CN1558457A - Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films - Google Patents

Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films Download PDF

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CN1558457A
CN1558457A CNA2004100391143A CN200410039114A CN1558457A CN 1558457 A CN1558457 A CN 1558457A CN A2004100391143 A CNA2004100391143 A CN A2004100391143A CN 200410039114 A CN200410039114 A CN 200410039114A CN 1558457 A CN1558457 A CN 1558457A
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acid
sulfonic acid
exchange membrane
condensation polymer
proton exchange
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CN1252842C (en
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Л
谢晓峰
徐景明
毛宗强
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Tsinghua University
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Tsinghua University
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention discloses a process for preparing modified sulfonic acid lateral group polybenzimidazole proton interchange film used in methyl alcohol fuel cells which comprises, subjecting fouramine group compounds, 3-alkyl-isophthalic acid and fat diprotonic acid to polycondensation in polyphosphoric acid system, obtaining homogeneous solution, subjecting the solution to neutralization, rinshing, filtering and dehumidification to obtain polycondensate crude product, dissolving the polycondensate crude product in strong inorganic acid, disposing in water to obtain the pure polycondensate product, dissolving the pure polycondensate in organic solvent to obtain homogeneous polycondensate solution, making films with pouring method or flowing method.

Description

The preparation method of modification sulfonic acid lateral group polybenzimidazole proton exchange membrane
Technical field
The invention belongs to fuel cell material technology of preparing scope, the modification sulfonic acid lateral group polybenzimidazole that particularly is used for direct methanol fuel cell prepares the preparation method of proton exchange membrane.
Background technology
The proton exchange membrane of using in direct methanol fuel cell is at present used perfluorocarbon polymer sulfonic acid type ion exchange membrane (Nafion) more.When this perfluorocarbon polymer sulfonic acid proton exchange film is used for direct methanol fuel cell, exist methyl alcohol and be penetrated into the problem that negative electrode hinders the electrochemical cathode reaction from anode, limited the development and application of direct methanol fuel cell widely, in order to address this problem, people have carried out the research of non-fluorine proton-conductive films.
Polybenzimidazoles (PBI) is a class high thermal stability material, has alkaline structure.Mix with acid or after the grafting of sulfonic acid alkyl, can improve the proton exchange membrane of the proton conductivity of PBI as direct methanol fuel cell.The acid doping normally is dipped in the PBI film in the certain density acid solution or is dissolved in acid back directly cast or casting film-forming, and the PBI film after the acid treatment only is 1/300 of a Nafion film to the methanol permeation rate in the time of 80 ℃; The grafting of sulfonic acid alkyl is exactly sulfonation PBI, and sulfonic group (as the p-sulfonic acid benzyl) is incorporated on imidazoles nitrogen or the phenyl ring.No matter PBI mixes with acid or sulfonic acid alkyl grafting processing, and its aim all is to improve the proton-conducting of PBI, satisfies the requirement that direct methanol fuel cell is used with proton exchange membrane.But, produce swelling behind the acid treatment PBI, the pliability of PBI film is increased, the what is called that the crisp indissoluble of matter then takes place in the PBI sulfonation " is stablized PBI ", has reduced the mechanical performance of film, has reduced useful life.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of modification sulfonic acid lateral group polybenzimidazole proton exchange membrane, it is characterized in that: use tetramine based compound, 3-alkyl acid-isophthalic acid, binary acid in polyphosphoric acids, to prepare the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification, in the PBI rigid chain segment, introduce flexible group, both guarantee the proton conductivity of proton exchange membrane, and can solve the problem of the crisp indissoluble of film again; This film has the characteristics of proton conductivity height, softness, solubility increase.Its preparation process is:
1). tetramine based compound, 3-alkyl acid-isophthalic acid, binary acid and polyphosphoric acids are mixed with 1: 0.5~1: 0.05~0.3: 18~22 (weight ratios), form uniform blend;
2). in inert atmosphere, under 100~250 ℃, stirring reaction 1~8 hour obtains homogeneous solution;
3). with in the 1N-2N sodium hydroxide solution and more than the homogeneous solution that obtains, be washed to neutrality, drying, the condensation polymer crude product after obtaining handling;
4). the above-mentioned condensation polymer that obtains is dissolved in the strong inorganic acid, and precipitating, filtration in water then is washed to neutrality, and drying obtains the pure product of condensation polymer;
5). the pure product of the above-mentioned condensation polymer that obtains are dissolved in the organic solvent, obtain condensation polymer solution; With above-mentioned condensation polymer solution casting or the casting film-forming that obtains, solidified under the room temperature 2~6 hours, 100~300 ℃ down or in the 100pa vacuum, 60~150 ℃ solidified 2~8 hours down, are cooled to room temperature, demoulding in the water in inert atmosphere then.
Described tetramine based compound is 2,3,4,5-tetramino benzene, 3,3 ', 4, and 4 '-tetramino connects benzene, 3,3 ', 4,4 '-tetramino sulfone, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino ketone, 3,3 ', 4, any one in 4 '-tetramino methyl.
Described 3-alkyl acid-isophthalic acid is any one in 3-methanesulfonic acid-isophthalic acid, 3-ethyl sulfonic acid-isophthalic acid, the 3-N-morpholinopropanesulfonic acid-isophthalic acid.
Described binary acid is any one in malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, the decanedioic acid.
Used organic solvent is the equal amount of mixture of any one or two kinds in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), the N-methyl pyrrolidone.
The invention has the beneficial effects as follows and introduce flexible group in the PBI rigid chain segment, solve the problem of the crisp indissoluble of film, make film have the advantages that good anti-methanol crossover ability, proton conductivity height, softness and solubility increase, can be used for direct methanol fuel cell as proton exchange membrane, improve the electrochemical cathode activity, improve the output characteristic of fuel cell.
Concrete embodiment
The present invention is a kind of preparation method of modification sulfonic acid lateral group polybenzimidazole proton exchange membrane.After tetramine based compound, 3-alkyl acid-isophthalic acid and binary acid mixed with 1: 0.5~1: 0.05~0.3 (weight ratio), adding weight ratio is in the polyphosphoric acids of (18~22), form uniform mixture, in inert atmosphere, under 100~250 ℃, stirring reaction 1~8 hour obtains homogeneous solution; Neutralization, washing, filtration, drying obtain the condensation polymer crude product; Condensation polymer is dissolved in the strong inorganic acid, and precipitating, filtration, washing, drying obtain the pure product of condensation polymer in the water; The pure product of condensation polymer are dissolved in the organic solvent, obtain condensation polymer solution; With condensation polymer solution casting or casting film-forming, solidified under the room temperature 2~6 hours, then in inert atmosphere, under 100~300 ℃ or in the 100pa vacuum, 60~150 ℃ solidified 2~8 hours down, were cooled to room temperature, and demoulding becomes modification sulfonic acid lateral group polybenzimidazole proton exchange membrane in the water
Described tetramine based compound is 2,3,4,5-tetramino benzene, 3,3 ', 4, and 4 '-tetramino connects benzene, 3,3 ', 4,4 '-tetramino sulfone, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino ketone, 3,3 ', 4, any one in 4 '-tetramino methyl.
Described 3-alkyl acid-isophthalic acid is any one in 3-methanesulfonic acid-isophthalic acid, 3-ethyl sulfonic acid-isophthalic acid, the 3-N-morpholinopropanesulfonic acid-isophthalic acid.
Described binary acid is any one in malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, the decanedioic acid.
Solvent for use is the equal amount of mixture of any one or two kinds in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), the N-methyl pyrrolidone.
Give an actual example below the present invention illustrated:
Example 1:
1). with 1 part 2,3,4,5-tetramino benzene or 3,3 ', 4,4 '-tetramino connects benzene, 0.58 part of 3-methanesulfonic acid-isophthalic acid and 0.31 part of adipic acid and is dissolved in 22 parts of polyphosphoric acids, forms uniform mixture;
2). in nitrogen atmosphere, 150 ℃ were reacted 2 hours down, obtain brown solution;
3). after brown solution is neutralized to neutrality with the 2N sodium hydroxide solution, filter, drying, obtain buff condensation polymer crude product;
4). the above-mentioned condensation polymer dissolving crude product that obtains in the 1N concentrated sulfuric acid, precipitating in the water, is filtered, is washed to neutrality, the following 80 ℃ of dryings of vacuum 24 hours, obtain the pure product of condensation polymer;
5). dissolve in the 12 parts of pure product to 100 of above-mentioned condensation polymer part dimethyl sulfoxide (DMSO)s, obtain uniform condensation polymer solution;
6). behind above condensation polymer solution casting or casting film-forming, solidified 2 hours under the room temperature, solidified 4 hours down for 100 ℃ at 1~3l/min nitrogen atmosphere at 1~3l/min then, be cooled to room temperature, demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
Example 2:
1) .1 part 3, and 3 ', 4,4 '-tetramino ketone, 0.78 part of 3-methanesulfonic acid-isophthalic acid, 0.08 part of adipic acid are dissolved in 18 parts of polyphosphoric acids, form uniform mixture;
2). in nitrogen atmosphere, 150 ℃ were reacted 3 hours down, obtain brown solutions;
3). after brown solutions is neutralized to neutrality with the 1N sodium hydroxide solution, filter, drying, obtain yellow condensation polymer crude product;
4). the above-mentioned condensation polymer dissolving crude product that obtains in the 1N concentrated sulfuric acid, precipitating in the water, is filtered, is washed to neutrality, the following 80 ℃ of dryings of vacuum 24 hours, obtain the pure product of condensation polymer;
5). dissolve in the 10 parts of pure product to 100 of above-mentioned condensation polymer part dimethylacetylamides, obtain uniform condensation polymer solution;
6). behind above condensation polymer solution casting or casting film-forming, solidified under the room temperature 3 hours, then at 1~3l/min nitrogen atmosphere, 140 ℃ solidified 4 hours down, were cooled to room temperature, and demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
Example 3:
1) .1 part 3, and 3 ', 4,4 '-tetramino sulfone, 0.64 part of 3-ethyl sulfonic acid-isophthalic acid, 0.06 part of adipic acid are dissolved in 20 parts of polyphosphoric acids, form uniform mixture;
2). in nitrogen atmosphere, 200 ℃ were reacted 1 hour down, obtain brown solution;
3). after brown solution is neutralized to neutrality with the 1N sodium hydroxide solution, filter, drying, obtain yellow condensation polymer crude product;
4). the above-mentioned yellow condensation polymer dissolving crude product that obtains in the 2N concentrated sulfuric acid, precipitating in the water, is filtered, is washed to neutrality, the following 80 ℃ of dryings of vacuum 24 hours, obtain the pure product of condensation polymer;
5). dissolve in the 8 parts of pure product to 100 of above-mentioned condensation polymer part dimethyl formamides, obtain uniform condensation polymer solution;
6). behind above condensation polymer solution casting or casting film-forming, solidified under the room temperature 2 hours, then at 1~3l/min nitrogen atmosphere, 120 ℃ solidified 6 hours down, were cooled to room temperature, and demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
Example 4:
1) .1 part 3, and 3 ', 4,4 '-tetramino diphenyl ether, 0.78 a part of 3-N-morpholinopropanesulfonic acid-benzene two, 0.1 part of adipic acid are dissolved in 18 parts of polyphosphoric acids, form uniform mixture;
2). in argon gas atmosphere, 250 ℃ were reacted 1 hour down, obtain deep brown solution;
3). after deep brown solution is neutralized to neutrality with the 2N sodium hydroxide solution, filter, drying, obtain yellow condensation polymer crude product;
4). the above-mentioned yellow condensation polymer dissolving crude product that obtains in the 1N concentrated sulfuric acid, precipitating in the water, is filtered, is washed to neutrality, the following 80 ℃ of dryings of vacuum 24 hours, obtain the pure product of condensation polymer;
5). dissolve in the 12 parts of pure product to 100 of above-mentioned condensation polymer part dimethylacetylamides, obtain uniform condensation polymer solution;
6). behind above condensation polymer solution casting or casting film-forming, solidified under the room temperature 2 hours, then in 1~3l/min argon gas atmosphere, 180 ℃ solidified 6 hours down, were cooled to room temperature, and demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
Only lift above-mentioned 4 examples, the sulfonic acid lateral group polybenzimidazole proton exchange membrane of all the other modifications, its technology is basic identical, is come to the same thing.

Claims (6)

1. the preparation method of modification sulfonic acid lateral group polybenzimidazole proton exchange membrane, it is characterized in that: the preparation process of the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification is:
1) tetramine based compound, 3-alkyl acid-isophthalic acid, binary acid are added in the polyphosphoric acids of weight ratio (18~22) after mixing with 1: 0.5~1: 0.05~0.3 (weight ratio), form uniform mixture;
2) in the inert atmosphere of 1~3l/min, under 100~250 ℃, stirring reaction 1~8 hour obtains homogeneous solution;
3) above-mentioned homogeneous solution is neutralized to neutrality with sodium hydroxide solution after, filter, drying, obtain the condensation polymer crude product;
4) with the above-mentioned condensation polymer dissolving crude product that obtains in sulfuric acid, be sunken in the deionized water water analyse, filter, with deionized water be washed to neutrality, drying obtains the pure product of condensation polymer;
5) the pure product of the above-mentioned condensation polymer that obtains are dissolved in the organic solvent, obtain condensation polymer solution;
6) with above-mentioned condensation polymer solution casting or the casting film-forming that obtains, solidified under the room temperature 2~6 hours, then in inert atmosphere, under 100~300 ℃ or in the 100pa vacuum, 60~150 ℃ solidified 2~8 hours down, be cooled to room temperature, demoulding in the water obtains the sulfonic acid lateral group polybenzimidazole proton exchange membrane of modification.
2. according to the sulfonic acid lateral group polybenzimidazole proton exchange membrane preparation method of the described modification of claim 1, it is characterized in that: described tetramine based compound is 2,3,4,5-tetramino benzene, 3,3 ', 4,4 '-tetramino connects benzene, 3,3 ', 4,4 '-tetramino sulfone, 3,3 ', 4,4 '-tetramino diphenyl ether, 3,3 ', 4,4 '-tetramino ketone, 3,3 ', 4, any one in 4 '-tetramino methyl.
3. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: described 3-alkyl acid-isophthalic acid is any one in 3-methanesulfonic acid-isophthalic acid, 3-ethyl sulfonic acid-isophthalic acid, the 3-N-morpholinopropanesulfonic acid-isophthalic acid.
4. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: described binary acid is any one in malonic acid, succinic acid, glutaric acid, hexanedioic acid, pimelic acid, suberic acid, azelaic acid, the decanedioic acid.
5. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: solvent for use is the mixture of any one or two kinds in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), the N-methyl pyrrolidone.
6. according to the preparation method of the described modification sulfonic acid lateral group polybenzimidazole of claim 1 proton exchange membrane, it is characterized in that: described inert gas is nitrogen or argon gas.
CNB2004100391143A 2004-02-06 2004-02-06 Process for preparing odified sulfonic acid lateral group polybenzimidazoles proton interchange films Expired - Fee Related CN1252842C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365858C (en) * 2005-04-05 2008-01-30 新源动力股份有限公司 Composite proton exchange membrane for high-temperature fuel battery and producing method thereof
CN101392060B (en) * 2008-10-21 2011-01-12 东华大学 Quaternized polybenzimidazoles and preparation method thereof
WO2011132152A1 (en) * 2010-04-22 2011-10-27 Basf Se Improved polymer electrolyte membrane based on polyazole
CN101709029B (en) * 2009-11-16 2013-01-02 清华大学 Polybenzimidazole material and midbody organic diacid thereof as well as preparation methods thereof
CN103086999A (en) * 2011-11-03 2013-05-08 清华大学 Novel fluorine-containing polybenzimidazole polymer, fluorinated organic diacid monomer as intermediate of the fluorine-containing polybenzimidazole polymer, and their preparation method
US9048478B2 (en) 2010-04-22 2015-06-02 Basf Se Polymer electrolyte membrane based on polyazole
CN108400362A (en) * 2018-02-05 2018-08-14 大连理工大学 A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof
CN114536915A (en) * 2022-03-11 2022-05-27 福建师范大学 Alkali-resistant bipolar membrane with main chain fluorocarbon-ferrocene catalyst layer and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365858C (en) * 2005-04-05 2008-01-30 新源动力股份有限公司 Composite proton exchange membrane for high-temperature fuel battery and producing method thereof
CN101392060B (en) * 2008-10-21 2011-01-12 东华大学 Quaternized polybenzimidazoles and preparation method thereof
CN101709029B (en) * 2009-11-16 2013-01-02 清华大学 Polybenzimidazole material and midbody organic diacid thereof as well as preparation methods thereof
WO2011132152A1 (en) * 2010-04-22 2011-10-27 Basf Se Improved polymer electrolyte membrane based on polyazole
US9048478B2 (en) 2010-04-22 2015-06-02 Basf Se Polymer electrolyte membrane based on polyazole
CN103086999A (en) * 2011-11-03 2013-05-08 清华大学 Novel fluorine-containing polybenzimidazole polymer, fluorinated organic diacid monomer as intermediate of the fluorine-containing polybenzimidazole polymer, and their preparation method
CN103086999B (en) * 2011-11-03 2014-09-17 清华大学 Novel fluorine-containing polybenzimidazole polymer, fluorinated organic diacid monomer as intermediate of the fluorine-containing polybenzimidazole polymer, and their preparation method
CN108400362A (en) * 2018-02-05 2018-08-14 大连理工大学 A kind of side chain type alkyl sulfonate polybenzimidazole amberplex and preparation method thereof
CN114536915A (en) * 2022-03-11 2022-05-27 福建师范大学 Alkali-resistant bipolar membrane with main chain fluorocarbon-ferrocene catalyst layer and preparation method thereof
CN114536915B (en) * 2022-03-11 2023-05-23 福建师范大学 Alkali-resistant bipolar membrane with main chain fluorocarbon-ferrocene catalytic layer and preparation method thereof

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