CN101314111B - Organic/inorganic hybridisation strong alkalinity anion exchange membrane and preparation method thereof - Google Patents
Organic/inorganic hybridisation strong alkalinity anion exchange membrane and preparation method thereof Download PDFInfo
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- CN101314111B CN101314111B CN2008100647285A CN200810064728A CN101314111B CN 101314111 B CN101314111 B CN 101314111B CN 2008100647285 A CN2008100647285 A CN 2008100647285A CN 200810064728 A CN200810064728 A CN 200810064728A CN 101314111 B CN101314111 B CN 101314111B
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Abstract
The invention provides an organic-inorganic hybrid strong-basicity anion exchange membrane and a preparation method thereof, relating to the anion exchange membrane and the preparation method thereof. The anion exchange membrane and the preparation method solve the problems in the prior art for preparing the anion exchange membrane, such as environmental pollution, unsafe operation process and poor product performance. The organic-inorganic hybrid strong-basicity anion exchange membrane is prepared by polyvinylidene fluoride, polyether-ether-ketone, divinyl benzene, ethylstyrene, dimethyl phthalate, organic solvent, nanometer aluminium oxide particles, glyceryl methacrylate and benzoyl peroxide. The method comprises the following steps of: 1. weighing required compositions by weight percentage; 2. ultrasonically mixing the nanometer aluminium oxide particles with the organic solvent; 3. adding other compositions into the mixture to produce a casting solution; 4. preparing the membrane by the casting solution; and 5. immersing and rinsing the membrane, putting the membrane in an HCL solvent for immersing, and cleaning the membrane once more, thereby obtaining the organic-inorganic hybrid strong-basicity anion exchange membrane. The organic-inorganic hybrid strong-basicity anion exchange membrane and the preparation method thereof have the advantages of no environmental pollution, safe operation process and good product performance.
Description
Technical field
The present invention relates to amberplex and preparation method thereof.
Background technology
Amberplex is the critical component of electric dialyzator; Because anion-exchange membrane is more complicated and difficult more in preparation than cation; And it receives the pollution of deposite attack and organic substance the most easily in electrodialytic process; Directly influence the life-span of desalination apparatus, so the development of carrying out anion-exchange membrane more has special and important meaning.
At present, the preparation anion-exchange membrane adopts the technology of " first polymerization-back chloromethylation-reamination ", but its existence is difficult to the shortcoming that overcomes as follows: (1) is in chloromethylation; A large amount of inferior methylene joins the secondary crosslinked generation of bridge; Cause properties of product poor, for example the ion selectivity transmission coefficient is merely 0.82～0.89, and film resistance is high; Bad mechanical property, contamination resistance is poor; (2) contain noxious materials such as volatile chloromethyl ether, formaldehyde and hydrogen chloride, serious environment pollution in the chloromethylation mother liquor; (3) chloromethyl ether (especially dichlormethyl ether) is seriously carcinogenic, and harmful to health, operating process is dangerous, and the production of anion exchange resin and the development and the production of film have all been brought very big influence.
Summary of the invention
To the present invention seeks to that there is contaminated environment in the prior art for preparing anion-exchange membrane, operating process is dangerous and the problem of properties of product difference in order solving, and organic/inorganic hybridisation strong alkalinity anion exchange membrane and preparation method thereof to be provided.
Organic/inorganic hybridisation strong alkalinity anion exchange membrane of the present invention is processed by 5.0%～30% Kynoar, 1%～20% polyether-ether-ketone, 0.5%～20% divinylbenzene, 1%～20% ethyl styrene, 1%～10% repefral, 20%～80% organic solvent, 0.01%～4.0% nano-aluminium oxide particle, 1.0%～45% GMA and 0.05%～2.0% benzoyl peroxide by weight percentage; Wherein organic solvent is N, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.
The method for preparing organic/inorganic hybridisation strong alkalinity anion exchange membrane realizes according to the following steps: one; Take by weighing 5.0%～30% Kynoar by weight percentage; 1%～20% polyether-ether-ketone; 0.5%～20% divinylbenzene; 1%～20% ethyl styrene; 1%～10% repefral; 20%～80% organic solvent; 0.01%～4.0% nano-aluminium oxide particle; 1.0%～45% GMA and 0.05%～2.0% benzoyl peroxide; Two, under the condition of ultrasonic oscillation, the nano-aluminium oxide particle that takes by weighing is joined in the organic solvent that takes by weighing; Three, after the GMA that adding takes by weighing in organic solvent again, divinylbenzene, ethyl styrene, repefral, benzoyl peroxide evenly mixed, standing and defoaming got casting solution; Four, under 20～30 ℃ condition, casting solution is processed film on glass plate; Dry 2～3h under 60～70 ℃ condition; Put into then under 100～110 ℃ the condition and react 2～3h; After the cooling, put into deionized water and be dipped to film and from glass plate, come off automatically, under the room temperature again with the film natural air drying; Five, at room temperature film being put into mass concentration is that 5%～33.3% trimethylamine solution floods 2～4d; Use rinsed with deionized water then; Again film being put into concentration is to use washed with de-ionized water after the HCl solution of 0.1mol/L floods 22～26h, promptly gets organic/inorganic hybridisation strong alkalinity anion exchange membrane; Wherein organic solvent is N in the step 1, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.
Avoided using volatile noxious material among the present invention, free from environmental pollution, do not use the carcinogen chloromethyl ether, safe operation process, film-forming process is simple, be easy to industrialization; The adding of nano-aluminium oxide particle has improved the mechanical performance of film, has improved the contamination resistance of film, and ion exchange capacity has improved 8%, and film resistance has reduced 11%, and the ion selectivity transmission coefficient is up to 0.92～0.96.Through regulating the film that various proportion of raw materials obtain different performance, the organic/inorganic hybridisation strong alkalinity anion exchange membrane of gained has application prospect widely among the present invention.
The specific embodiment
The specific embodiment one: this embodiment organic/inorganic hybridisation strong alkalinity anion exchange membrane is by weight percentage by 5.0%～30% Kynoar; 1%～20% polyether-ether-ketone; 0.5%～20% divinylbenzene; 1%～20% ethyl styrene; 1%～10% repefral; 20%～80% organic solvent; 0.01%～4.0% nano-aluminium oxide particle; 1.0%～45% GMA and 0.05%～2.0% benzoyl peroxide are processed; Wherein organic solvent is N, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.
The specific embodiment two: this embodiment and the specific embodiment one are different is that organic/inorganic hybridisation strong alkalinity anion exchange membrane is processed by 10% Kynoar, 8% polyether-ether-ketone, 9% divinylbenzene, 9% ethyl styrene, 4% repefral, 32% organic solvent, 2.0% nano-aluminium oxide particle, 25% GMA and 1.0% benzoyl peroxide by weight percentage; Wherein organic solvent is N, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.Other is identical with the specific embodiment one.
The molecular weight of Kynoar is 350000～500000 dalton in this embodiment.
The specific embodiment three: this embodiment is different with the specific embodiment one or two is that the average grain diameter of nano-aluminium oxide particle is 5nm～100nm.Other is identical with the specific embodiment one or two.
The specific embodiment four: the method that this embodiment prepares organic/inorganic hybridisation strong alkalinity anion exchange membrane realizes according to the following steps: one; Take by weighing 5.0%～30% Kynoar by weight percentage; 1%～20% polyether-ether-ketone; 0.5%～20% divinylbenzene; 1%～20% ethyl styrene; 1%～10% repefral; 20%～80% organic solvent; 0.01%～4.0% nano-aluminium oxide particle; 1.0%～45% GMA and 0.05%～2.0% benzoyl peroxide; Two, under the condition of ultrasonic oscillation, the nano-aluminium oxide particle that takes by weighing is joined in the organic solvent that takes by weighing; Three, after the GMA that adding takes by weighing in organic solvent again, divinylbenzene, ethyl styrene, repefral, benzoyl peroxide evenly mixed, standing and defoaming got casting solution; Four, under 20～30 ℃ condition, casting solution is processed film on glass plate; Dry 2～3h under 60～70 ℃ condition; Put into then under 100～110 ℃ the condition and react 2～3h; After the cooling, put into deionized water and be dipped to film and from glass plate, come off automatically, under the room temperature again with the film natural air drying; Five, at room temperature film being put into mass concentration is that 5%～33.3% trimethylamine solution floods 2～4d; Use rinsed with deionized water then; Again film being put into concentration is to use washed with de-ionized water after the HCl solution of 0.1mol/L floods 22～26h, promptly gets organic/inorganic hybridisation strong alkalinity anion exchange membrane; Wherein organic solvent is N in the step 1, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.
The specific embodiment five: this embodiment and the specific embodiment four are different is to take by weighing 10% Kynoar, 8% polyether-ether-ketone, 9% divinylbenzene, 9% ethyl styrene, 4% repefral, 32% organic solvent, 2.0% nano-aluminium oxide particle, 25% GMA and 1.0% benzoyl peroxide in the step 1 by weight percentage.Other step and parameter are identical with the specific embodiment four.
The specific embodiment six: what this embodiment and the specific embodiment four were different is under 25 ℃ condition, casting solution to be processed film on glass plate in the step 4, and dry 2.5h under 65 ℃ condition puts into then under 105 ℃ the condition and reacts 2.5h.Other step and parameter are identical with the specific embodiment four.
The specific embodiment seven: this embodiment and the specific embodiment four are different is that at room temperature film to be put into mass concentration in the step 4 be that 30% trimethylamine solution floods 3d; Use rinsed with deionized water then, use washed with de-ionized water after again film being put into the HCl solution dipping 24h that concentration is 0.1mol/L.Other step and parameter are identical with the specific embodiment four.
The specific embodiment eight: the method that this embodiment prepares organic/inorganic hybridisation strong alkalinity anion exchange membrane realizes according to the following steps: one, take by weighing 10% Kynoar, 8% polyether-ether-ketone, 9% divinylbenzene, 9% ethyl styrene, 4% repefral, 32% N by weight percentage, N-dimethylacetylamide, 2.0% alundum (Al particle, 25% GMA and 1.0% benzoyl peroxide; Two, under the condition of ultrasonic oscillation, the nano-aluminium oxide particle that takes by weighing is joined the N that takes by weighing, in the N-dimethylacetylamide; Three, again to N, after the GMA that adding takes by weighing in the N-dimethylacetylamide, divinylbenzene, ethyl styrene, repefral, benzoyl peroxide evenly mixed, standing and defoaming got casting solution; Four, under 25 ℃ condition, casting solution is processed film on glass plate; Dry 2.5h under 65 ℃ condition puts into then under 105 ℃ the condition and reacts 2.5h, under the room temperature after the cooling; Put into deionized water and be dipped to film and from glass plate, come off automatically, again with the film natural air drying; Five, at room temperature film being put into mass concentration is that 30% trimethylamine solution floods 3d; Use rinsed with deionized water then; Use washed with de-ionized water after again film being put into the HCl solution dipping 24h that concentration is 0.1mol/L, promptly get organic/inorganic hybridisation strong alkalinity anion exchange membrane.
The gained organic/inorganic hybridisation strong alkalinity anion exchange membrane is through test in this embodiment, and the ion selectivity transmission coefficient is up to 0.95.
Claims (7)
1. organic/inorganic hybridisation strong alkalinity anion exchange membrane is characterized in that organic/inorganic hybridisation strong alkalinity anion exchange membrane processed by 5.0%～30% Kynoar, 1%～20% polyether-ether-ketone, 0.5%～20% divinylbenzene, 1%～20% ethyl styrene, 1%～10% repefral, 20%～80% organic solvent, 0.01%～4.0% nano-aluminium oxide particle, 1.0%～45% GMA and 0.05%～2.0% benzoyl peroxide by weight percentage; Preparation method: one, take by weighing above-mentioned raw materials by weight percentage; Two, under the condition of ultrasonic oscillation, the nano-aluminium oxide particle that takes by weighing is joined in the organic solvent that takes by weighing; Three, after the GMA that adding takes by weighing in organic solvent again, divinylbenzene, ethyl styrene, repefral, benzoyl peroxide evenly mixed, standing and defoaming got casting solution; Four, under 20～30 ℃ condition, casting solution is processed film on glass plate; Dry 2～3h under 60～70 ℃ condition; Put into then under 100～110 ℃ the condition and react 2～3h; After the cooling, put into deionized water and be dipped to film and from glass plate, come off automatically, under the room temperature again with the film natural air drying; Five, at room temperature film being put into mass concentration is that 5%～33.3% trimethylamine solution floods 2～4d; Use rinsed with deionized water then; Again film being put into concentration is to use washed with de-ionized water after the HCl solution of 0.1mol/L floods 22～26h, promptly gets organic/inorganic hybridisation strong alkalinity anion exchange membrane; Wherein organic solvent is N, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.
2. organic/inorganic hybridisation strong alkalinity anion exchange membrane according to claim 1 is characterized in that organic/inorganic hybridisation strong alkalinity anion exchange membrane processed by 10% Kynoar, 8% polyether-ether-ketone, 9% divinylbenzene, 9% ethyl styrene, 4% repefral, 32% organic solvent, 2.0% nano-aluminium oxide particle, 25% GMA and 1.0% benzoyl peroxide by weight percentage; Wherein organic solvent is N, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.
3. organic/inorganic hybridisation strong alkalinity anion exchange membrane according to claim 1 and 2, the average grain diameter that it is characterized in that the nano-aluminium oxide particle is 5nm～100nm.
4. the method for preparing organic/inorganic hybridisation strong alkalinity anion exchange membrane as claimed in claim 1 is characterized in that the method for preparing organic/inorganic hybridisation strong alkalinity anion exchange membrane realizes according to the following steps: one, take by weighing 5.0%～30% Kynoar, 1%～20% polyether-ether-ketone, 0.5%～20% divinylbenzene, 1%～20% ethyl styrene, 1%～10% repefral, 20%～80% organic solvent, 0.01%～4.0% nano-aluminium oxide particle, 1.0%～45% GMA and 0.05%～2.0% benzoyl peroxide by weight percentage; Two, under the condition of ultrasonic oscillation, the nano-aluminium oxide particle that takes by weighing is joined in the organic solvent that takes by weighing; Three, after the GMA that adding takes by weighing in organic solvent again, divinylbenzene, ethyl styrene, repefral, benzoyl peroxide evenly mixed, standing and defoaming got casting solution; Four, under 20～30 ℃ condition, casting solution is processed film on glass plate; Dry 2～3h under 60～70 ℃ condition; Put into then under 100～110 ℃ the condition and react 2～3h; After the cooling, put into deionized water and be dipped to film and from glass plate, come off automatically, under the room temperature again with the film natural air drying; Five, at room temperature film being put into mass concentration is that 5%～33.3% trimethylamine solution floods 2～4d; Use rinsed with deionized water then; Again film being put into concentration is to use washed with de-ionized water after the HCl solution of 0.1mol/L floods 22～26h, promptly gets organic/inorganic hybridisation strong alkalinity anion exchange membrane; Wherein organic solvent is N in the step 1, N-dimethylacetylamide, N, dinethylformamide or methyl-sulfoxide.
5. the method for preparing organic/inorganic hybridisation strong alkalinity anion exchange membrane according to claim 4 is characterized in that taking by weighing by weight percentage in the step 1 10% Kynoar, 8% polyether-ether-ketone, 9% divinylbenzene, 9% ethyl styrene, 4% repefral, 32% organic solvent, 2.0% nano-aluminium oxide particle, 25% GMA and 1.0% benzoyl peroxide.
6. according to claim 4 in the method for preparing organic/inorganic hybridisation strong alkalinity anion exchange membrane; It is characterized in that under 25 ℃ condition, casting solution being processed film on glass plate in the step 4; Dry 2.5h under 65 ℃ condition puts into then under 105 ℃ the condition and reacts 2.5h.
7. according to claim 4 in the method for preparing organic/inorganic hybridisation strong alkalinity anion exchange membrane; It is characterized in that in the step 5 that at room temperature it is that 30% trimethylamine solution floods 3d that film is put into mass concentration; Use rinsed with deionized water then, use washed with de-ionized water after again film being put into the HCl solution dipping 24h that concentration is 0.1mol/L.
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| WO2002096979A2 (en) * | 2001-05-30 | 2002-12-05 | Porex Technologies Corporation | Functionalized porous materials and applications in medical devices |
| CN1724586A (en) * | 2005-03-15 | 2006-01-25 | 哈尔滨工业大学 | Nanometer aluminium oxide modified polyvinilidene fluoride film and its preparation method and application |
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| WO2002096979A2 (en) * | 2001-05-30 | 2002-12-05 | Porex Technologies Corporation | Functionalized porous materials and applications in medical devices |
| CN1724586A (en) * | 2005-03-15 | 2006-01-25 | 哈尔滨工业大学 | Nanometer aluminium oxide modified polyvinilidene fluoride film and its preparation method and application |
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