CN109954410B - Preparation method of semi-homogeneous anion exchange membrane - Google Patents
Preparation method of semi-homogeneous anion exchange membrane Download PDFInfo
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- CN109954410B CN109954410B CN201711427141.1A CN201711427141A CN109954410B CN 109954410 B CN109954410 B CN 109954410B CN 201711427141 A CN201711427141 A CN 201711427141A CN 109954410 B CN109954410 B CN 109954410B
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses a preparation method of a semi-homogeneous anion exchange membrane. Dissolving polyvinylidene fluoride, chloromethylated polystyrene, a cross-linking agent and an initiator in an organic solvent to prepare a uniform mixed membrane casting solution, coating the membrane casting solution on reinforced gridding cloth after ultrasonic defoaming, passing the membrane through a hot water tank, removing the organic solvent and forming a cross-linking structure in the membrane to prepare a continuous coiled semi-homogeneous chloromethylated membrane, soaking the membrane in a trimethylamine aqueous solution for a certain time, transforming by a sodium chloride solution, and washing by water to prepare the continuous coiled semi-homogeneous anion exchange membrane. The preparation method of the semi-homogeneous anion exchange membrane simplifies membrane production equipment and a membrane preparation process, improves production efficiency, and the membrane is continuously coiled and has a high-molecular interpenetrating network structure, the ion exchange groups on the surface and in the whole membrane are uniform, the membrane resistance is low, the strength is high, the size stability is good, and the comprehensive performance is close to that of a homogeneous ion exchange membrane.
Description
Technical Field
The invention relates to the technical field of anion exchange membrane preparation, in particular to a preparation method of a semi-homogeneous anion exchange membrane.
Background
The ion exchange membrane has unique ion exchange characteristics, plays an increasingly important role in the aspects of clean production, environmental protection, energy conversion and the like, is particularly suitable for the requirements of modern industry on new energy, energy conservation, low-grade raw material reutilization and environmental pollution treatment, is widely applied in the fields of seawater desalination and the like, and becomes an important component part for realizing economic sustainable development strategy.
The continuous production method of polyvinyl chloride semi-homogeneous anion-cation exchange membrane disclosed in Chinese patent 201510347434.6 is characterized by adopting double screw extrusion to form membrane, adhering mesh cloth on two sides of the membrane, and rolling by four rollers to produce roll polyvinyl chloride semi-homogeneous ion exchange membrane. The ion exchange membrane resin powder in the early stage of the method adopts a PVC impregnation monomer, and the impregnation is uneven, so that the method has certain limitation; in addition, the processing temperature is high, PVC and functional ions are easy to degrade, and particularly the PVC semi-homogeneous anion exchange membrane;
the preparation method of polystyrene ion exchange alloy membrane disclosed in Chinese patent application No. 201110417296.3 comprises the steps of firstly granulating polyvinylidene fluoride, obtaining polymer absorption particles by absorbing and immersing styrene polymerization solution, then carrying out suspension polymerization on the polymer absorption particles to obtain polymer alloy particles, obtaining cation or anion exchange alloy resin by sulfonation or chloromethylation amination, and finally adopting intermittent production (i.e. banburying, open refining, sheet pulling and hot pressing). The membrane obtained in this patent is an ion exchange membrane of semi-homogeneous structure. The intermittent production method for producing the ion exchange membrane has the defects of low production efficiency, high labor cost and the like.
Chinese patent application No. 201110004257.0, chinese patent application No. 94106397.6, and chinese patent application No. 201510002532.3 are all ion exchange membranes prepared by a base membrane imbibition method, i.e., the base membrane imbibition method generally uses an inert polymer base membrane to imbibe monomers, and then polymerizes, forms a membrane, and functionalizes, and a typical example is to use a polyene base membrane to imbibe styrene/divinylbenzene monomers and an initiator to prepare a cation exchange membrane or an anion exchange membrane respectively by hot pressing, polymerization, sulfonation, or chloromethyl/quaternization.
The ionic exchange membrane is manufactured by a slurry coating method by Nippon mountain Caoda company, for example, styrene, divinylbenzene, polyvinyl chloride powder, an initiator and the like are mixed in proportion, stirred, pulped, slurry coated, hot pressed and polymerized to prepare a base membrane, and then the base membrane is functionalized to obtain a cation exchange membrane and an anion exchange membrane (see the basic principle and application of the ionic exchange membrane, Kudzuvine Dai, Ningchun translation, and the pages 8 to 9, published by the chemical industry publishers, 2010).
The ion exchange membrane prepared by the method is usually prepared into a base membrane firstly, and then functional group reaction is carried out to introduce ion exchange groups. If the most common styrene/divinylbenzene system is adopted, strong-basicity anion exchange groups are introduced through chloromethyl/quaternization, the method is relatively complex, particularly the difficulty in controlling the uniformity of the ion exchange groups on the surface and inside of the whole membrane is high, the chemical reaction process is difficult, a very precise control means is required, the requirements on hot-pressing polymerization and membrane functionalization equipment are high, and the technical difficulty is high. The membranes produced by both methods are also essentially semi-homogeneous ion exchange membranes.
Disclosure of Invention
The invention aims to provide a preparation method of a semi-homogeneous anion exchange membrane aiming at the technical defects in the prior art.
The technical scheme adopted for realizing the purpose of the invention is as follows:
a method for preparing a semi-homogeneous anion exchange membrane comprises the following steps:
a. polyvinylidene fluoride, chloromethylated polystyrene, an organic solvent, a cross-linking agent and an initiator are mixed according to a mass ratio of 8-20: 80-200: 0.7-3: 0.1-0.5, preparing a uniform casting solution;
b. coating the membrane casting solution on reinforced gridding cloth after ultrasonic defoaming to form a semi-homogeneous chloromethylated membrane with uniform thickness;
c. and (2) passing the membrane through a hot water tank, removing the organic solvent, forming a cross-linked structure in the membrane, soaking in a trimethylamine aqueous solution for a certain time, transforming by using a sodium chloride solution, and washing by water to obtain the continuous coiled semi-homogeneous anion exchange membrane.
In the step c, the crosslinking degree of the membrane is controlled well, and if the crosslinking degree is not high or is too low, the membrane is seriously swelled, the dimensional stability is poor, and the application is difficult; if the degree of crosslinking is too high, the exchange capacity loss of the membrane is large, so that the resistance of the membrane is large, and the energy consumption of the membrane in the application process is increased, and preferably, the degree of crosslinking is 6-9.
Preferably, the chlorine content of the chloromethylated polystyrene in the step a is 12-25%;
preferably, the organic solvent of step a is one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the crosslinking agent of step a is divinylbenzene or ethylene glycol dimethacrylate.
Preferably, the initiator of step a is dibenzoyl peroxide or azobisisobutyronitrile.
Preferably, the viscosity of the casting solution of step a is 2000cps to 4000 cps. If the viscosity of the casting film liquid is too high, the film is too thick and the film coating efficiency is low; if the viscosity of the casting solution is too low, the casting solution is too thin or difficult to form a film, and therefore, the viscosity of the casting solution is preferably 2000cps to 4000cps, and may be specifically selected from 2000cps to 4000cps depending on the thickness of the film.
Preferably, the reinforcing mesh fabric of step b is one of nylon, polypropylene and ultra-high molecular weight polyethylene.
Preferably, the temperature of hot water in the hot water tank in the step c is 50-100 ℃, and the heat treatment time is 15-30 min.
Preferably, the soaking time of the semi-homogeneous chloromethylation membrane in the step c in the trimethylamine water solution is 12-48 h, and the soaking temperature is 25-40 ℃.
Preferably, the chloromethylated polystyrene is a non-crosslinked polymer. Since the crosslinked polymer exhibits insolubility, chloromethylated polystyrene is a non-crosslinked polymer in order to dissolve chloromethylated polystyrene in an organic solvent.
The invention adopts the technology of semi-homogeneous anion exchange membrane, the prepared ion exchange membrane is continuously coiled, has a high molecular interpenetrating network structure, high strength, good dimensional stability, low membrane resistance and comprehensive performance close to that of homogeneous ion exchange membrane; the uniformity of ion exchange groups on the surface and inside of the whole membrane can be effectively controlled, the process that the whole membrane needs chemical reaction is avoided, the technical difficulty of coiled membrane production is reduced, and the requirements of production equipment are lowered; can also improve the production efficiency and reduce the labor cost.
The invention solves the technical problems of complex semi-homogeneous anion exchange membrane preparation process, high difficulty in continuous roll production, low production efficiency, high labor cost, high difficulty in controlling the uniformity of ion exchange groups on the surface and inside of the whole membrane, high requirement on membrane functionalized equipment, high technical difficulty and the like in the prior art because of difficult chemical reaction process, and the like.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1:
a) the mass ratio of polyvinylidene fluoride, chloromethylated polystyrene (chlorine content is 15%), N-dimethylacetamide, ethylene glycol dimethacrylate and dibenzoyl peroxide is as follows: 12: 20: 150: 2: 0.4, preparing a uniform casting solution according to the mixture ratio, wherein the viscosity is about 2900 cps;
b) coating the membrane casting solution on ultra-high molecular weight polyethylene mesh cloth after ultrasonic defoaming to form a semi-homogeneous chloromethylated polystyrene membrane with the thickness of 0.16 mm;
c) and (c) passing the membrane formed in the step (b) through a hot water tank, placing the membrane into hot water, performing hot water heat treatment, treating for 5min at the hot water temperature of 50 ℃, treating for 25min at the hot water temperature of 90 ℃, removing N, N-dimethylacetamide, forming a cross-linking structure inside the membrane at the same time, preparing a continuous roll of semi-homogeneous phase chloromethylation membrane, soaking the continuous roll of semi-homogeneous phase chloromethylation membrane in trimethylamine aqueous solution for 48h at the soaking temperature of 25 ℃, cleaning the membrane with clear water after soaking is finished, performing transformation by using 1mol/L sodium chloride solution for 1.5h, taking out the membrane, and washing the membrane with water to obtain the continuous roll of semi-homogeneous phase anion exchange membrane.
Example 2:
a) polyvinylidene fluoride, chloromethylated polystyrene (the chlorine content is 23 percent), N-methyl pyrrolidone, divinylbenzene and azodiisobutyronitrile are mixed according to the mass ratio: 18: 20: 150: 2: 0.27, preparing a uniform casting solution according to the mixture ratio, wherein the viscosity is about 3500 cps;
b) coating the casting solution on polypropylene mesh cloth after ultrasonic defoaming to form a semi-homogeneous chloromethylated polystyrene film with the thickness of 0.19 mm;
c) and (c) passing the membrane formed in the step (b) through a hot water tank, placing the membrane into hot water, performing hot water heat treatment, treating for 10min at the hot water temperature of 60 ℃, treating for 20min at the hot water temperature of 90 ℃, removing the N-methyl pyrrolidone, forming a cross-linking structure in the membrane at the same time, preparing a continuous roll of semi-homogeneous phase chloromethylation membrane, soaking the continuous roll of semi-homogeneous phase chloromethylation membrane in a trimethylamine aqueous solution for 12h at the soaking temperature of 40 ℃, cleaning the membrane with clear water after soaking is finished, performing transformation by using 1mol/L sodium chloride solution for 2h, taking out, and washing with water to obtain the continuous roll of semi-homogeneous phase anion exchange membrane.
Example 3:
a) polyvinylidene fluoride, chloromethylated polystyrene (chlorine content is 18%), N-dimethylformamide, divinylbenzene and dibenzoyl peroxide in a mass ratio of: 15: 15: 130: 1.5: 0.3, preparing a uniform casting solution according to the mixture ratio, wherein the viscosity is about 3200 cps;
b) coating the membrane casting solution on nylon mesh cloth after ultrasonic defoaming to form a semi-homogeneous chloromethylation membrane with the thickness of 0.18 mm;
c) and (c) passing the membrane formed in the step (b) through a hot water tank, placing the membrane into hot water, performing hot water heat treatment, treating for 5min at the hot water temperature of 50 ℃, treating for 22min at the hot water temperature of 85 ℃, removing N, N-dimethylformamide, forming a cross-linking structure inside the membrane at the same time, preparing a continuous roll of semi-homogeneous phase chloromethylation membrane, soaking the membrane in a trimethylamine aqueous solution for 24h at the soaking temperature of 30 ℃, cleaning the membrane with clear water after soaking is finished, performing transformation by using 1mol/L sodium chloride solution for 1.5h, taking out the membrane, and washing with water to obtain the continuous roll of semi-homogeneous phase anion exchange membrane.
Table 1 shows the membrane performance test data for each example:
TABLE 1
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing a semi-homogeneous anion exchange membrane is characterized by comprising the following steps:
a. polyvinylidene fluoride, chloromethylated polystyrene, an organic solvent, a cross-linking agent and an initiator are mixed according to a mass ratio of 8-20: 80-200: 0.7-3: 0.1-0.5, preparing a uniform casting solution;
b. coating the membrane casting solution on reinforced gridding cloth after ultrasonic defoaming to form a semi-homogeneous chloromethylated membrane with uniform thickness;
c. and (2) passing the membrane through a hot water tank, removing the organic solvent, forming a cross-linked structure in the membrane, soaking in a trimethylamine aqueous solution for a certain time, transforming by using a sodium chloride solution, and washing by water to obtain the continuous coiled semi-homogeneous anion exchange membrane.
2. The method according to claim 1, wherein the chloromethylated polystyrene of step a has a chlorine content of 12-25%.
3. The method of claim 1, wherein the organic solvent of step a is one of N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.
4. The process for the preparation of a semi-homogeneous anion exchange membrane according to claim 1, wherein the cross-linking agent of step a is divinylbenzene or ethylene glycol dimethacrylate.
5. The method of claim 1, wherein the initiator of step a is dibenzoyl peroxide or azobisisobutyronitrile.
6. The method for preparing a semi-homogeneous anion-exchange membrane according to claim 1, wherein the viscosity of the casting solution of step a is 2000cps to 4000 cps.
7. The method of claim 1, wherein the reinforced mesh fabric of step b is one of nylon, polypropylene, and ultra-high molecular weight polyethylene.
8. The preparation method of the semi-homogeneous anion-exchange membrane according to claim 1, wherein the hot water temperature in the hot water tank in the step c is 50-100 ℃ and the heat treatment time is 15-30 min.
9. The method for preparing a semi-homogeneous anion exchange membrane according to claim 1, wherein the semi-homogeneous chloromethylated membrane obtained in the step c is soaked in the trimethylamine water solution for 12-48 h at a temperature of 25-40 ℃.
10. The method of claim 1, wherein the chloromethylated polystyrene is a non-crosslinked polymer.
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| CN101306331A (en) * | 2008-02-01 | 2008-11-19 | 中国科学技术大学 | Homogeneous phase anion-exchange membrane and preparation method thereof |
| CN102580572A (en) * | 2012-03-06 | 2012-07-18 | 中国科学技术大学 | Anion-exchange membrane and preparation method thereof |
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| CN103682212A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of basic porous membrane in liquid flow energy storage battery |
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| JPS59202227A (en) * | 1983-04-28 | 1984-11-16 | Nok Corp | Anion exchange membrane and its production |
| JPH05214125A (en) * | 1992-02-03 | 1993-08-24 | Asahi Chem Ind Co Ltd | Anion exchange membrane excellent in selectivity between anion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101306331A (en) * | 2008-02-01 | 2008-11-19 | 中国科学技术大学 | Homogeneous phase anion-exchange membrane and preparation method thereof |
| CN102580572A (en) * | 2012-03-06 | 2012-07-18 | 中国科学技术大学 | Anion-exchange membrane and preparation method thereof |
| CN103682212A (en) * | 2012-09-06 | 2014-03-26 | 中国科学院大连化学物理研究所 | Application of basic porous membrane in liquid flow energy storage battery |
| CN103223306A (en) * | 2013-04-24 | 2013-07-31 | 浙江大学宁波理工学院 | Polystyrene /polystyrene anion exchange alloy film preparation method |
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