CN114588786A - Microporous membrane containing cross-linked hydrophilic polymer and preparation method thereof - Google Patents
Microporous membrane containing cross-linked hydrophilic polymer and preparation method thereof Download PDFInfo
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- 239000012982 microporous membrane Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 229920001477 hydrophilic polymer Polymers 0.000 title claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 61
- 239000000243 solution Substances 0.000 claims abstract description 56
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 50
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 41
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 40
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 16
- 238000004132 cross linking Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000002791 soaking Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000002033 PVDF binder Substances 0.000 claims description 22
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 22
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 13
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- 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
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 229940015043 glyoxal Drugs 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 5
- 239000004800 polyvinyl chloride Substances 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000015572 biosynthetic process Effects 0.000 claims 3
- 238000000926 separation method Methods 0.000 abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 229920006324 polyoxymethylene Polymers 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 239000012510 hollow fiber Substances 0.000 description 13
- 238000005345 coagulation Methods 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 9
- 238000009987 spinning Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention relates to the field of microporous separation membranes, and discloses a microporous membrane containing a crosslinked hydrophilic polymer and a preparation method thereof, wherein the raw materials comprise a microporous membrane main body material and the crosslinked hydrophilic polymer, and the crosslinked hydrophilic polymer is crosslinked polyvinyl acetal; the preparation method comprises the following steps: (1) preparing a film preparation solution: adding a microporous membrane main body material, polyvinyl acetal and a film-making non-solvent into a solvent, and dissolving to obtain a film-making solution; (2) film preparation: preparing the obtained membrane preparation solution into a polymer microporous membrane through a phase inversion process; (3) and (3) crosslinking: and (3) soaking the polymer microporous membrane in an aqueous solution of a cross-linking agent, and treating to obtain the microporous membrane containing the cross-linked hydrophilic polymer. The invention blends polyvinyl acetal polymer in the polymer film material body and cross-links the hydroxyl in the polyvinyl acetal molecule, which can ensure the hydrophilic stability of the film material.
Description
Technical Field
The invention relates to the technical field of microporous separation membranes, in particular to a microporous membrane containing a cross-linked hydrophilic polymer and a preparation method thereof.
Background
The membrane separation technology is widely applied in the fields of liquid separation such as water treatment, material separation and the like due to simple process and high separation efficiency. The polyvinylidene fluoride, polysulfone, polyvinyl chloride and other polymer materials have stable performance, easily obtained solvent and better chemical agent resistance, and are widely applied to the field of separation membranes. However, common membrane-making materials such as polyvinylidene fluoride, polysulfone and polyvinyl chloride have low surface energy, belong to hydrophobic materials, and are easy to absorb common pollutants such as humic acid and protein in water on the membrane surface in the application process of the membrane as a water treatment separation membrane, so that the membrane surface is polluted, and the operation performance of the separation membrane is reduced. Therefore, the improvement of the hydrophilicity of the polymer separation membrane and the reduction of membrane pollution become important work of continuous research in the industry.
As a common hydrophilic modification technology for membrane materials, the hydrophilicity of a polymer separation membrane is improved by blending hydrophilic high molecular polymers in the industry at present. For example, in CN200410055572.6, polyvinylpyrrolidone (PVP) was added during membrane preparation to improve the hydrophilicity of polyvinylidene fluoride membrane. But PVP belongs to a water-soluble polymer material and is easy to dissolve out gradually in the using process, so that the polyvinylidene fluoride membrane loses hydrophilicity. In CN 200810061388.0, an amphiphilic polymer is added in the membrane preparation process to improve the hydrophilicity of the polyvinylidene fluoride ultrafiltration membrane. Although the water solubility of the amphiphilic polymer is improved compared with that of the PVP polymer, the amphiphilic polymer still has the problem of loss due to water dissolution in the using process.
Polyvinyl acetal contains a large amount of hydrophilic hydroxyl groups, has hydrophilicity, and is insoluble in water due to acetal chain links, so that the polyvinyl acetal is used as a blended hydrophilic polymer for research in membrane materials, for example, the publication of 'a polyvinyl acetal/polyvinylidene fluoride blended hollow fiber microporous membrane and a preparation method thereof' in Chinese patent literature has a publication number CN101559333, the section of the hollow fiber microporous membrane prepared by the invention is of a through branch-shaped microporous structure, the pore diameter of the microporous is 0.05-0.5 mu m, and the porosity is 60-80%; the main film forming matter is polyvinyl acetal 50-75%, polyvinylidene fluoride 20-45% and additive 0.1-7%.
However, because the polyvinyl alcohol polymer contains a large number of hydroxyl groups and has high affinity with water or alcohol, ether and ketone substances, the membrane material added with the polyvinyl acetal has unstable size in the dry-wet change process, and when the membrane material meets a filtering solution containing alcohol, ether and ketone, the polyvinyl acetal is easy to dissolve and run off in the operation process, so that the hydrophilic stability of the membrane is reduced, and the separation performance of the membrane is influenced.
Disclosure of Invention
The invention provides a microporous membrane containing a cross-linked hydrophilic polymer and a preparation method thereof, aiming at overcoming the problems that the size of a membrane material added with polyvinyl acetal is unstable in the process of dry-wet change and the polyvinyl acetal is easy to dissolve out and run off in the operation process when a filtering solution containing alcohol, ether and ketone is encountered in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the microporous membrane containing the cross-linked hydrophilic polymer comprises a microporous membrane main body material and the cross-linked hydrophilic polymer, wherein the cross-linked hydrophilic polymer is cross-linked polyvinyl acetal.
The invention also discloses a preparation method of the microporous membrane, which comprises the following steps:
(1) preparing a film preparation solution: adding a microporous membrane main body material, polyvinyl acetal and a film-making non-solvent into a solvent, and dissolving to obtain a film-making solution;
(2) film preparation: preparing the obtained membrane preparation solution into a polymer microporous membrane through a phase inversion process;
(3) and (3) crosslinking: and (3) soaking the polymer microporous membrane in an aqueous solution of a cross-linking agent, and treating to obtain the microporous membrane containing the cross-linked hydrophilic polymer.
According to the invention, a main material of the microporous membrane and polyvinyl acetal are mixed to prepare a polymer microporous membrane, then the polymer microporous membrane is soaked in a cross-linking agent solution after being formed, and the polyvinyl acetal in the microporous membrane is fixed in a microporous membrane body in a chemical cross-linking mode by utilizing the reaction of hydroxyl of vinyl alcohol chain links in the polyvinyl acetal and the cross-linking agent. After crosslinking, due to the existence of crosslinking points, the water resistance and the solvent resistance of the polyvinyl acetal are enhanced, even if the polyvinyl acetal is soaked by common solvents such as alcohol, ether and ketone, the polyvinyl acetal cannot run off from the microporous membrane, and can be stably remained on the body and the surface of the microporous membrane, thereby realizing permanent hydrophilic modification of a hydrophobic microporous membrane material.
Meanwhile, due to the adoption of the technical scheme of blending with the film making material body instead of surface modification, even if part of surface hydrophilic substances are corroded to be lost, the hydrophilic substances still exist in the microporous film body, so that the hydrophilicity of the film material can be kept without serious loss.
Preferably, the polyvinyl acetal is selected from one or more of polyvinyl formal, polyvinyl acetal, polyvinyl formal and polyvinyl butyral.
Preferably, the polyvinyl acetal has a molecular chain with a mass content of vinyl alcohol units of not less than 10%. The content of vinyl alcohol chain units is less than 10 percent, the hydrophilicity of polyvinyl acetal is poor, the hydrophilic modification effect cannot be realized, and meanwhile, the vinyl alcohol chain units are few, so that the crosslinking reaction of the vinyl alcohol chain units and a subsequent crosslinking agent is not easy to realize.
Preferably, the microporous membrane main body material is selected from one or more of polyvinylidene fluoride, polyvinyl chloride and polysulfone polymers.
Preferably, in the film-forming solution obtained in step (1), the mass ratio of the polyvinyl acetal to the microporous membrane host material is less than 1: 1; the mass concentration of the microporous membrane main body material in the membrane preparation solution is 10-20%.
Preferably, the film-forming non-solvent in step (1) is one or more selected from ethanol, glycerol, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether, and the mass concentration of the film-forming non-solvent in the film-forming solution is 0 to 20%; the solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
Preferably, the phase inversion process in step (2) is a non-solvent immersion phase inversion or a non-solvent vapor induced phase inversion.
Preferably, the cross-linking agent in step (3) is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid, malic acid, formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, and adipaldehyde; the mass concentration of the water solution of the cross-linking agent is 1-10%, and the pH value is 0-4.
Preferably, the treatment temperature in the step (3) is 20-90 ℃, and the treatment time is 2-120 min. The invention adopts the cross-linking agent aqueous solution with stronger acidity and carries out treatment at higher temperature to promote the rapid proceeding of the cross-linking reaction.
Therefore, the invention has the following beneficial effects: permanent hydrophilic modification of the polymer film material can be realized by blending polyvinyl acetal polymers in the polymer film material body and crosslinking hydroxyl groups in polyvinyl acetal molecules. The cross-linked polyvinyl acetal in the polymer membrane material is not easy to be washed out by common solvents of polyvinyl acetal such as alcohol, ether, ketone and the like, and the hydrophilic stability of the membrane material is ensured.
Detailed Description
The invention is further described with reference to specific embodiments.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
General example:
a method for preparing a microporous membrane comprising a crosslinked hydrophilic polymer, comprising the steps of:
(1) preparing a film preparation solution: adding a microporous membrane main body material, polyvinyl acetal and a film-making non-solvent into a solvent, and dissolving to obtain a film-making solution;
the microporous membrane is characterized by comprising a membrane preparation solution, a microporous membrane main body material and a membrane separation solution, wherein the microporous membrane main body material is selected from one or more of polyvinylidene fluoride, polyvinyl chloride and polysulfone polymers, and the mass fraction of the microporous membrane main body material in the membrane preparation solution is 10-20%;
the polyvinyl acetal is selected from one or more of polyvinyl formal, polyvinyl acetal, polyvinyl methylaldehyde and polyvinyl butyral, the mass content of vinyl alcohol chain units in molecular chains of the polyvinyl acetal is not less than 10%, and the mass ratio of the polyvinyl acetal to the microporous membrane main material is less than 1: 1;
the film-making non-solvent is selected from one or more of ethanol, glycerol, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether and ethylene glycol dimethyl ether, and the mass fraction of the film-making non-solvent in the film-making solution is 0-20%;
the solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide;
(2) film preparation: preparing the obtained membrane preparation solution into a polymer microporous membrane by a phase inversion process, wherein the phase inversion process is non-solvent immersion phase inversion or non-solvent steam induced phase inversion;
(3) and (3) crosslinking: soaking the polymer microporous membrane in a water solution of a cross-linking agent, and treating at 20-90 ℃ for 2-120 min to obtain a microporous membrane containing a cross-linked hydrophilic polymer; wherein the cross-linking agent is selected from one or more of oxalic acid, malonic acid, succinic acid, citric acid, malic acid, formaldehyde, glyoxal, succinaldehyde, glutaraldehyde and adipaldehyde; the mass concentration of the water solution of the cross-linking agent is 1-10%, and the pH value is 0-4.
Example 1:
a method for preparing a microporous membrane comprising a crosslinked hydrophilic polymer, comprising the steps of:
(1) preparing a film preparation solution: polyvinylidene fluoride, polyvinyl butyral (the mass content of a vinyl alcohol chain link is 20 percent) and polyethylene glycol 400 are added into N, N-dimethylacetamide, and dissolved at 70 ℃ to obtain a film preparation solution; in the obtained film-making solution, the mass concentration of polyvinylidene fluoride is 12%, and the mass concentration of polyvinyl butyral is 5%; the mass concentration of the polyethylene glycol 400 is 13 percent;
(2) film preparation: extruding the obtained membrane preparation solution through an annular spinning jet, and taking a 40 wt% aqueous solution of N, N-dimethylacetamide as an external coagulation bath and a 50 wt% aqueous solution of N, N-dimethylacetamide as an internal coagulation bath to prepare a polymer hollow fiber membrane;
(3) and (3) crosslinking: after full rinsing, the polymer hollow fiber membrane is soaked in glutaraldehyde aqueous solution with the mass concentration of 1% and the pH value of 1.0, treated for 20min at the temperature of 90 ℃, taken out, and rinsed with deionized water to obtain the microporous membrane containing the crosslinked hydrophilic polymer.
Example 2:
a method for preparing a microporous membrane comprising a crosslinked hydrophilic polymer, comprising the steps of:
(1) preparing a film preparation solution: polyvinylidene fluoride, polyvinyl butyral (the mass content of a vinyl alcohol chain is 10 percent) and polyethylene glycol 400 are added into N, N-dimethylacetamide, and dissolved at 70 ℃ to obtain a film preparation solution; in the obtained film-making solution, the mass concentration of polyvinylidene fluoride is 10%, the mass concentration of polyvinyl butyral is 8%, and the mass concentration of polyethylene glycol 400 is 12%;
(2) film preparation: extruding the obtained membrane preparation solution through an annular spinning jet, and taking a 40 wt% aqueous solution of N, N-dimethylacetamide as an external coagulation bath and a 50 wt% aqueous solution of N, N-dimethylacetamide as an internal coagulation bath to prepare a polymer hollow fiber membrane;
(3) and (3) crosslinking: after full rinsing, the polymer hollow fiber membrane is soaked in glutaraldehyde aqueous solution with the mass concentration of 4% and the pH value of 1.0, treated for 120min at the temperature of 70 ℃, taken out, and rinsed with deionized water to obtain the microporous membrane containing the crosslinked hydrophilic polymer.
Example 3:
a method for preparing a microporous membrane comprising a crosslinked hydrophilic polymer, comprising the steps of:
(1) preparing a film preparation solution: adding polyvinylidene fluoride, polyvinyl formal acetaldehyde (the mass content of vinyl alcohol chain links is 30%) and glycerol into N, N-dimethylacetamide, and dissolving at 70 ℃ to obtain a membrane preparation solution; in the obtained film-making solution, the mass concentration of polyvinylidene fluoride is 15%, the mass concentration of polyvinyl butyral is 2%, and the mass concentration of glycerin is 8%;
(2) film preparation: extruding the obtained membrane preparation solution through an annular spinning jet, and taking a 40 wt% aqueous solution of N, N-dimethylacetamide as an external coagulation bath and a 50 wt% aqueous solution of N, N-dimethylacetamide as an internal coagulation bath to prepare a polymer hollow fiber membrane;
(3) and (3) crosslinking: after full rinsing, the polymer hollow fiber membrane is soaked in glyoxal water solution with the mass concentration of 4% and the pH value of 2.0, treated for 60min at the temperature of 70 ℃, taken out, and rinsed by deionized water to obtain the microporous membrane containing the crosslinked hydrophilic polymer.
Example 4:
a method for preparing a microporous membrane comprising a crosslinked hydrophilic polymer, comprising the steps of:
(1) preparing a film preparation solution: adding polyvinylidene fluoride, polyvinyl formal acetaldehyde (the mass content of vinyl alcohol chain links is 20%) and polyethylene glycol 400 into N, N-dimethylacetamide, and dissolving at 70 ℃ to obtain a film preparation solution; in the obtained film-forming solution, the mass concentration of polyvinylidene fluoride was 16%, the mass concentration of polyvinyl butyral was 2%, and the mass concentration of glycerin was 6%;
(2) film preparation: extruding the obtained membrane preparation solution through an annular spinning jet, and taking a 50 wt% aqueous solution of N, N-dimethylacetamide as an external coagulation bath and a 60 wt% aqueous solution of N, N-dimethylacetamide as an internal coagulation bath to prepare a polymer hollow fiber membrane;
(3) and (3) crosslinking: after full rinsing, the polymer hollow fiber membrane is soaked in glyoxal water solution with the mass concentration of 4% and the pH value of 2.0, treated for 60min at the temperature of 70 ℃, taken out, and rinsed by deionized water to obtain the microporous membrane containing the crosslinked hydrophilic polymer.
Comparative example 1:
a method for preparing a microporous membrane comprising a hydrophilic polymer, comprising the steps of:
(1) preparing a film preparation solution: polyvinylidene fluoride, polyvinyl butyral (the mass content of a vinyl alcohol chain link is 20 percent) and polyethylene glycol 400 are added into N, N-dimethylacetamide, and dissolved at 70 ℃ to obtain a film preparation solution; in the obtained film-making solution, the mass concentration of polyvinylidene fluoride is 12%, and the mass concentration of polyvinyl butyral is 5%; the mass concentration of the polyethylene glycol 400 is 13 percent;
(2) film preparation: and extruding the obtained membrane preparation solution through an annular spinning jet, and taking a 40 wt% aqueous solution of N, N-dimethylacetamide as an external coagulation bath and a 50 wt% aqueous solution of N, N-dimethylacetamide as an internal coagulation bath to prepare the polymer hollow fiber membrane.
Comparative example 2:
a method for preparing a microporous membrane comprising a crosslinked hydrophilic polymer, comprising the steps of:
(1) preparing a film preparation solution: polyvinylidene fluoride, polyvinyl butyral (the mass content of a vinyl alcohol chain is 5 percent) and polyethylene glycol 400 are added into N, N-dimethylacetamide, and dissolved at 70 ℃ to obtain a film preparation solution; in the obtained film-making solution, the mass concentration of polyvinylidene fluoride is 12%, and the mass concentration of polyvinyl butyral is 5%; the mass concentration of the polyethylene glycol 400 is 13 percent;
(2) film preparation: extruding the obtained membrane preparation solution through an annular spinning jet, and taking a 40 wt% aqueous solution of N, N-dimethylacetamide as an external coagulation bath and a 50 wt% aqueous solution of N, N-dimethylacetamide as an internal coagulation bath to prepare a polymer hollow fiber membrane;
(3) and (3) crosslinking: after full rinsing, the polymer hollow fiber membrane is soaked in glutaraldehyde aqueous solution with the mass concentration of 1% and the pH value of 1.0, treated for 20min at the temperature of 90 ℃, taken out, and rinsed with deionized water to obtain the microporous membrane containing the crosslinked hydrophilic polymer.
The microporous membranes prepared in the above examples and comparative examples were tested for material stability and hydrophilicity, and the results are shown in table 1.
The method for testing the stability and the hydrophilicity of the material comprises the following steps: soaking the obtained microporous membrane in an ethanol solution at room temperature for 24 hours, measuring the dry weight of the membrane before and after soaking, and calculating the weight loss rate of the membrane; and simultaneously measuring the contact angle between the surface of the membrane material and water before and after soaking.
Table 1: weight loss condition of microporous membrane and water contact angle measurement result on surface of membrane material
As can be seen from table 1, the microporous membranes prepared by the methods of embodiments 1 to 4 have low weight loss rate and good hydrophilic stability after being soaked in ethanol for 24 hours. In contrast, in comparative example 1, polyvinyl acetal was not crosslinked with a crosslinking agent, and the hydrophilic stability of the microporous membrane after soaking in ethanol was significantly lower than that in example 1. The mass content of vinyl alcohol chain units in the polyvinyl acetal added in the comparative example 2 is too low, so that the crosslinking reaction of the vinyl alcohol chain units and a subsequent crosslinking agent is not easy to realize, and the hydrophilic stability of the microporous membrane is also reduced.
Claims (10)
1. The microporous membrane containing the cross-linked hydrophilic polymer is characterized in that raw materials comprise a microporous membrane main body material and the cross-linked hydrophilic polymer, wherein the cross-linked hydrophilic polymer is cross-linked polyvinyl acetal.
2. The microporous membrane according to claim 1, wherein the polyvinyl acetal is selected from one or more of polyvinyl formal, polyvinyl acetal, polyvinyl formal, and polyvinyl butyral.
3. The crosslinked hydrophilic polymer-containing microporous membrane according to claim 1 or 2, wherein the polyvinyl acetal has a molecular chain content of not less than 10% by mass of vinyl alcohol segments.
4. The microporous membrane containing a crosslinked hydrophilic polymer according to claim 1, wherein the microporous membrane is made of one or more materials selected from polyvinylidene fluoride, polyvinyl chloride, and polysulfone polymers.
5. A method for producing a microporous membrane according to any one of claims 1 to 4, comprising the steps of:
(1) preparing a film preparation solution: adding a microporous membrane main body material, polyvinyl acetal and a film-making non-solvent into a solvent, and dissolving to obtain a film-making solution;
(2) film preparation: preparing the obtained membrane preparation solution into a polymer microporous membrane through a phase inversion process;
(3) and (3) crosslinking: and (3) soaking the polymer microporous membrane in an aqueous solution of a cross-linking agent, and treating to obtain the microporous membrane containing the cross-linked hydrophilic polymer.
6. The method for producing a microporous membrane according to claim 5, wherein the mass ratio of the polyvinyl acetal to the microporous membrane host material in the membrane-forming solution obtained in step (1) is less than 1: 1; the mass concentration of the microporous membrane main body material in the membrane preparation solution is 10-20%.
7. The method for producing a microporous membrane according to claim 5 or 6, wherein the non-solvent for membrane formation in the step (1) is one or more selected from ethanol, glycerin, ethylene glycol, polyethylene glycol, ethylene glycol monomethyl ether, and ethylene glycol dimethyl ether, and the mass concentration of the non-solvent for membrane formation in the membrane formation solution is 0 to 20%; the solvent is one or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
8. The method for preparing a microporous membrane according to claim 5, wherein the phase inversion process in the step (2) is a non-solvent immersion phase inversion or a non-solvent vapor-induced phase inversion.
9. The method of claim 5, wherein the cross-linking agent in step (3) is one or more selected from oxalic acid, malonic acid, succinic acid, citric acid, malic acid, formaldehyde, glyoxal, succinaldehyde, glutaraldehyde, and adipaldehyde; the mass concentration of the water solution of the cross-linking agent is 1-10%, and the pH value is 0-4.
10. The method for producing a microporous membrane according to claim 5 or 9, wherein the treatment temperature in the step (3) is 20 to 90 ℃ and the treatment time is 2 to 120 min.
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