CN105789669B - A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation and preparation method thereof - Google Patents
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to poly- imino group benzimidazole high temperature proton exchange films of a kind of phosphonic acids doping cross-linking sulfonation and preparation method thereof, and the proton exchange membrane is prepared via a method which to obtain：1) in a nitrogen atmosphere, diamino disulfonic acid is dissolved in solvent and obtains diamino disulphonic acid, benzidine, aminophenyl benzimidazole and naphthalenetetracarbacidic acidic dianhydride are added into diamino disulphonic acid, stir thoroughly at room temperature is uniform, heating reaction, subsequent cooled to room temperature, add diluent, it is sufficiently stirred, filters, the solid matter filtered out is washed, is dried to obtain the poly- imino group benzimidazole of sulfonation；2) the poly- imino group benzimidazole of sulfonation is dissolved in dimethyl sulfoxide, obtains solution, add dibromodiphenyl ether, after mixing in high temperature proton exchange film is obtained by the reaction；3) high temperature proton exchange film is placed in aminotrimethylenephosphonic acid aqueous solution and is impregnated, then washed, the poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is obtained by the reaction in heating.
Description
Technical field
The invention belongs to field of fuel cell technology, and in particular to a kind of poly- imino group benzo miaow of phosphonic acids doping cross-linking sulfonation
Azoles high temperature proton exchange film and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells is a kind of new fuel cell converting fuel chemical energy to electric energy, has nothing and makes an uproar
Sound, pollution-free and efficient advantage.Proton exchange membrane is the critical material of Proton Exchange Membrane Fuel Cells, is widely used at present
Be E.I.Du Pont Company nafion films, transmit proton mainly by the sulfonic acid group of intramolecular, but sulfonic acid group is to ambient humidity
There is very high requirement, proton conductivity drastically reduces under high temperature low humidity conditions, and the use environment of proton exchange membrane requires it
With higher mechanical performance, high temperature resistance, chemical-resistance, it is needed still to have stability and high efficiency in high temperature low humidity conditions
Proton conduction property.So the novel proton exchange membranes that synthesis can work under high temperature low moisture environments have far-reaching significance.
Phosphonic acids is a kind of both sexes acid, can both be used as proton donor, can also be used as proton acceptor, and phosphate group has certainly
Dissociative, even if proton transfer still can be carried out under the high temperature conditions, so based on the high temperature proton exchange film of phosphonic acid base at
For the hot spot studied instantly.Phosphonic acids is there are mainly two types of state in high temperature proton exchange film, and one is by passing through of phosphate group
The mode for learning bonding is grafted with molecular backbone, and another kind is to make phosphate group and intramolecular main chain by way of doping
On atom form certain interaction force, with have the function that transmit proton.But phosphate proton prepared at present is handed over
It changes film and still has the problems such as cannot being used under the conditions of thermal stability is poor, proton conductivity is low and high-temperature anhydrous.
Invention content
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of phosphonic acids to mix
Miscellaneous cross-linked poly- imino group benzimidazole high temperature proton exchange film and preparation method thereof, contains in the proton exchange membrane backbone structure
There is benzene ring structure, having good toughness and thermal stability, (high temperature resistant temperature reaches 262-283 DEG C, and tensile strength reaches 51.7-
67.6MPa), still there is higher proton conductivity (proton conductivity under 180 DEG C of dry anhydrous conditions under the conditions of high-temperature anhydrous
Up to 0.058-0.073S/cm).
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is provided, it is by following methods system
It is standby to obtain：
1) in a nitrogen atmosphere, diamino disulfonic acid is dissolved in solvent and obtains diamino disulphonic acid, to diamino
Benzidine, benzimidazole containing aminophenyl and naphthalenetetracarbacidic acidic dianhydride are added in disulphonic acid, stir thoroughly at room temperature is uniform, in 70-
90 DEG C of heating 5-6h, then heat 18-24h in 165-180 DEG C, and cooled to room temperature adds diluent, is sufficiently stirred,
Filtering, the solid matter filtered out is washed, is dried to obtain the poly- imino group benzimidazole of sulfonation；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in dimethyl sulfoxide, obtains the poly- imino group benzo miaow of sulfonation
Azoles solution, adds dibromodiphenyl ether, and it is 1 to make amino and benzyl bromide molar ratio in solution:1, it is anti-in 75-80 DEG C after mixing
18-24h is answered, then 2-4h is heated in 150-160 DEG C, obtains high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is placed in aminotrimethylenephosphonic acid aqueous solution and impregnates 36-48h, then used
Deionized water is washed, and then heats 5-6h in 70-90 DEG C, and finally heating 18-24h in 150-160 DEG C obtains phosphonic acids doping cross-linking
The poly- imino group benzimidazole high temperature proton exchange film of sulfonation.
By said program, step 1) the diamino disulfonic acid is 4,4'- diamino -2,2'- disulfonic acid, 4,4'- diaminos
One kind in base talan -2,2'- disulfonic acid, 4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid.
By said program, the step 1) solvent is m-cresol and triethylamine 18-25 by volume:1 is mixed to get
Mixed solvent；A concentration of 0.05-0.12mol/L of diamino disulphonic acid.
By said program, the step 1) benzidine is 3,3 '-bis- (4- sulphenyls) benzidine；The benzene containing aminophenyl
And imidazoles is 6,6 '-bis- [2- (4- aminophenyls)] benzimidazoles；The benzidine, benzimidazole containing aminophenyl and naphthalene tetracid dianhydride
Molar ratio be 1.4-1.8:1:2-2.6, and the molar ratio of diamino disulfonic acid and the benzimidazole containing aminophenyl is 1:1.
By said program, the step 1) diluent be between phenyl methylcarbamate and acetone mixture, in-between phenyl methylcarbamate and third
Ketone volume ratio is 1：5.
Preferably, the mass concentration of the poly- imino group benzimidazole solution of the step 2) sulfonation is 6%.
By said program, step 3) the aminotrimethylenephosphonic acid concentration of aqueous solution is 0.08-0.12mol/L.
The invention also includes the preparation methods of above-mentioned high temperature proton exchange film, and its step are as follows：
1) in a nitrogen atmosphere, diamino disulfonic acid is dissolved in solvent and obtains diamino disulphonic acid, to diamino
Benzidine, benzimidazole containing aminophenyl and naphthalenetetracarbacidic acidic dianhydride are added in disulphonic acid, stir thoroughly at room temperature is uniform, in 70-
90 DEG C of heating 5-6h, then heat 18-24h in 165-180 DEG C, and cooled to room temperature adds diluent, is sufficiently stirred,
Filtering, the solid matter filtered out is washed, is dried to obtain the poly- imino group benzimidazole of sulfonation；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in dimethyl sulfoxide, obtains the poly- imino group benzo miaow of sulfonation
Azoles solution, adds dibromodiphenyl ether, and it is 1 to make amino and benzyl bromide molar ratio in solution:1, it is anti-in 75-80 DEG C after mixing
18-24h is answered, then 2-4h is heated in 150-160 DEG C, obtains high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is placed in aminotrimethylenephosphonic acid aqueous solution and impregnates 36-48h, then used
Deionized water is washed, and then heats 5-6h in 70-90 DEG C, and finally heating 18-24h in 150-160 DEG C obtains phosphonic acids doping cross-linking
The poly- imino group benzimidazole high temperature proton exchange film of sulfonation.
Cross-linked poly- (the imino group benzimidazole) that main chain contains benzene ring structure is a kind of with good physical behavior
Material, phenyl ring and similar benzene ring structure on main chain make the polymer have very high toughness, good thermal stability and anti-oxidant
Property.Contain multiple N atoms on molecular backbone, hydrogen bond network can be formed with phosphate group, be conducive to attachment and the proton of phosphonic acids
It transmits.Benzimidazole polymer is same to proton both with electron or with electron-withdrawing.This substance is in matter
Proton can easily be completed to transmit in sub- transmittance process.
The present invention uses 6,6 '-bis- [2- (4- aminophenyls)] benzimidazoles to be carried for the poly- imino group benzimidazole strand of sulfonation
N-H keys have been supplied, have been added after crosslinking agent dibromodiphenyl ether, the bromine in dibromodiphenyl ether and N- in the poly- imino group benzimidazole of sulfonation
Substitution reaction occurs for the hydrogen on H keys, following reaction occurs so that the poly- imino group benzimidazole molecule of two sulfonation is by dibromo hexichol
Ether is crosslinked together：
The beneficial effects of the present invention are：1, preparation method of the present invention is simple, and experiment condition is of less demanding and experimentation
It is easy to operate；2, the poly- imino group benzimidazole high temperature proton exchange film main chain of phosphonic acids doping cross-linking sulfonation prepared by the present invention contains
Benzene ring structure, thus with good mechanical performance, high temperature resistance and antioxygenic property (high temperature resistant temperature reaches 262-283 DEG C,
Tensile strength reaches 51.7-67.6MPa), not only there are sulfonic acid group, also phosphonyl group, phosphonic acids and molecular backbone in molecular side chain
On N form continuous hydrogen bond network, make proton membrane have very high proton conductivity, even if under 180 DEG C, anhydrous condition,
Proton conductivity still reaches 0.058-0.073S/cm.Therefore, the cross-linked poly- (imino group based on phosphonic acid base that prepared by the present invention
Benzimidazole) proton exchange membrane has the foreground of being widely applied.
Specific implementation mode
To make those skilled in the art more fully understand technical scheme of the present invention, the present invention is made with reference to embodiment
It is described in further detail.
Raw material as used in the following examples is that analysis is pure, and purity is more than 98wt%.
Embodiment 1
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is prepared, steps are as follows：
1) 15mL m-cresols and 0.8mL triethylamines is added in 1.8mmol4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid
In the mixed solvent, be passed through nitrogen, be sufficiently stirred, until all dissolving obtains diamino disulphonic acid for diamino disulfonic acid,
Bis- (4- sulphenyls) benzidine of 1.4mmol 3,3 '-, the bis- [2- (4- of 1mmol 6,6 '-are added into diamino disulphonic acid
Aminophenyl)] benzimidazole and 2mmol Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidic dianhydrides stir 10min at room temperature, prior to 80 DEG C at heat
5h, then heated for 24 hours at 180 DEG C, cooled to room temperature, adds 12mL m-cresols and 100mL acetone as diluent,
It is filtered after being sufficiently stirred, filters out fibery precipitate, sediment is washed 3-5 times with acetone, then vacuum at a temperature of 80 DEG C
The poly- imino group benzimidazole of sulfonation is obtained after dry 10h；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in and obtains the sulphur that mass concentration is 6% in dimethyl sulfoxide
Change poly- imino group benzimidazole solution, add 1mmol dibromodiphenyl ethers, makes in the amino and dibromodiphenyl ether in benzimidazole
Benzyl bromide molar ratio is 1:1, it pours into polytetrafluoroethylene (PTFE) mould, is heated at 80 DEG C for 24 hours, then in 160 DEG C after mixing
3h is heated, its is made full cross-linked to obtain high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is put into the aminotrimethylenephosphonic acid aqueous solution of 0.1mol/L,
48h is impregnated under room temperature, is then taken out, is washed with deionized, then heats 5h at 80 DEG C, is then heated at 160 DEG C
The poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is obtained for 24 hours.
After tested, the linear swelling coefficient under the proton exchange membrane room temperature prepared by the present embodiment is 6.24%, illustrates to hand over
It changes film to have good stability in water, thermal stable temperature is 265 DEG C, tensile strength 52.1MPa, and ion exchange capacity is
0.80mmol/g illustrates that phosphonic acids content is high in exchange membrane, and it is 0.058S/cm that conductivity is measured under 180 DEG C of anhydrous conditions.
Embodiment 2
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is prepared, steps are as follows：
1) 15mL m-cresols and 0.8mL triethylamines is added in 1.8mmol4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid
In the mixed solvent, be passed through nitrogen, be sufficiently stirred, until all dissolving obtains diamino disulphonic acid for diamino disulfonic acid,
Bis- (4- sulphenyls) benzidine of 1.4mmol 3,3 '-, the bis- [2- (4- of 1mmol 6,6 '-are added into diamino disulphonic acid
Aminophenyl)] benzimidazole and 2.2mmol Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidic dianhydrides are sufficiently stirred at room temperature, prior to 80 DEG C at heat
5h, then heated for 24 hours at 180 DEG C, cooled to room temperature, adds 12mL m-cresols and 100mL acetone as diluent,
It is filtered after being sufficiently stirred, filters out fibery precipitate, sediment is washed with acetone, then be dried in vacuo to obtain the poly- imido of sulfonation
Base benzimidazole；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in and obtains the sulphur that mass concentration is 6% in dimethyl sulfoxide
Change poly- imino group benzimidazole solution, add 1mmol dibromodiphenyl ethers, makes in the amino and dibromodiphenyl ether in benzimidazole
Benzyl bromide molar ratio is 1:1, it pours into polytetrafluoroethylene (PTFE) mould, is heated at 80 DEG C for 24 hours, then in 160 DEG C after mixing
3h is heated, its is made full cross-linked to obtain high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is put into the aminotrimethylenephosphonic acid aqueous solution of 0.1mol/L,
48h is impregnated under room temperature, is then taken out, is washed with deionized, then heats 5h at 80 DEG C, is then heated at 160 DEG C
The poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is obtained for 24 hours.
After tested, the linear swelling coefficient under the proton exchange membrane room temperature prepared by the present embodiment is 8.34%, thermostabilization
Temperature is 270 DEG C, tensile strength 53.1MPa, ion exchange capacity 0.90mmol/g and is measured under 180 DEG C of anhydrous conditions
Conductivity is 0.061S/cm.
Embodiment 3
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is prepared, steps are as follows：
1) 15mL m-cresols and 0.8mL triethylamines is added in 1.8mmol4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid
In the mixed solvent, be passed through nitrogen, be sufficiently stirred, until all dissolving obtains diamino disulphonic acid for diamino disulfonic acid,
Bis- (4- sulphenyls) benzidine of 1.4mmol 3,3 '-, the bis- [2- (4- of 1mmol 6,6 '-are added into diamino disulphonic acid
Aminophenyl)] benzimidazole and 2.4mmol Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidic dianhydrides are sufficiently stirred at room temperature, prior to 80 DEG C at heat
5h, then heated for 24 hours at 180 DEG C, cooled to room temperature, adds 12mL m-cresols and 100mL acetone as diluent,
It is filtered after being sufficiently stirred, filters out fibery precipitate, sediment is washed with acetone, then be dried in vacuo to obtain the poly- imido of sulfonation
Base benzimidazole；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in and obtains the sulphur that mass concentration is 6% in dimethyl sulfoxide
Change poly- imino group benzimidazole solution, add 1mmol dibromodiphenyl ethers, makes in the amino and dibromodiphenyl ether in benzimidazole
Benzyl bromide molar ratio is 1:1, it pours into polytetrafluoroethylene (PTFE) mould, is heated at 80 DEG C for 24 hours, then in 160 DEG C after mixing
3h is heated, its is made full cross-linked to obtain high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is put into the aminotrimethylenephosphonic acid aqueous solution of 0.1mol/L,
48h is impregnated under room temperature, is then taken out, is washed with deionized, then heats 5h at 80 DEG C, is then heated at 160 DEG C
The poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is obtained for 24 hours.
After tested, the linear swelling coefficient under the proton exchange membrane room temperature prepared by the present embodiment is 8.96%, thermostabilization
Temperature is 273 DEG C, tensile strength 55.7MPa, ion exchange capacity 0.95mmol/g and is measured under 180 DEG C of anhydrous conditions
Conductivity is 0.067S/cm.
Embodiment 4
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is prepared, steps are as follows：
1) 15mL m-cresols and 0.8mL triethylamines is added in 1.8mmol4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid
In the mixed solvent, be passed through nitrogen, be sufficiently stirred, until all dissolving obtains diamino disulphonic acid for diamino disulfonic acid,
Bis- (4- sulphenyls) benzidine of 1.6mmol 3,3 '-, the bis- [2- (4- of 1mmol 6,6 '-are added into diamino disulphonic acid
Aminophenyl)] benzimidazole and 2mmol Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidic dianhydrides are sufficiently stirred at room temperature, prior to 80 DEG C at heat 5h,
It is heated at 180 DEG C again for 24 hours, cooled to room temperature, adds 12mL m-cresols and 100mL acetone as diluent, fill
It is filtered after dividing stirring, filters out fibery precipitate, sediment is washed with acetone, then be dried in vacuo to obtain the poly- imino group of sulfonation
Benzimidazole；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in and obtains the sulphur that mass concentration is 6% in dimethyl sulfoxide
Change poly- imino group benzimidazole solution, add 1mmol dibromodiphenyl ethers, makes in the amino and dibromodiphenyl ether in benzimidazole
Benzyl bromide molar ratio is 1:1, it pours into polytetrafluoroethylene (PTFE) mould, is heated at 80 DEG C for 24 hours, then in 160 DEG C after mixing
3h is heated, its is made full cross-linked to obtain high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is put into the aminotrimethylenephosphonic acid aqueous solution of 0.1mol/L,
48h is impregnated under room temperature, is then taken out, is washed with deionized, then heats 5h at 80 DEG C, is then heated at 160 DEG C
The poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is obtained for 24 hours.
After tested, the linear swelling coefficient under the proton exchange membrane room temperature prepared by the present embodiment is 6.73%, thermostabilization
Temperature is 262 DEG C, tensile strength 51.7MPa, ion exchange capacity 0.75mmol/g and is measured under 180 DEG C of anhydrous conditions
Conductivity is 0.064S/cm.
Embodiment 5
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is prepared, steps are as follows：
1) 15mL m-cresols and 0.8mL triethylamines is added in 1.8mmol4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid
In the mixed solvent, be passed through nitrogen, be sufficiently stirred, until all dissolving obtains diamino disulphonic acid for diamino disulfonic acid,
Bis- (4- sulphenyls) benzidine of 1.8mmol 3,3 '-, the bis- [2- (4- of 1mmol 6,6 '-are added into diamino disulphonic acid
Aminophenyl)] benzimidazole and 2mmol Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidic dianhydrides are sufficiently stirred at room temperature, prior to 80 DEG C at heat 5h,
It is heated at 180 DEG C again for 24 hours, cooled to room temperature, adds 12mL m-cresols and 100mL acetone as diluent, fill
It is filtered after dividing stirring, filters out fibery precipitate, sediment is washed with acetone, then be dried in vacuo to obtain the poly- imino group of sulfonation
Benzimidazole；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in and obtains the sulphur that mass concentration is 6% in dimethyl sulfoxide
Change poly- imino group benzimidazole solution, add 1mmol dibromodiphenyl ethers, makes in the amino and dibromodiphenyl ether in benzimidazole
Benzyl bromide molar ratio is 1:1, it pours into polytetrafluoroethylene (PTFE) mould, is heated at 80 DEG C for 24 hours, then in 160 DEG C after mixing
3h is heated, its is made full cross-linked to obtain high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is put into the aminotrimethylenephosphonic acid aqueous solution of 0.1mol/L,
48h is impregnated under room temperature, is then taken out, is washed with deionized, then heats 5h at 80 DEG C, is then heated at 160 DEG C
The poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is obtained for 24 hours.
After tested, the linear swelling coefficient under the proton exchange membrane room temperature prepared by the present embodiment is 7.36%, thermostabilization
Temperature is 275 DEG C, tensile strength 54.6MPa, ion exchange capacity 0.87mmol/g and is measured under 180 DEG C of anhydrous conditions
Conductivity is 0.067S/cm.
Embodiment 6
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is prepared, steps are as follows：
1) 15mL m-cresols and 0.8mL triethylamines is added in 1.8mmol4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid
In the mixed solvent, be passed through nitrogen, be sufficiently stirred, until all dissolving obtains diamino disulphonic acid for diamino disulfonic acid,
Bis- (4- sulphenyls) benzidine of 1.8mmol 3,3 '-, the bis- [2- (4- of 1mmol 6,6 '-are added into diamino disulphonic acid
Aminophenyl)] benzimidazole and 2.2mmol Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidic dianhydrides are sufficiently stirred at room temperature, prior to 80 DEG C at heat
5h, then heated for 24 hours at 180 DEG C, cooled to room temperature, adds 12mL m-cresols and 100mL acetone as diluent,
It is filtered after being sufficiently stirred, filters out fibery precipitate, sediment is washed with acetone, then be dried in vacuo to obtain the poly- imido of sulfonation
Base benzimidazole；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in and obtains the sulphur that mass concentration is 6% in dimethyl sulfoxide
Change poly- imino group benzimidazole solution, add 1mmol dibromodiphenyl ethers, makes in the amino and dibromodiphenyl ether in benzimidazole
Benzyl bromide molar ratio is 1:1, it pours into polytetrafluoroethylene (PTFE) mould, is heated at 80 DEG C for 24 hours, then in 160 DEG C after mixing
3h is heated, its is made full cross-linked to obtain high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is put into the aminotrimethylenephosphonic acid aqueous solution of 0.1mol/L,
48h is impregnated under room temperature, is then taken out, is washed with deionized, then heats 5h at 80 DEG C, is then heated at 160 DEG C
The poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is obtained for 24 hours.
After tested, the linear swelling coefficient under the proton exchange membrane room temperature prepared by the present embodiment is 8.95%, thermostabilization
Temperature is 277 DEG C, tensile strength 61.3MPa, ion exchange capacity 0.85mmol/g and is measured under 180 DEG C of anhydrous conditions
Conductivity is 0.069S/cm.
Embodiment 7
A kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation is prepared, steps are as follows：
1) 15mL m-cresols and 0.8mL triethylamines is added in 1.8mmol4,4 '-diaminodiphenyl ethers -2,2 '-disulfonic acid
In the mixed solvent, be passed through nitrogen, be sufficiently stirred, until all dissolving obtains diamino disulphonic acid for diamino disulfonic acid,
Bis- (4- sulphenyls) benzidine of 1.8mmol 3,3 '-, the bis- [2- (4- of 1mmol 6,6 '-are added into diamino disulphonic acid
Aminophenyl)] benzimidazole and 2.4mmol Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidic dianhydrides are sufficiently stirred at room temperature, prior to 80 DEG C at heat
5h, then heated for 24 hours at 180 DEG C, cooled to room temperature, adds 12mL m-cresols and 100mL acetone as diluent,
It is filtered after being sufficiently stirred, filters out fibery precipitate, sediment is washed with acetone, then be dried in vacuo to obtain the poly- imido of sulfonation
Base benzimidazole；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in and obtains the sulphur that mass concentration is 6% in dimethyl sulfoxide
Change poly- imino group benzimidazole solution, add 1mmol dibromodiphenyl ethers, makes in the amino and dibromodiphenyl ether in benzimidazole
Benzyl bromide molar ratio is 1:1, it pours into polytetrafluoroethylene (PTFE) mould, is heated at 80 DEG C for 24 hours, then in 160 DEG C after mixing
3h is heated, its is made full cross-linked to obtain high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is put into 0.1mol/L aminotrimethylenephosphonic acid aqueous solutions, in room
48h is impregnated under the conditions of temperature, is then taken out, is washed with deionized, then heats 5h at 80 DEG C, is then heated for 24 hours at 160 DEG C
Obtain the poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation.
After tested, the linear swelling coefficient under the proton exchange membrane room temperature prepared by the present embodiment is 9.34%, thermostabilization
Temperature is 283 DEG C, tensile strength 67.6MPa, ion exchange capacity 0.97mmol/g and is measured under 180 DEG C of anhydrous conditions
Conductivity is 0.073S/cm.
Bound, section value and the technological parameter of each raw material and each raw material of the present invention cited by the present invention
Bound, the section value of (such as temperature, time) can realize the present invention, embodiment numerous to list herein.
Claims (8)
1. a kind of poly- imino group benzimidazole high temperature proton exchange film of phosphonic acids doping cross-linking sulfonation, which is characterized in that it is by following
Method is prepared：
1) in a nitrogen atmosphere, diamino disulfonic acid is dissolved in solvent and obtains diamino disulphonic acid, to two sulphur of diamino
Benzidine, benzimidazole containing aminophenyl and naphthalenetetracarbacidic acidic dianhydride are added in acid solution, stir thoroughly at room temperature is uniform, in 70-90 DEG C
5-6h is heated, then heats 18-24h in 165-180 DEG C, cooled to room temperature adds diluent, is sufficiently stirred, and filters,
The solid matter filtered out is washed, is dried to obtain the poly- imino group benzimidazole of sulfonation；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in dimethyl sulfoxide, it is molten obtains the poly- imino group benzimidazole of sulfonation
Liquid adds dibromodiphenyl ether, and it is 1 to make amino and benzyl bromide molar ratio in solution:1, after mixing in 75-80 DEG C of reaction
Then 18-24h heats 2-4h in 150-160 DEG C, obtains high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is placed in aminotrimethylenephosphonic acid aqueous solution and impregnates 36-48h, then spend from
Then sub- water washing heats 5-6h in 70-90 DEG C, finally heating 18-24h in 150-160 DEG C obtains phosphonic acids doping cross-linking sulfonation
Poly- imino group benzimidazole high temperature proton exchange film；
Step 1) the solvent is m-cresol and triethylamine 18-25 by volume:1 mixed solvent being mixed to get；It is described dilute
Release agent be between phenyl methylcarbamate and acetone mixture.
2. high temperature proton exchange film according to claim 1, it is characterised in that step 1) the diamino disulfonic acid is 4,
4'- diamino -2,2'- disulfonic acid, 4,4'- diaminobenzil -2,2'- disulfonic acid, 4,4 '-diaminodiphenyl ethers -2,2 ' -
One kind in disulfonic acid.
3. high temperature proton exchange film according to claim 1, it is characterised in that the step 1) solvent be m-cresol with
Triethylamine 18-25 by volume:1 mixed solvent being mixed to get；A concentration of 0.05- of diamino disulphonic acid
0.12mol/L。
4. high temperature proton exchange film according to claim 1, it is characterised in that the step 1) benzidine is 3, and 3 '-is bis-
(4- sulphenyls) benzidine；The benzimidazole containing aminophenyl is 6,6 '-bis- [2- (4- aminophenyls)] benzimidazoles；It is described
The molar ratio of aniline, benzimidazole containing aminophenyl and naphthalene tetracid dianhydride is 1.4-1.8:1:2-2.6, and diamino disulfonic acid with
The molar ratio of the benzimidazole containing aminophenyl is 1:1.
5. high temperature proton exchange film according to claim 1, it is characterised in that the step 1) diluent be between phenyl methylcarbamate
With the mixture of acetone, in-between phenyl methylcarbamate is 1 with acetone volume ratio：5.
6. high temperature proton exchange film according to claim 1, it is characterised in that the poly- imino group benzo of the step 2) sulfonation
The mass concentration of imidazole solution is 6%.
7. high temperature proton exchange film according to claim 1, it is characterised in that step 3) the aminotrimethylenephosphonic acid water
Solution concentration is 0.08-0.12mol/L.
8. a kind of preparation method of any high temperature proton exchange films of claim 1-7, it is characterised in that steps are as follows：
1) in a nitrogen atmosphere, diamino disulfonic acid is dissolved in solvent and obtains diamino disulphonic acid, to two sulphur of diamino
Benzidine, benzimidazole containing aminophenyl and naphthalenetetracarbacidic acidic dianhydride are added in acid solution, stir thoroughly at room temperature is uniform, in 70-90 DEG C
5-6h is heated, then heats 18-24h in 165-180 DEG C, cooled to room temperature adds diluent, is sufficiently stirred, and filters,
The solid matter filtered out is washed, is dried to obtain the poly- imino group benzimidazole of sulfonation；
2) the poly- imino group benzimidazole of sulfonation obtained by step 1) is dissolved in dimethyl sulfoxide, it is molten obtains the poly- imino group benzimidazole of sulfonation
Liquid adds dibromodiphenyl ether, and it is 1 to make amino and benzyl bromide molar ratio in solution:1, after mixing in 75-80 DEG C of reaction
Then 18-24h heats 2-4h in 150-160 DEG C, obtains high temperature proton exchange film；
3) high temperature proton exchange film obtained by step 2) is placed in aminotrimethylenephosphonic acid aqueous solution and impregnates 36-48h, then spend from
Then sub- water washing heats 5-6h in 70-90 DEG C, finally heating 18-24h in 150-160 DEG C obtains phosphonic acids doping cross-linking sulfonation
Poly- imino group benzimidazole high temperature proton exchange film.
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| CN101891955A (en) * | 2010-07-15 | 2010-11-24 | 上海大学 | Method for preparing high-temperature-resistant BPO4-ABPBI nanometer composite proton exchange membrane for fuel cell |
| CN102842726A (en) * | 2011-06-21 | 2012-12-26 | 东丽纤维研究所（中国）有限公司 | Silsesquioxane hybridized sulfonated polyimide proton exchange membrane and its preparation method |
| CN103094587A (en) * | 2013-01-21 | 2013-05-08 | 常州大学 | Preparation method of high-temperature resistant sulfonated polyimide-zirconium phosphate proton exchange composite membrane |
| CN103724630A (en) * | 2013-12-06 | 2014-04-16 | 同济大学 | Synthesis method for block-type sulfonated polyimides-polybenzimidazole proton exchange membrane material |
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| JP4845609B2 (en) * | 2005-06-28 | 2011-12-28 | 三星エスディアイ株式会社 | Polymer electrolyte membrane for fuel cell, membrane-electrode assembly for fuel cell including the same, and fuel cell system including the same |
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| CN101891955A (en) * | 2010-07-15 | 2010-11-24 | 上海大学 | Method for preparing high-temperature-resistant BPO4-ABPBI nanometer composite proton exchange membrane for fuel cell |
| CN102842726A (en) * | 2011-06-21 | 2012-12-26 | 东丽纤维研究所（中国）有限公司 | Silsesquioxane hybridized sulfonated polyimide proton exchange membrane and its preparation method |
| CN103094587A (en) * | 2013-01-21 | 2013-05-08 | 常州大学 | Preparation method of high-temperature resistant sulfonated polyimide-zirconium phosphate proton exchange composite membrane |
| CN103724630A (en) * | 2013-12-06 | 2014-04-16 | 同济大学 | Synthesis method for block-type sulfonated polyimides-polybenzimidazole proton exchange membrane material |
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