CN105817272A - Preparation method of anion-exchange membrane based on ion liquid polymerization - Google Patents
Preparation method of anion-exchange membrane based on ion liquid polymerization Download PDFInfo
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- CN105817272A CN105817272A CN201610267407.XA CN201610267407A CN105817272A CN 105817272 A CN105817272 A CN 105817272A CN 201610267407 A CN201610267407 A CN 201610267407A CN 105817272 A CN105817272 A CN 105817272A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
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- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- 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
Abstract
The invention relates to the technical field of membrane separation. A preparation method of an anion-exchange membrane based on ion liquid polymerization comprises the following steps: 1, preparing a liquid solution containing unsaturated double-bond ions; 2, filling pores of supporting cloth with the liquid solution through an impregnating method; 3, heating the supporting cloth filled with the liquid solution containing the unsaturated double-bond ions without oxygen to initiate an ion liquid polymerization reaction; and 4, drying to form an electrodialysis membrane. The liquid solution containing the unsaturated double-bond ions is used for preparing the anion-exchange membrane, and the liquid solution containing the unsaturated double-bond ions is prepared by mixing an amino-containing organic monomer, an organic small molecule containing a carboxylic group, an organic solvent, a cross-linking agent and an initiator, wherein the amino-containing organic monomer is methacryloyloxyethyl trimethyl ammonium chloride, the organic small molecule containing the carboxylic group is acetic acid, propionic acid, butyric acid or benzoic acid; the cross-linking agent is ethyleneglycol dimethacrylate or divinyl benzene; and the initiator is 2,2'-azobis(2-methylpropionitrile) or benzoyl peroxide. The preparation method provided by the invention adopts a simple preparation process and is relatively low in preparation cost.
Description
Technical field
The present invention relates to technical field of membrane separation, be specifically related to the preparation method of a kind of anion exchange membrane based on ion liquid polymerization.
Background technology
The selective penetrated property utilizing semipermeable membrane is referred to as dialysis to the method separating different solute particles (such as ion).When carrying out dialysis under electric field action, the phenomenon that the charged solute particles (such as ion) in solution is migrated by film is referred to as electrodialysis.Electrodialytic process is electrochemical process and the combination of dialysis diffusion process, under the driving of applying direct current electric field, (i.e. cation can pass through cation exchange membrane to utilize the selective penetrated property of electrodialytic membranes, anion can pass through anion exchange membrane), anions and canons is respectively to anode and movable cathode.In ion migration processes, if the fixed charge of film and the opposite charge of ion, then ion can pass through；If their electric charge is identical, then ion is ostracised, thus realize solution desalinate, concentrate, the purpose such as refined or purification.
Electrodialysis is a technology more ripe in membrane separating process, is widely used to the unconventional water resource such as desalinization, bitter desalination and utilizes field.Electrodialysis is widely used in food, the industry such as medical and chemical equally, and waste water is carried out resource and zero discharge treatment.As: clean from acid solution and the waste liquid that metal surface is formed reclaims acid and metal, from electroplating wastewater, reclaim heavy metal ion, from synthetic fibers waste water, reclaim sulfate, from spent pulping liquor, reclaim sulphite, etc..
The electrodialytic membranes that electrodialytic process uses includes cation exchange membrane and two kinds of anion exchange membrane.In electrolyte aqueous solution, the macromolecular scaffold of cation exchange membrane is containing electronegative anionic group, it is allowed to positively charged cation permeable and repel stop anion；The macromolecular scaffold of anion exchange membrane is containing positively charged cation level segment, it is allowed to electronegative anion-permeable and repel stop cation, here it is the selective penetrated property of ion exchange membrane.In electrodialytic process, electrodialytic membranes exchanges with certain ion in aqueous solution unlike ion exchange resin, and the ion that difference is electrical simply plays selectivity and is not required to regeneration through effect, i.e. ion exchange membrane.The compartment of the electrode of electrodialysis process and film composition is referred to as room, pole, and the electrochemical reaction wherein occurred is identical with common electrode reaction.Oxidation reaction occurs in anode chamber, and anode water is acidity, and anode itself is easily corroded；Reduction reaction occurs in cathode chamber, and negative electrode water is alkalescence, easy fouling on negative electrode.
Electrodialytic membranes need to possess good chemical property, i.e. low resistance and Thief zone selectivity.Low resistance can reduce the voltage of running, so that the operation energy consumption of electrodialytic process is relatively low；Permselective property height makes electrodialytic membranes that counter ion (fixing the ion that charged group is the most contrary with film) is had high osmosis, but substantially impervious the most homo-ion (fixing the ion that charged group is the most identical with film), so that the operational efficiency of electrodialytic process is higher.Electrodialytic membranes also needs possess suitable mechanical stability, chemical stability and heat stability.As: can bear the operational stresses induced during being installed to electrodialysis plant and in electrodialytic process the hydraulic pressure of film both sides poor, it is possible to maintain a long-term stability when solution ph is between 2 to 12, it is possible to be not higher than 45 in temperatureoCan maintain a long-term stability during C.
Electrodialytic membranes can be prepared by different methods and technique, and wherein the radical polymerization containing unsaturated double-bond monomer is common method.United States Patent (USP) US4,024,043 preparation method describing a kind of anion exchange membrane, with polyethylene film as substrate, immerse in the solution of styrene, divinylbenzene and benzoyl peroxide composition, be sandwiched between two plate glass, pressurization, add thermal polymerization and obtain basement membrane, then in the chloromethyl ether of anhydrous stannic chloride, carry out chloromethylation, finally carry out quaterisation with trimethylamine acetone soln, prepare anion exchange membrane.PCT Patent WO2010/013861 describes and is immersed by porous polyethylene film in the solution containing 1-chloro-4-methyl-benzene, divinylbenzene and benzoyl peroxide composition, it is sandwiched between two plate glass and is polymerized to obtain basement membrane, then carry out quaterisation at trimethylamine aqueous solution and obtain anion exchange membrane.United States Patent (USP) US4,231,855 describe modacrylic are impregnated with dimethylaminoethyl methacrylate, ethylene glycol dimethacrylate fat and the solution of azodiisobutyronitrile composition, add and form basement membrane after thermal polymerization, then quaternary ammoniated in dimethyl sulfate ester solution.United States Patent (USP) US6,221,248 describe polypropylene cloth impregnation styrene sulfonic acid lithium, divinylbenzene and the solution of azo two methyl isobutyrate composition, obtain cation exchange membrane after adding thermal polymerization；Styrene sulfonic acid lithium is added Lithium hydrate by Sodium styrene sulfonate after hydrogen type cation exchange resin exchanges and makes.
Summary of the invention
Solve above-mentioned technical problem, the invention provides the preparation method of a kind of anion exchange membrane based on ion liquid polymerization, prepared by the radical polymerization containing unsaturated double-bond ionic liquid, preparation technology is simple, preparation cost is relatively low, the removing of prepared film salinity be applicable to aqueous solution or concentration.
In order to achieve the above object, the technical solution adopted in the present invention is, the preparation method of a kind of anion exchange membrane based on ion liquid polymerization, comprises the following steps: 1, preparation ionic liquid solution Han unsaturated double-bond；2, in supporting cloth hole, it is packed into this by wetting method and contains unsaturated double-bond ionic liquid solution；3, under the conditions of isolation oxygen, the support cloth heating containing unsaturated double-bond ionic liquid solution will be packed into, cause ion liquid polymerization reaction；4, cloth will be supported after polyreaction to dry, and be formed and support the cloth pore filling electrodialytic membranes of cross linked polymer.
Further, the described ionic liquid solution containing unsaturated double-bond is used for making anion exchange membrane, described mixes by by amino-contained organic monomer, carboxy-containing acid group's organic molecule, organic solvent, cross-linking agent and initiator containing unsaturated double-bond ionic liquid solution.
Further, the wherein preferred MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride of amino-contained organic monomer, the preferred acetic acid of carboxy-containing acid group's organic molecule, propanoic acid, butanoic acid or benzoic acid, the preferred Ethylene glycol dimethacrylate of cross-linking agent or divinylbenzene, the preferred azodiisobutyronitrile of initiator or benzoyl peroxide.
Further, wherein the molar ratio of carboxy-containing acid group's organic molecule and amino-contained organic monomer is 50-150:100, preferably 80-120:100；Cross-linking agent is 1-40:100, preferably 5-30:100 with the molar ratio of amino-contained organic monomer；Initiator molal quantity is 0.1-5:100, preferably 0.2-2:100 with the ratio of amino-contained organic monomer and cross-linking agent molal quantity sum.
Further, described support cloth is non-woven fabrics or microporous membrane, and preferably support cloth thickness, between 30 microns to 200 microns, supports between further preferred 40 microns to 120 microns of cloth thickness.
The present invention is by using technique scheme, compared with prior art, have the advantage that the preparation method that the invention discloses a kind of anion exchange membrane (homogeneous ion-exchange membrane) based on ion liquid polymerization, this way prepares electrodialytic membranes by the radical polymerization in non-woven fabrics or microporous membrane containing unsaturated double-bond ionic liquid monomer, prepared electrodialytic membranes has good chemical property, film uniform, Stability Analysis of Structures mutually, surface resistance is low, it is adaptable to various aqueous solution desalinations and salt concentrate application.Present invention process is simple, and cost is relatively low, it is not necessary to use substantial amounts of functional reagent to carry out " quaternized ", is the production technology of a kind of green economy.
In the present invention, the functional group of monomer and organic molecule define ionic liquid due to electrostatic interaction, enhance monomer dissolubility in organic solvent, decrease solvent load, contribute to preparing the finest and close electrodialytic membranes.
Detailed description of the invention
As a specific embodiment, the preparation method of the anion exchange membrane based on ion liquid polymerization of the present invention, including 1, preparation ionic liquid solution Han unsaturated double-bond；2, in supporting cloth hole, it is packed into this by wetting method and contains unsaturated double-bond ionic liquid solution；3, under the conditions of supporting cloth upper and lower both sides isolation oxygen, the support cloth heating containing unsaturated double-bond ionic liquid solution will be packed into, cause ion liquid polymerization reaction；4, cloth will be supported after polyreaction to dry, and be formed and support the cloth pore filling electrodialytic membranes of cross linked polymer.
In the lab, after preparing ionic liquid solution, support cloth is dipped in solution, take out after when one section, in supporting cloth hole, it is packed into this by wetting method and contains unsaturated double-bond ionic liquid solution, support cloth both sides cover aggregation thing thin slice, remove thin slice and the bubble supported between cloth, under the conditions of supporting cloth upper and lower both sides isolation oxygen, support cloth and foil laminates body are placed under 60-120oC temperature conditions and make initiator initiated polymerization, after polyreaction completes, dry, after peeling off two thin slices, i.e. obtain polymeric membrane.
In order to better illustrate the preparation method of the present embodiment, below by: 3 embodiments further illustrate technical solution of the present invention
Embodiment 1:
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 262.7g, acetic acid 60.7g and N-Methyl pyrrolidone 161.6g are mixed to form homogeneous solution, add ethylene glycol dimethacrylate fat 40.0g and AIBN1.66g, be mixed to form uniform solution.By aperture 0.45 μm, porosity be 50%, thickness be that the microporous membrane of 100 μm is dipped in solution, take out after infiltration 30min, it is positioned in the middle of two panels polyethylene terephthalate thin film, and removes the bubble supported between cloth and thin film, make base material form complex with two panels thin film.Complex is placed in 80oC baking oven placement 8h, after then being peeled off by two panels thin film, i.e. obtains anion exchange membrane.
Anion exchange membrane is soaked in 0.5M sodium chloride solution, tests membrane surface resistance.Surface resistance is between 3-5 Ω cm2。
Embodiment 2:
MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride 279.4g, benzoic acid 123.3g and N-Methyl pyrrolidone 201.4g are mixed to form homogeneous solution, add ethylene glycol dimethacrylate fat 40.0g and AIBN1.66g, be mixed to form uniform solution.By aperture 0.45 μm, porosity be 50%, thickness be that the microporous membrane of 50 μm is dipped in solution, take out after infiltration 30min, it is positioned in the middle of two panels polyethylene terephthalate thin film, and removes the bubble supported between cloth and thin film, make base material form complex with two panels thin film.Complex is placed in 80oC baking oven placement 8h, after then being peeled off by two panels thin film, i.e. obtains anion exchange membrane.
Anion exchange membrane is soaked in 0.5M sodium chloride solution, tests membrane surface resistance.Surface resistance is between 2-4 Ω cm2。
Although specifically showing in conjunction with preferred embodiment and describing the present invention; but those skilled in the art should be understood that; in the spirit and scope of the present invention limited without departing from appended claims; the present invention can be made a variety of changes in the form and details, be protection scope of the present invention.
Claims (4)
1. the preparation method of an anion exchange membrane based on ion liquid polymerization, it is characterised in that: (1) preparation ionic liquid solution Han unsaturated double-bond；(2) in supporting cloth hole, it is packed into this by wetting method and contains unsaturated double-bond ionic liquid solution；(3) under the conditions of isolation oxygen, the support cloth heating containing unsaturated double-bond ionic liquid solution will be packed into, cause ion liquid polymerization reaction；(4) cloth will be supported after polyreaction to dry, and be formed and support the cloth pore filling electrodialytic membranes of cross linked polymer.The described ionic liquid solution containing unsaturated double-bond is used for making anion exchange membrane, described mix by amino-contained organic monomer, carboxy-containing acid group's organic molecule, organic solvent, cross-linking agent and initiator containing unsaturated double-bond ionic liquid solution, wherein amino-contained organic monomer is MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, carboxy-containing acid group's organic molecule is acetic acid, propanoic acid, butanoic acid or benzoic acid, cross-linking agent is Ethylene glycol dimethacrylate or divinylbenzene, and initiator is azodiisobutyronitrile or benzoyl peroxide.
The preparation method of a kind of anion exchange membrane based on ion liquid polymerization the most according to claim 1, it is characterised in that: wherein carboxy-containing acid group's organic molecule is 50-150:100 with the molar ratio of amino-contained organic monomer；Cross-linking agent is 1-40:100 with the molar ratio of amino-contained organic monomer；Initiator molal quantity is 0.1-5:100 with the ratio of amino-contained organic monomer and cross-linking agent molal quantity sum.
3. according to claim 1 or the preparation method of described a kind of based on ion liquid polymerization anion exchange membrane, it is characterised in that: described support cloth is non-woven fabrics or microporous membrane.
4. according to the preparation method of a kind of based on ion liquid polymerization the anion exchange membrane described in Claims 2 or 3, it is characterised in that: support cloth thickness between 30 microns to 200 microns.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110813096A (en) * | 2019-10-30 | 2020-02-21 | 中国农业科学院麻类研究所 | Microfiltration membrane and preparation method and application thereof |
| CN111111478A (en) * | 2019-12-23 | 2020-05-08 | 山东天维膜技术有限公司 | Preparation method of PVDF-based cation exchange membrane |
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| CN101412776A (en) * | 2008-11-18 | 2009-04-22 | 浙江大学 | Preparation of high strength ionic liquid gel |
| CN101619115A (en) * | 2009-07-30 | 2010-01-06 | 苏州大学 | High-temperature proton-exchange polymer film and preparation method thereof |
| CN103657448A (en) * | 2013-12-31 | 2014-03-26 | 山东天维膜技术有限公司 | Preparing method of anion-exchange membrane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412776A (en) * | 2008-11-18 | 2009-04-22 | 浙江大学 | Preparation of high strength ionic liquid gel |
| CN101619115A (en) * | 2009-07-30 | 2010-01-06 | 苏州大学 | High-temperature proton-exchange polymer film and preparation method thereof |
| CN103657448A (en) * | 2013-12-31 | 2014-03-26 | 山东天维膜技术有限公司 | Preparing method of anion-exchange membrane |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813096A (en) * | 2019-10-30 | 2020-02-21 | 中国农业科学院麻类研究所 | Microfiltration membrane and preparation method and application thereof |
| CN110813096B (en) * | 2019-10-30 | 2022-04-08 | 中国农业科学院麻类研究所 | Microfiltration membrane and preparation method and application thereof |
| CN111111478A (en) * | 2019-12-23 | 2020-05-08 | 山东天维膜技术有限公司 | Preparation method of PVDF-based cation exchange membrane |
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