And skilled artisan would appreciate that; above example is only several exemplary embodiments of the present invention; when without departing from or when not necessarily departing from scope; technical solutions and their implementation methods of the present invention have multiple modification, improvement or equivalent variations, and these all should fall within the scope of protection of the present invention。
Claims (9)
1. a dissaving polymer polyamide composite reverse osmosis membrane, the polyamide desalination layer formed by interfacial polymerization by porous support layer and its surface, it is characterized in that: described polyamide desalination layer is dissaving polymer aramid layer, described dissaving polymer aramid layer is formed by interfacial polymerization by Hyperbranched Polymer with Terminal Amido, polyamine and aromatic series acyl chlorides；Preparation method comprises the following steps:
(1), at the mixed aqueous solution of the hygrometric state porous support layer surface dip-coating dissaving polymer cleaned up Yu linear multiple amine, then removing surface liquid, the time of described dip-coating is 3s ~ 300s；The total mass fraction of described dissaving polymer and linear multiple amine mixed aqueous solution is 2% ~ 10%；Described dissaving polymer is molecular weight is 2000 ~ 5000 Hyperbranched Polymer with Terminal Amidos；Described linear multiple amine is at least one in diethylamine, triethylamine, propane diamine, butanediamine, pentanediamine, hexamethylene diamine, piperazine, 4-aminomethylpiperazine, m-diaminobenzene., o-phenylenediamine and p-phenylenediamine；
(2), contact scribbling Hyperbranched Polymer with Terminal Amido with the organic solution of aromatic series acyl chlorides with the porous support layer surface of linear multiple amine mixed aqueous solution, obtain aramid layer after carrying out interfacial polymerization on the surface of porous support layer, the time of described interfacial polymerization is 3s ~ 120s；The mass fraction of described aromatic series acyl chlorides organic solution is 0.05% ~ 2%, described aromatic series acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride, at least one faced in phthalyl chloride, paraphthaloyl chloride and benzene-disulfo-chloride, and the solvent of described organic solution is at least one in the aliphatic hydrocarbon containing 4 ~ 10 carbon atoms；Then drop is except the residual reaction solution on surface, and at room temperature dries in the shade, described in time of drying in the shade be 4s ~ 300s；
(3) porous support layer with aramid layer desalination layer prepared by step (2), adopt following four aqueous solution rinse last drying successively to complex reverse osmosis membrane；Described solution is followed successively by: mass fraction is a solution of 3% ~ 15%, and described a is any one in maleic acid, maleic anhydride, citric acid, oxalic acid, lactic acid；Mass fraction is the b solution of 3% ~ 15%, and described b is methanol or ethanol；Mass fraction is the c solution of 0.05% ~ 5%, and described c is any one in nano TiO 2 carrying silver, nano zine oxide, nanometer silver, nano titanium oxide；Mass fraction is the d solution of 5% ~ 10%, and described d is at least one in glycerol, camphorsulfonic acid, sodium sulfite。
2. dissaving polymer polyamide composite reverse osmosis membrane according to claim 1, it is characterised in that described dissaving polymer aramid layer thickness is 30nm ~ 200nm。
3. dissaving polymer polyamide composite reverse osmosis membrane according to claim 1, it is characterized in that, described porous support layer is any one in polyacrylonitrile, polyether sulfone, modified polyvinilidene fluoride and polysulfones micro-filtration membrane or ultrafilter membrane, and described open support layer thickness is 60 μm ~ 120 μm；Described complex reverse osmosis membrane is Flat Membrane, hollow-fibre membrane or tubular membrane；The pore-size distribution of described complex reverse osmosis membrane is 0.5 ~ 10nm。
4. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 1, it is characterised in that the total mass fraction of described Hyperbranched Polymer with Terminal Amido and linear multiple amine mixed aqueous solution is 3% ~ 5%；The mass fraction of described aromatic series acyl chlorides organic solution is 0.1% ~ 0.3%；Described aromatic series acyl chlorides is pyromellitic trimethylsilyl chloride；The solvent of described organic solution is normal hexane。
5. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 1, it is characterised in that described a is lactic acid, and the mass fraction of lactic acid solution is 5% ~ 7%；Described b is ethanol, and the mass fraction of alcoholic solution is 5% ~ 7%；Described c is nano TiO 2 carrying silver, and the mass fraction of nano TiO 2 carrying silver solution is 0.6% ~ 1%。
6. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 1, it is characterized in that, also including the surfactant that mass fraction is 0.05% ~ 0.8% in described mixed aqueous solution, described surfactant is at least one in dodecylbenzene sodium sulfonate, sodium glycocholate, dioctyl succinate disulfonate acid, sodium lauryl sulphate, sodium laurylsulfate。
7. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 6, it is characterised in that described surfactant is dodecylbenzene sodium sulfonate, and its mass fraction is 0.15%。
8. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 4, it is characterised in that the temperature of described drying is 75 ~ 100 DEG C, the time is 2min ~ 40min；The rinsing time of four kinds of described solution is 60s。
9. the preparation method of dissaving polymer polyamide composite reverse osmosis membrane according to claim 8, it is characterised in that the temperature of described drying is 85 DEG C, the time is 3min。
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Inventor after: Cai Xiangyu Inventor after: Wang Shuang Inventor after: Wang Wei Inventor after: Zhang Yingying Inventor after: Wang Xiaoyan Inventor after: Wei Guoqiang Inventor before: Wang Wei Inventor before: Yu Wanli Inventor before: Cai Xiangyu Inventor before: Wang Shuang Inventor before: Zhang Yingying Inventor before: Wang Xiaoyan Inventor before: Wei Guoqiang |
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Denomination of invention: Hyperbranched polymer polyamide composite reverse osmosis membrane and preparation method thereof Effective date of registration: 20161206 Granted publication date: 20160622 Pledgee: Commercial Bank of China Limited by Share Ltd. Dongying Kenli branch Pledgor: SHANDONG JOZZON MEMBRANE TECHNOLOGY CO.,LTD. Registration number: 2016990001064 |
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Denomination of invention: Hyperbranched polymer polyamide composite reverse osmosis membrane and preparation method thereof Effective date of registration: 20171211 Granted publication date: 20160622 Pledgee: Commercial Bank of China Limited by Share Ltd. Dongying Kenli branch Pledgor: SHANDONG JOZZON MEMBRANE TECHNOLOGY CO.,LTD. Registration number: 2017990001137 |
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Effective date of registration: 20230707 Address after: 100080 room 909, No.9, North Fourth Ring Road West, Haidian District, Beijing Patentee after: BEIJING JIUZHANG ENVIRONMENTAL ENGINEERING Co.,Ltd. Address before: 257500 No. 56, Shengxing Road, Kenli Economic Development Zone, Dongying City, Shandong Province Patentee before: SHANDONG JOZZON MEMBRANE TECHNOLOGY CO.,LTD. |