CN101306331A - Homogeneous phase anion-exchange membrane and preparation method thereof - Google Patents
Homogeneous phase anion-exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a homogeneous anion exchange membrane as well as the preparation method thereof. The invention is characterized in that the homogeneous anion exchange membrane takes chloromethylated styrene, styrene or/and alkyl styrene as monomers, takes divinyl benzene as a cross-linking agent, takes benzoyl peroxide or azobisisobutyronitrile as an initiator, and takes bromomethylation poly (1,4- dimethyl2, 6- phenylene oxide) or chloroacetylized poly (1,4-dimethyl2, 6-phenylene oxide) as a polymer reinforcing agent, so as to prepare a uniform solution which is used for pasting a membrane on reinforced fabrics, and the homogeneous anion exchange membrane can be obtained by pretreating a basal membrane obtained by polymerization and then carrying out quaternary ammoniation. The invention obtains a functional group through adopting aromatic polymer, thereby the obtained anion exchange membrane has high exchange capacity, good electrochemical properties, uniform structure and good heat resistance; the slurry is homogeneous, thereby being easy for pasting; the monomers serving as the solvent can be polymerized, thereby being a green and solvent free process; the polymer content and the cross-linking degree can be adjusted, and the types of the sustainer can be changed, thereby obtaining products with different structural morphologies and functions.
Description
Technical field
The invention belongs to the membrane technology field, particularly homogeneous-phase anion exchange film and online polymerization thereof, solvent free preparation method.
Background technology
Anion-exchange membrane is widely used at aspects such as electrodialysis, diffusion dialysis, film electrolysis, fuel cell, electrochemical sensors, and its exploitation and improvement receive the concern of theoretical circles and industrial quarters always.Homogeneous-phase anion exchange film since its fixed group and film mutually main body have advantages such as even structure, resistance are little with the chemical bond combination, the application in electrodialysis and PEM is more extensive.
A kind of pasty state legal system that Chinese patent ZL 90103412.6 announces is equipped with the method for anion-exchange membrane; this film is by acrylic acid epoxy alkane ester class or alkyl acrylic alkylene oxide ester class (monomer); divinylbenzene etc. (crosslinking agent); polyvinyl acetate or vinyl chloride-vinyl acetate copolymer (reinforcing agent); phthalic acid dialkyl class (flexibilizing agent) and benzoyl peroxide or azodiisobutyronitrile are polymerized; its preparation method is: earlier said components is made into slurries; be coated in then and strengthen that the pressurized, heated polymerization obtains basement membrane on the fabric; carry out aminating reaction with aminated compounds again, promptly obtain having certain flexible anion-exchange membrane.In order to be coated with slurries uniformly, this method has taked to add a large amount of polymeric additives, but these additives itself can not be by amination in the amination process, and the film of gained still is half equal phase structure.
Holland " membrane science and technical journal " (Journal of Membrane Scie nce, 2003,221,2298-231) reported a kind of preparation method of anion-exchange membrane of semi-intercrossing network, low-density polyethylene film (60 microns of thickness) immersion is contained styrene, chloromethylation styrene, divinylbenzene, fully soak suction in the solution of benzoyl peroxide, be placed on after the taking-up between two polyester films, irradiation polymerization obtains basement membrane under ultraviolet light, behind the homopolymers with dichloroethanes flush away surface, at 50 ℃, 0.5M trimethylamine solution in quaternized 30-120 minute and obtain this anion-exchange membrane, this method step complexity, need the polyethylene film swelling to soak the suction monomer, and monomer can destroy the structure of polymer itself in the polyethylene film interior polymeric, cause final basement membrane mechanical strength not high, polyethylene film itself can not be by quaternized, so the film of gained still is half equal phase structure.
U.S.'s " using polymer magazine " (Journal of Applied Polymer, 2006,100 (3): 2248-2251) reported a kind of method for preparing anion-exchange membrane by radical polymerization, at first 2,2 '-azodiisobutyronitrile is done under the situation of initator and is obtained 4-brominated polyphenylether vinylpyridine and cinnamic copolymer by radical polymerization, then this copolymer and the reaction of 1-bromooctane are formed pyridiniujm, then the polymer 1g with the salify of this form is dissolved in the 10ml nitromethane, obtain casting solution, this casting solution is coated in forms basement membrane on the screen cloth, nitromethane is wherein removed by natural evaporation at room temperature.This method step complexity needs the evaporation organic solvent, can produce serious pollution to environment, and since this film formed be the form of weakly alkaline pyridiniujm, so exchange capacity is restricted.
Summary of the invention
The objective of the invention is to propose a kind of homogeneous-phase anion exchange film and preparation method thereof,, provide the approach of a solvent free for the preparation of homogeneous-phase anion exchange film to overcome the above-mentioned defective of prior art.
Homogeneous-phase anion exchange film of the present invention is made up of high-molecular copolymer, macromolecule reinforcing agent and enhancing fabric; It is characterized in that: described high-molecular copolymer is that chloromethylation styrene, styrene are or/and alkyl-substituted styrene and divinylbenzene copolymer; Described macromolecule reinforcing agent is bromomethylation poly-(1,4-dimethyl 2,6-penylene oxygen) or chloroacetylation poly-(1,4-dimethyl 2,6-penylene oxygen); Described enhancing fabric is glass fabric, polypropylene cloth, polyvinyl chloride cloth or teflon cloth; The proportioning of described anion exchange membrane component is: the ratio of the quality of macromolecule reinforcing agent and polymer copolymerization amount is 1-5/10; The water content of this anion-exchange membrane is 4.0%-43.6%, and ion exchange capacity is 0.43-1.66mmol/g-dry membrane, and film resistance is 1.27-18.56 Ω cm
2, transference number of ions is 0.83-0.98.
The preparation method of homogeneous-phase anion exchange film of the present invention comprises the preparation of monomer, crosslinking agent, macromolecule reinforcing agent and initator mixed solution, polymerization film formation, preliminary treatment and amination step;
Being formulated as of described monomer, crosslinking agent, macromolecule reinforcing agent and initator mixed solution: the mixed solution that at first accounts for mixed liquor volume mark 2%-15% preparation crosslinking agent and monomer by crosslinking agent, it is characterized in that: the ratio of macromolecule reinforcing agent in the above-mentioned mixed solution dissolving of every 10ml 1-5g macromolecule reinforcing agent is dissolved in the above-mentioned mixed solution, in this solution, dissolves the ratio dissolving initator of 0.3-1.8g initator again in the mixed solution of every 10ml divinylbenzene and monomer;
Described polymerization film formation step is: after being evenly coated in above-mentioned final mixed solution on the enhancing fabric, at 6-10 hour polymerization film formation of 70-90 ℃ of heating;
Described preliminary treatment and amination step are: earlier will the above-mentioned film that makes be in 20-30 ℃ of immersion 10-20 hour in the pretreated water solution of 5-20% at the mass fraction of amine, it is in the aqueous solution of 10-40% quaternized 24-48 hour at the trimethylamine mass fraction again, taking-up spends the deionised water drying, promptly gets anion-exchange membrane.
Described monomer comprises chloromethylation styrene, styrene or/and alkyl-substituted styrene, and its structure is:
Described initator is benzoyl peroxide or azodiisobutyronitrile.
Described macromolecule reinforcing agent is bromomethylation poly-(1,4-dimethyl 2,6-penylene oxygen), and its structure is:
Or chloroacetylation poly-(1,4-dimethyl 2,6-penylene oxygen), its structure is:
Described pretreated water solution comprises N, N, N ', the N '-4-methyl hexamethylene diamine aqueous solution, methylamine water solution, dimethylamine agueous solution, ethylenediamine solution or ammoniacal liquor.
Described enhancing fabric comprises glass fabric, polypropylene cloth, polyvinyl chloride cloth or teflon cloth.
The preparation method of the anion-exchange membrane of announcing with Chinese patent ZL 90103412.6 compares, the present invention uses aromatic polymer to replace linear polymer such as the polyvinyl acetate or the vinyl chloride-vinyl acetate copolymer of the soluble nonionic in this patent, thereby can introduce quaternary ammonium group, not only guarantee the membrane structure of formation homogeneous phase but also can improve ion exchange capacity; With Holland " membrane science and technical journal " (Journal of Membrane Scie nce, 2003,221,2298-231) preparation method of the anion-exchange membrane of Bao Dao half interpenetrating network structure compares, dissolve each other because monomer of the present invention and polymer can mix in varing proportions, the suction of soaking of monomer is not limited by polymer, and very big adjustability is arranged, polymer itself can be formed full homogeneous ion-exchange membrane structure by amination; Owing to can introduce fabric, film strength is bigger, does not especially need with an organic solvent pre-swelling and removal homopolymers step subsequently, and is pollution-free, easier realization scale; With U.S.'s " using polymer magazine " (Journal of Applied Polymer, 2006,100 (3): 2248-2251) Bao Dao anion-exchange membrane is compared, the present invention is not with an organic solvent, do not need to handle residual solvent, and film has cross-linked structure, and intensity is bigger, and dimensional stability is better.Therefore, the present invention combines the plurality of advantages of existing anion-exchange membrane, the performance of film can be regulated and control by the ratio of different aromatic polymer content and kind, monomer and crosslinking agent, obtains the homogeneous-phase anion exchange film of different exchange capacities, stable performance.The inventive method has easy, rapid and safe advantage from work angle; From performance perspective, the film that makes has homogeneous phase stable performance, ion exchange capacity height, the strong characteristics of resistance tocrocking, but and seriation exploitation, satisfy the needs in different application field.
The specific embodiment
Further describe the preparation method of homogeneous-phase anion exchange film of the present invention by the following examples.
Embodiment 1:
The volume fraction that 3g methyl brominated polyphenylether room temperature is dissolved in the 10ml divinylbenzene is in the mixed solution of 6% chloromethylation styrene and divinylbenzene, fully stir homogeneous solution, add 0.8g benzoyl peroxide initator again, get uniform coating liquid after treating to dissolve fully; This coating liquid is coated on the polypropylene fabric that thickness is 0.10mm, obtained basement membrane in 8 hours 80 ℃ of polymerizations; Taking out basement membrane, in soaking 24 hours in mass fraction is 10% ammonia spirit under the room temperature, is in 10% the trimethylamine solution quaternized 12 hours at mass fraction with this basement membrane then, is immersed in the NaCl solution of 1mol/l again and changes into the Cl type.
Basement membrane after above-mentioned processing is carried out infrared test, and the result is: 500-600cm
-1The stretching vibration peak of C-Br in the corresponding brominated polyphenylether, 790-810cm
-1The stretching vibration peak of C-Cl in the corresponding chloromethylation styrene, 3,000-3,100cm
-1Correspond respectively to the C-H and the C-C stretching vibration peak of phenyl ring with 1620-1580, show that existing methyl brominated polyphenylether has chloromethylated polystyrene again in the basement membrane.After the basement membrane amination, at 990-810cm
-1The corresponding N in the new peak that occurs
+-(CH
3)
3, proved the existence of quaternary ammonium group.
Water content and ion exchange capacity test shows, the water content of the film after quaternized and anion-exchange capacity are respectively 15.4% and 1.55mmol/g-dry membrane, and film resistance is 1.78 Ω cm
2, transference number of ions is 0.96.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 2:
Adopt operating process similarly to Example 1, just wherein the consumption of methyl brominated polyphenylether changes 1g into, and the consumption of initator changes 0.3g into, has obtained the similar film of structure.
Record the water content of the anion-exchange membrane that is prepared by present embodiment and ion exchange capacity and be respectively 12.4% and 0.91mmol/g-drymembrane, film resistance is 16.69 Ω cm
2, transference number of ions is 0.83.
Embodiment 3:
Adopt operating process similarly to Example 1, and change the consumption of methyl brominated polyphenylether into 4g, the consumption of initator changes 1.4g into, has obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 19.9% and 1.53mmol/g-dry membrane, film resistance is 2.79 Ω cm
2, transference number of ions is 0.96.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 4:
Adopt operating process similarly to Example 1, but change the consumption of methyl brominated polyphenylether into 5g, the consumption of initator changes 1.8g into, has obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 16.7% and 1.33mmol/g-dry membrane, film resistance is 4.93 Ω cm
2, transference number of ions is 0.95.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 5:
Adopt operating process similarly to Example 1, and change the volume fraction of divinylbenzene into 2%, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 43.6% and 1.66mmol/g-dry membrane, film resistance is 1.27 Ω cm
2, transference number of ions is 0.98.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 6:
Adopt operating process similarly to Example 1, but change the volume fraction of divinylbenzene into 10%, obtained the fine and close more film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 14.1% and 0.81mmol/g-dry membrane, film resistance is 4.45 Ω cm
2, transference number of ions is 0.92.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 7:
Adopt operating process similarly to Example 1, but change the volume fraction of divinylbenzene into 15%, obtained the fine and close more film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 5.3% and 0.43mmol/g-dry membrane, film resistance is 18.56 Ω cm
2, transference number of ions is 0.87.
Embodiment 8:
Adopt operating process similarly to Example 1, and change ammoniacal liquor into ethylenediamine, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 6.5% and 1.16mmol/g-dry membrane, film resistance is 4.69 Ω cm
2, transference number of ions is 0.93.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 9:
Adopt operating process similarly to Example 1, but change ammoniacal liquor into dimethylamine, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 5.0% and 1.03mmol/g-dry membrane, film resistance is 5.36 Ω cm
2, transference number of ions is 0.92.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 10:
Adopt operating process similarly to Example 1, change ammoniacal liquor into methylamine, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 4.0% and 0.58mmol/g-dry membrane, film resistance is 13.55 Ω cm
2, transference number of ions is 0.85.
Embodiment 11:
Adopt operating process similarly to Example 1, change ammoniacal liquor into N, N, N ', N '-4-methyl hexamethylene diamine has obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 5.3% and 0.76mmol/g-dry membrane, film resistance is 11.98 Ω cm
2, transference number of ions is 0.86.
Embodiment 12:
Adopt operating process similarly to Example 1, change supporter into polytetrafluoroethylene (PTFE) screen cloth that thickness is 0.16mm, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be 17.5% and 1.34mmol/g-dry membrane, film resistance is 2.12 Ω cm
2, transference number of ions is 0.96.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 13:
Adopt operating process similarly to Example 1, change supporter into polyvinyl chloride screen cloth that thickness is 0.08-0.10mm, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 18.3% and 1.53mmol/g-dry membrane, film resistance is 1.64 Ω c m
2, transference number of ions is 0.97.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 14:
Adopt operating process similarly to Example 1, change 3g methyl brominated polyphenylether into 3g chloroacetylation polyphenylene oxide, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 14.2% and 1.03mmol/g-dry membrane, film resistance is 5.13 Ω cm
2, transference number of ions is 0.93.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Embodiment 15:
Adopt operating process similarly to Example 1, change the 0.8g benzoyl peroxide into the 0.8g azodiisobutyronitrile, obtained the similar film of structure.
Record anion-exchange membrane water content that present embodiment prepares and ion exchange capacity and be respectively 15.2% and 1.51mmol/g-dry membrane, film resistance is 1.82 Ω cm
2, transference number of ions is 0.96.Experimental data shows that this film has good electric conductivity and high anion selectivity, can be applied to the electrodialysis field.
Claims (7)
1, a kind of homogeneous-phase anion exchange film, homogeneous-phase anion exchange film is made up of high-molecular copolymer, macromolecule reinforcing agent and enhancing fabric; It is characterized in that: described high-molecular copolymer is that chloromethylation styrene, styrene are or/and alkyl-substituted styrene and divinylbenzene copolymer; Described macromolecule reinforcing agent is bromomethylation poly-(1,4-dimethyl 2,6-penylene oxygen) or chloroacetylation poly-(1,4-dimethyl 2,6-penylene oxygen); Described enhancing fabric is glass fabric, polypropylene cloth, polyvinyl chloride cloth or teflon cloth; The proportioning of described anion exchange membrane component is: the ratio of the quality of macromolecule reinforcing agent and polymer copolymerization amount is 1-5/10; The water content of this anion-exchange membrane is 4.0%-43.6%, and ion exchange capacity is 0.43-1.66mmol/g-dry membrane, and film resistance is 1.27-18.56 Ω cm
2, transference number of ions is 0.83-0.98.
2 ,-kind according to claim 1 the preparation method of homogeneous-phase anion exchange film comprises the preparation of monomer, crosslinking agent, macromolecule reinforcing agent and initator mixed solution, polymerization film formation, preliminary treatment and amination step;
Being formulated as of described monomer, crosslinking agent, macromolecule reinforcing agent and initator mixed solution: the mixed solution that at first accounts for mixed liquor volume mark 2%-15% preparation crosslinking agent and monomer by crosslinking agent, it is characterized in that: the ratio of macromolecule reinforcing agent in the above-mentioned mixed solution dissolving of every 10ml 1-5g macromolecule reinforcing agent is dissolved in the above-mentioned mixed solution, in this solution, dissolves the ratio dissolving initator of 0.3-1.8g initator again in the mixed solution of every 10ml divinylbenzene and monomer;
Described polymerization film formation step is: after being evenly coated in above-mentioned final mixed solution on the enhancing fabric, at 6-10 hour polymerization film formation of 70-90 ℃ of heating;
Described preliminary treatment and amination step are: earlier will the above-mentioned film that makes be in 20-30 ℃ of immersion 10-20 hour in the pretreated water solution of 5-20% at the mass fraction of amine, it is in the aqueous solution of 10-40% quaternized 24-48 hour at the trimethylamine mass fraction again, taking-up spends the deionised water drying, promptly gets anion-exchange membrane.
3, as the preparation method of homogeneous-phase anion exchange film as described in the claim 2, be characterised in that described monomer comprises that chloromethylation styrene, styrene are or/and alkyl-substituted styrene.
4, as the preparation method of homogeneous-phase anion exchange film as described in the claim 2, be characterised in that described initator is benzoyl peroxide or azodiisobutyronitrile.
5,, be characterised in that described macromolecule reinforcing agent is bromomethylation poly-(1,4-dimethyl 2,6-penylene oxygen) or chloroacetylation poly-(1,4-dimethyl 2,6-penylene oxygen) as the preparation method of homogeneous-phase anion exchange film as described in the claim 2.
6, as the preparation method of homogeneous-phase anion exchange film as described in the claim 2, be characterised in that described pretreated water solution comprises N, N, N ', the N '-4-methyl hexamethylene diamine aqueous solution, methylamine water solution, dimethylamine agueous solution, ethylenediamine solution or ammoniacal liquor.
7, as the preparation method of homogeneous-phase anion exchange film as described in the claim 2, be characterised in that described enhancing fabric comprises glass fabric, polypropylene cloth, polyvinyl chloride cloth or teflon cloth.
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| CN110560180B (en) * | 2019-09-16 | 2022-03-08 | 德蓝水技术股份有限公司 | Polytetrafluoroethylene-based homogeneous anion exchange membrane and preparation method thereof |
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