CN102190810B - Method for preparing brominated-polyphenylene-ether-guanidination-based homogeneous anion exchange membrane - Google Patents
Method for preparing brominated-polyphenylene-ether-guanidination-based homogeneous anion exchange membrane Download PDFInfo
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- CN102190810B CN102190810B CN201110056534A CN201110056534A CN102190810B CN 102190810 B CN102190810 B CN 102190810B CN 201110056534 A CN201110056534 A CN 201110056534A CN 201110056534 A CN201110056534 A CN 201110056534A CN 102190810 B CN102190810 B CN 102190810B
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Abstract
The invention discloses a method for preparing a brominated-polyphenylene-ether-guanidination-based homogeneous anion exchange membrane. The method is characterized by comprising the following steps of: dissolving bromomethylated poly(2,6-dimethyl 1,4-phenylene oxide), namely brominated polyphenylene ether of which the degree of methyl bromination is 5 to 100 percent into an organic solvent, adding organic micromolecules 1,1,2,3,3-pentamethyl substituent carbamidine in a molar weight which is 0.5 to 10 times that of bromine methyl groups contained in the brominated polyphenylene ether, stirring the solution at the temperature of between 0 and 100 DEG C, reacting for 6 to 48 hours, directly coating casting film solution on the matrix or coating the casting film on reinforced fabrics, and removing the solvent to obtain the anion exchange membrane. In the method, the properties of the anion exchange membrane are controlled by controlling the degree of substitution of the bromine methyl groups of the brominated polyphenylene, so that the homogeneous anion exchange membrane having the advantages of proper water content, high ion exchange content, high thermal stability and mechanical strength and excellent OH-conductivity and alkali resistance can be selected.
Description
Technical field
The invention belongs to the membrane technique field, particularly based on the preparation method of the homogeneous-phase anion exchange film of brominated polyphenylether guanidine radicalsization.
Background technology
Because anion-exchange membrane has a wide range of applications at aspects such as seawater (slightly salty) desalination, tap water hard-off, electrodialysis, diffusion dialysis, electrochemical sensing and fuel cells, it uses and develops and receives people's attention always.The homogeneous-phase anion film since in himself structure the fixed ion-exchange group be connected through chemical bond with the film main body, have even structure, resistance is little and steady performance, makes it have application widely in electrodialysis and fuel cell field.
One Chinese patent application numbers 200810019008.7 announced a kind of will be with of the small molecules copolymerization of benzyl chloride small molecules with the band organoalkoxysilane; Add small molecules silane; Carry out quaternized and sol gel reaction again and obtain coating liquid; Then coating liquid is coated on the matrix, makes the method for anion-exchange membrane after the dry thermosetting.Adopt film loading capacity that this method makes than higher, good thermal stability.But the water ratio of this film is low, snappiness is poor, and electricity is led very low, and these shortcomings have greatly limited the application of this film.
The preparation method of a kind of anion-exchange membrane of one Chinese patent application number 200510123023.2 announcements; Carry out the halo acylations through Fu-Ke reaction pair superpolymer; Dissolving forms film-casting liquid; Standing and defoaming, again that this film is quaternized in tertiary amine solution in film forming on the matrix, be drying to obtain homogeneous-phase anion exchange film.Although the homogeneous-phase anion exchange film with the preparation of this method has higher IX content, lead lowlyer owing to its electricity, limited its use.
Even the method that more than prepares anion-exchange membrane all adopts and carries out quaternized through Trimethylamine 99 to film in the process to film realization functionalization film lotus positive electricity.Because Trimethylamine 99 is alkaline relatively poor, therefore exist the electricity of film to lead not high shortcoming, simultaneously because the quaternary ammonium structure that Trimethylamine 99 reaction back forms exists big suddenly graceful degraded and methyl hydrogen degraded, so the less stable of film.Under alkaline condition, have more serious degraded, make this film application especially the application in alkaline fuel cell received very large restriction.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of homogeneous-phase anion exchange film based on the brominated polyphenylether guanidine radicalsization is to overcome the above-mentioned defective of prior art.
The present invention is based on the preparation method of the homogeneous-phase anion exchange film of brominated polyphenylether guanidine radicalsization, it is characterized in that with methyl bromination degree be 5%-100% the gathering of bromomethylation (2,6-dimethyl-1; 4-penylene oxygen) (brominated polyphenylether) is dissolved in the organic solvent, and the 0.5-10 according to the molar weight of contained brooethyl in the brominated polyphenylether extraordinarily goes into organic molecule 1,1 again; 2,3, the 3-pentamethyl-replaces guanidine; At 0 ℃ of-100 ℃ of stirring reaction 6-48h, obtain containing the polymkeric substance film-casting liquid of side chain guanidine radicals, then film-casting liquid is directly being filmed on the matrix or film-casting liquid is being filmed on reinforced fabric; After removing solvent, promptly obtain anion-exchange membrane.
Said brominated polyphenylether reaches the repeating unit that does not contain brooethyl by the repeating unit that contains brooethyl to be formed, and its structural formula is:
Said methyl bromination degree is meant that the repeating unit that contains brooethyl in the brominated polyphenylether accounts for the molar percentage of all repeating units, the x in the promptly top structural formula.
Said organic solvent is selected from toluene, chlorobenzene or N-Methyl pyrrolidone.
Said 1,1,2,3, the structural formula that the 3-pentamethyl-replaces guanidine does
The said structural formula that contains the polymkeric substance of side chain guanidine radicals is:
Said matrix is selected from polyethylene film, polyfluortetraethylene plate or sheet glass.
Said reinforced fabric is selected Vilaterm cloth, Vestolen PP 7052 cloth, woven dacron, polyamide fabric, nylon cloth or SE cloth for use.
Said method of filming can be selected knifing, sprinkling, dipping for use, flow or the rotation coating.
The method of said removal solvent can select for use room temperature volatilization, rotary evaporation perhaps at 30-130 ℃ of heating, drying.
With carry out quaterisation with Trimethylamine 99 again after employing Fu-Ke reaction pair superpolymer that one Chinese patent application numbers 200510123023.2 is announced carries out the halo acylations and obtain the anionresin membrane method and compare since among the present invention with 1,1,2,3 of brominated polyphenylether reaction; The 3-pentamethyl-replaces the pKa of guanidine up to 13.8, and the pKa that is usually used in the quaternised Trimethylamine 99 of anion-exchange membrane is 10.5, so compare 1,1 with Trimethylamine 99; 2,3, the 3-pentamethyl-replaces guanidine and has stronger alkalescence, and because 1; 1,2,3,3 pentamethyl-s replace 1 of guanidine and brominated polyphenylether reaction back formation; 1,2,2,3; The 3-hexamethyl replaces guanidinesalt and forms resonance structure, and this structure has higher alkali resistance, thus compare with the quaternised film of traditional Trimethylamine 99, with 1; 1,2,3, the film that 3-pentamethyl-replacement guanidine carries out the season guanidineization has higher electroconductibility and alkali resistance.Simultaneously, adopt preparation method of the present invention, can select the more excellent anion-exchange membrane of character easily through regulating the methyl bromination degree of brominated polyphenylether.
Compare with the method for preparing anion-exchange membrane that one Chinese patent application numbers 200810019008.7 is announced, adopt the prepared anion-exchange membrane of the inventive method to have suitable water-content and higher IX content, good thermostability and physical strength, good OH
-Conductivity and alkali resistance can be used for having a good application prospect in the alkaline fuel cell.
Embodiment
Below pass through the preparation method of embodiment further explain homogeneous-phase anion exchange film of the present invention.
Embodiment 1:
With 1g methyl bromination degree is that (brooethyl: 0.4mmol) be dissolved in the 10ml toluene, add 0.5ml 1,1,2,3, the 3-pentamethyl-replaces guanidine (4.0mmol, 10 equivalents), and ice-water bath (0 ℃) stirring reaction 6h obtains film-casting liquid for 5% brominated polyphenylether; This film-casting liquid is scraped on polyethylene film, after room temperature vapors away solvent, obtained homogeneous-phase anion exchange film.This film is immersed in 1mol L
-124h in the NaOH aqueous solution promptly is converted into OH
-The type anion-exchange membrane.
To brominated polyphenylether and the OH that finally obtains
-The infrared test that carries out of type anion-exchange membrane finds that originally the pairing stretching vibration peak of C-Br is 742cm in the brominated polyphenylether
-1, and in the prepared in the present embodiment anion-exchange membrane that obtains, above-mentioned C-Br peak has disappeared, simultaneously at 1600cm
-1And 1397cm
-1The vibration peak of C=N and C-N key appears respectively in the place, explains that the level of response of brooethyl and pentamethyl-replacement guanidine is higher.
The character of other of test anion-exchange membrane is following: water-content 6.4%, IX content 0.37mmolg
-1, tensile strength is 60MPa, heat decomposition temperature is 190 ℃, OH
-Specific conductivity is 0.005S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 2:
With 1g methyl bromination degree is that (brooethyl: 2.7mmol) be dissolved in the 20ml N-Methyl pyrrolidone, add 0.7ml 1,1,2,3, the 3-pentamethyl-replaces guanidine (5.4mmol, 2 equivalents), at 25 ℃ of stirring reaction 24h, obtains film-casting liquid for 42% brominated polyphenylether; This film-casting liquid is scraped on sheet glass, placed baking oven,, obtain homogeneous-phase anion exchange film 30 ℃ of oven dry.This film is immersed in 1mol L
-124h in the NaOH aqueous solution promptly is converted into OH
-The type anion-exchange membrane.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is higher to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 57.1%, IX content 2.32mmolg
-1, tensile strength is 50MPa, heat decomposition temperature is 230 ℃, OH
-Specific conductivity is 0.063S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 3:
With 1g methyl bromination degree is that (brooethyl: 5.0mmol) be dissolved in the 40ml chlorobenzene, add 0.32ml 1,1,2,3, the 3-pentamethyl-replaces guanidine (2.5mmol, 0.5 equivalent), at 25 ℃ of stirring reaction 48h, obtains film-casting liquid for 100% brominated polyphenylether; This film-casting liquid is coated in the polyfluortetraethylene plate surface, places baking oven,, obtain homogeneous-phase anion exchange film 130 ℃ of oven dry.This film is immersed in 1mol L
-124h in the NaOH aqueous solution promptly is converted into OH
-The type anion-exchange membrane.
The infrared test that carries out to brominated polyphenylether and final OH type anion-exchange membrane finds that originally the pairing stretching vibration peak of C-Br is 742cm in the brominated polyphenylether
-1, above-mentioned C-Br peak still exists in the prepared anion-exchange membrane of present embodiment, simultaneously at 1600cm
-1And 1397cm
-1The vibration peak of C=N and C-N key appears respectively in the place, and this is because of here 1,1,2; 3, it is to add according to 50% of brooethyl molar weight in the brominated polyphenylether that the 3-pentamethyl-replaces guanidine, so C-Br and 1,1; 2,3, the reaction that the 3-pentamethyl-replaces guanidine is to have taken place, but reaction not exclusively.
The character of other of test anion-exchange membrane is following: water-content 60.1%, IX content 2.24mmolg
-1, tensile strength is 45MPa, heat decomposition temperature is 240 ℃, OH
-Specific conductivity is 0.071S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 4:
With 1g methyl bromination degree is that (brooethyl: 2.7mmol) be dissolved in the 40ml N-Methyl pyrrolidone, add 0.7ml 1,1,2,3, the 3-pentamethyl-replaces guanidine (5.4mmol, 2 equivalents), at 100 ℃ of stirring reaction 24h, obtains film-casting liquid for 42% brominated polyphenylether; With this film-casting liquid mobile film forming on sheet glass, place baking oven, 30 ℃ of oven dry, obtain homogeneous-phase anion exchange film.This film is immersed in 1mol L
-124h in the NaOH aqueous solution promptly is converted into OH
-The type anion-exchange membrane.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is higher to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 40%, IX content 2.01mmolg
-1, tensile strength is 70MPa, heat decomposition temperature is 225 ℃, OH
-Specific conductivity is 0.042S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 5:
Adopt and embodiment 4 similar methods system films, just film liquid is immersed on the Vestolen PP 7052 cloth, obtain the film of similar structures.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is high to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 43%, IX content 1.93mmolg
-1, tensile strength is 68MPa, heat decomposition temperature is 232 ℃, OH
-Specific conductivity is 0.044S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 6:
Adopt and embodiment 4 similar methods system films, just film liquid is coated on the SE cloth, obtain the film of similar structures.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is higher to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 38%, IX content 1.87mmolg
-1, tensile strength is 71MPa, heat decomposition temperature is 240 ℃, OH
-Specific conductivity is 0.040S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 7:
Adopt and embodiment 4 similar methods system films, just film liquid is sprayed on the Vilaterm cloth, obtain the film of similar structures.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is higher to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 35%, IX content 1.80mmolg
-1, tensile strength is 75MPa, heat decomposition temperature is 228 ℃, OH
-Specific conductivity is 0.035S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 8:
Adopt and embodiment 4 similar methods system films, just the rotation of film liquid is coated on the woven dacron, obtain the film of similar structures.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is higher to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 53%, IX content 2.12mmolg
-1, tensile strength is 62MPa, heat decomposition temperature is 230 ℃, OH
-Specific conductivity is 0.055S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 9:
Adopt and embodiment 4 similar methods system films, just film liquid is flowed on polyamide fabric and film, obtain the film of similar structures.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is higher to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 49%, IX content 2.02mmolg
-1, tensile strength is 64MPa, heat decomposition temperature is 245 ℃, OH
-Specific conductivity is 0.051S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
Embodiment 10:
Adopt and embodiment 4 similar methods system films, just film liquid is coated on the nylon cloth, obtain the film of similar structures.
The result of the infrared test among the result who the prepared anion-exchange membrane that obtains in the present embodiment is carried out infrared test and the embodiment 1 is similar, and it is higher to explain that brooethyl and pentamethyl-replace the level of response of guanidine.
The character of other of test anion-exchange membrane is following: water-content 50%, IX content 1.91mmolg
-1, tensile strength is 57MPa, heat decomposition temperature is 232 ℃, OH
-Specific conductivity is 0.053S cm
-1And at 1molL
-1Soaking after 8 days electricity among the NaOH leads and remains unchanged.
Above-mentioned test result shows that film prepared in the present embodiment has excellent mechanical intensity, good thermostability, good OH
-Electricity is led and alkali resistance, can be applied in the alkaline fuel cell.
The result of above embodiment shows that through changing the methyl bromination degree and 1,1,2,3 of brominated polyphenylether, the 3-pentamethyl-replaces the consumption of guanidine, can effectively control the character of anion-exchange membrane, thereby satisfy different application requiring.In addition, through the control reaction conditions, can make prepared anion-exchange membrane have higher loading capacity, suitable water-content, high OH
-Electricity is led, and can be applied in the alkaline fuel cell.
Claims (5)
1. preparation method based on the homogeneous-phase anion exchange film of brominated polyphenylether guanidine radicalsization, it is characterized in that with methyl bromination degree be 5%-100% the gathering of bromomethylation (2,6-dimethyl-1; 4-penylene oxygen) or claim that brominated polyphenylether is dissolved in the organic solvent, extraordinarily go into organic molecule 1,1 according to the 0.5-10 of the molar weight of contained brooethyl in the brominated polyphenylether again; 2,3, the 3-pentamethyl-replaces guanidine; At 0 ℃ of-100 ℃ of stirring reaction 6-48h, obtain containing the polymkeric substance film-casting liquid of side chain guanidine radicals, then film-casting liquid is directly being filmed on the matrix or film-casting liquid is being filmed on reinforced fabric; After removing solvent, promptly obtain anion-exchange membrane;
Said brominated polyphenylether reaches the repeating unit that does not contain brooethyl by the repeating unit that contains brooethyl to be formed, and its structural formula is:
Said methyl bromination degree is meant that the repeating unit that contains brooethyl in the brominated polyphenylether accounts for the molar percentage of all repeating units, the x in the promptly top structural formula;
Said organic solvent is selected from toluene, chlorobenzene or N-Methyl pyrrolidone;
Said 1,1,2,3, the structural formula that the 3-pentamethyl-replaces guanidine is:
The said structural formula that contains the polymkeric substance of side chain guanidine radicals is:
2. according to claim 1 based on the preparation method of the homogeneous-phase anion exchange film of brominated polyphenylether guanidine radicalsization, be characterised in that said matrix is selected from polyethylene film, polyfluortetraethylene plate or sheet glass.
3. according to claim 1 based on the preparation method of the homogeneous-phase anion exchange film of brominated polyphenylether guanidine radicalsization, be characterised in that said reinforced fabric selects Vilaterm cloth, Vestolen PP 7052 cloth, woven dacron, polyamide fabric, nylon cloth or SE cloth for use.
4. according to claim 1 based on the preparation method of the homogeneous-phase anion exchange film of brominated polyphenylether guanidine radicalsization, be characterised in that said method of filming selects knifing, sprinkling, dipping for use, flows or rotation applies.
5. according to claim 1 based on the preparation method of the homogeneous-phase anion exchange film of brominated polyphenylether guanidine radicalsization, the method that is characterised in that said removal solvent can be selected room temperature volatilization, rotary evaporation for use or at 30-130 ℃ of heating, drying.
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| CN103372381B (en) * | 2012-04-19 | 2015-04-08 | 中国科学技术大学 | Anion-exchange film, preparation method thereof and fuel cell |
| CN106188529B (en) * | 2016-07-20 | 2018-04-10 | 大连理工大学 | A kind of long-chain branch polyphenylene oxide anionic membrane and preparation method thereof |
| CN106374125A (en) * | 2016-09-07 | 2017-02-01 | 辽宁石油化工大学 | Preparation method for full interpenetration type anion exchange membrane containing crosslinked guanidine molecules |
| CN110003462B (en) * | 2019-03-26 | 2020-10-27 | 北京化工大学 | Polyphenylene ether type anion exchange membrane loaded with quaternary tetra-amino phosphonium cation unit and preparation method thereof |
| CN111393696B (en) * | 2020-04-08 | 2022-04-12 | 福州大学 | Guanidine-based functionalized anion exchange membrane with cross-linked network structure and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1978038A (en) * | 2005-12-09 | 2007-06-13 | 中国科学技术大学 | Method for preparing homogeneous-phase anion exchange film |
| 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 |
| CN101352657A (en) * | 2008-02-29 | 2009-01-28 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
| CN101845215A (en) * | 2010-04-02 | 2010-09-29 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
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| JPS57125223A (en) * | 1981-01-27 | 1982-08-04 | Teijin Ltd | Amphoteric composite membrane with ion permeability |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1978038A (en) * | 2005-12-09 | 2007-06-13 | 中国科学技术大学 | Method for preparing homogeneous-phase anion exchange film |
| 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 |
| CN101352657A (en) * | 2008-02-29 | 2009-01-28 | 中国科学技术大学 | Homogeneous phase cation exchange film and preparation method thereof |
| CN101845215A (en) * | 2010-04-02 | 2010-09-29 | 中国科学技术大学 | Preparation method based on brominated polyphenylether blending of hybrid anion exchange membrane |
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