CN108384170B - Cross-linked organic phosphonic acid high-temperature proton exchange membrane and preparation method thereof - Google Patents

Cross-linked organic phosphonic acid high-temperature proton exchange membrane and preparation method thereof Download PDF

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CN108384170B
CN108384170B CN201810533833.2A CN201810533833A CN108384170B CN 108384170 B CN108384170 B CN 108384170B CN 201810533833 A CN201810533833 A CN 201810533833A CN 108384170 B CN108384170 B CN 108384170B
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phosphonic acid
organic phosphonic
proton exchange
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胡金波
何正标
李铃春
陈佳孝
祝传贺
邓玲
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The invention provides a cross-linked organic phosphonic acid high-temperature proton exchange membrane and a preparation method thereof, and particularly relates to a high-temperature proton exchange membrane which is formed by compounding a polybenzimidazole compound A, an acid-base organic phosphonic acid polymer B and an organic micromolecule cross-linking agent C serving as raw materials, wherein the acid-base organic phosphonic acid polymer B is a copolymer formed by copolymerizing an alkaline olefin monomer D and an organic phosphonic acid monomer E. The cross-linked organic phosphonic acid high-temperature proton exchange membrane has high proton conductivity, high mechanical strength, high thermal stability, high oxidation resistance stability and low phosphonic acid loss rate, and is very suitable for proton exchange membrane fuel cells.

Description

Cross-linked organic phosphonic acid high-temperature proton exchange membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a cross-linked organic phosphonic acid high-temperature proton exchange membrane and a preparation method thereof.
Background
Currently, the proton exchange membrane widely used in high temperature proton exchange membrane fuel cells is a PBI (polybenzimidazole) type proton exchange membrane. PBI membranes were first marketed by Hoechst Celanese corporation of america. Since the film must be doped with inorganic phosphoric acid and relies on inorganic phosphoric acid to conduct protons, it has the greatest disadvantage of the loss of inorganic phosphoric acid. Since water is generated during the operation of the fuel cell and the generated water is discharged from the membrane, the inorganic phosphoric acid is lost along with the discharge of the generated water, so that the proton conductivity of the membrane is reduced, the performance of the fuel cell is attenuated, and the stable service life of the fuel cell is shortened. Therefore, loading phosphonic acid on the high temperature resistant polymer to prevent its loss has become an important way to solve the phosphoric acid loss. Organic phosphonic acid high temperature proton exchange membranes have become a necessary direction of development.
At present, the preparation methods of the organic phosphonic acid high-temperature proton exchange membrane reported mainly include three main types, namely an acid-base mixed type, an acid-base organic phosphonic acid polymer type and an acid organic phosphonic acid polymer type. However, these methods have some problems, such as: (1) the organic phosphonic acid polymer is difficult to prepare and is not suitable for large-scale production; (2) the film-making process is complicated, for example, the process is very complicated in the product released by BASF company; (3) the phosphonic acid content can not be accurately controlled, and the conductivity is difficult to regulate and control; (4) insufficient mechanical strength, etc.
In conclusion, a high-temperature proton exchange membrane with concise preparation of organic phosphonic acid polymer, simple membrane preparation process, accurate and controllable organic phosphonic acid content and proton conductivity and high mechanical strength and a preparation method thereof are not available in the field.
Disclosure of Invention
The invention aims to provide a cross-linked organic phosphonic acid high-temperature proton exchange membrane and a preparation method thereof.
The invention provides a cross-linked organic phosphonic acid high-temperature proton exchange membrane, which is formed by compounding a polybenzimidazole compound A, another acid-base organic phosphonic acid polymer B and an organic small molecule cross-linking agent C as raw materials, wherein the molar ratio nA to nB is 1:0.01-99.99, and the molar ratio nA to nC is 1: 0.01-5.00;
and the acid-base organic phosphonic acid polymer B is a copolymer formed by copolymerizing a basic olefin monomer D and an organic phosphonic acid monomer E, wherein the basic olefin monomer D is a monomer selected from the following group:
Figure BDA0001677180690000021
the organic phosphonic acid monomer E is selected from the following group:
Figure BDA0001677180690000022
R2selected from the group consisting of: H. substituted or unsubstituted C1-C9 alkyl, phenyl (Ph), TMS (Me)3Si, trimethylsilyl), TES (Et)3Si, triethylsilyl), TBS (tert-butyldimethylsilyl), TIPS (triisopropylsilyl), TBDPS (tert-butyldiphenylsilyl).
In another preferred embodiment, the polybenzimidazole based polymer a is selected from the group consisting of:
Figure BDA0001677180690000031
wherein n is 2-10000;
r is selected from the group consisting of: none, O, S, NH, C (O), S (O)2Unsubstituted or halogenated C1-C6 alkylene, unsubstituted or halogenated C2-C6 alkenylene;
R1selected from the group consisting of:
Figure BDA0001677180690000032
in another preferred embodiment, the polybenzimidazole type compound a is selected from the group consisting of:
Figure BDA0001677180690000041
in another preferred embodiment, in the "acid-base" type organic phosphonic acid polymer B, the molar ratio of monomer D copolymerized with monomer E is nD: nE ═ 1:0.01 to 99.99, preferably, the molar ratio of monomer D copolymerized with monomer E is nD: nE ═ 1:1 to 20.
In another preferred embodiment, the "acid-base" type organic phosphonic acid polymer B is prepared by the following method: and (3) carrying out polymerization reaction on the monomer D and the organic phosphonic acid monomer E in deionized water to obtain the polymer B.
In another preferred embodiment, the reaction is carried out under the protection of nitrogen.
In another preferred embodiment, the reaction is carried out in the presence of an initiator; preferably, the initiator is a free radical chain initiator; more preferably, the molar amount of the initiator is 0.1 to 5 percent of the total molar amount of the monomer D and the organic phosphonic acid monomer E.
In another preferred embodiment, the "acid-base" type organic phosphonic acid polymer B is prepared by the following method:
(1) under the protection of nitrogen, sequentially adding a monomer D and an organic phosphonic acid monomer E into a three-mouth reaction bottle, taking deionized water as a solvent, and then adding a free radical chain initiator Azobisisobutyronitrile (AIBN), wherein the molar weight of the AIBN is 0.1-5% of the total molar weight of the monomer D and the organic phosphonic acid monomer E;
(2) stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. And pouring the reaction solution into ethyl acetate, continuously stirring, separating out solids, filtering and drying to obtain the acid-base organic phosphonic acid polymer B.
In another preferred embodiment, the organic small molecule cross-linking agent C is selected from the group consisting of:
Figure BDA0001677180690000051
in another preferred embodiment, the molar ratio of a to B, nA: nB, is 1: 0.1-40, and the molar ratio of A to C nC is 1: 0.02-5.00.
In a second aspect of the present invention, there is provided a method for preparing a cross-linked organophosphonic acid high-temperature proton exchange membrane according to the first aspect of the present invention, the method for preparing the cross-linked organophosphonic acid high-temperature proton exchange membrane comprises:
(i) providing a polybenzimidazole type compound A and an acid-base type organic phosphonic acid polymer B;
(ii) under the protection of inert gas, dissolving the mixture of the two in an organic solvent to prepare a mixed solution;
(iii) cooling to room temperature, adding the organic small molecular cross-linking agent C, and stirring until the mixture is uniformly mixed;
(iv) filtering to remove insoluble substances to obtain mixed filtrate;
(v) degassing the mixed filtrate;
(vi) and (3) forming a membrane from the mixed filtrate subjected to degassing treatment to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane.
In another preferred embodiment, the molar ratio of the polybenzimidazole type compound a to the "acid-base" type organic phosphonic acid polymer B is 1:0.1 to 40.
In another preferred embodiment, the organic solvent is a strongly polar organic solvent, and is more preferably selected from the group consisting of: DMSO (dimethyl sulfoxide), DMF (N, N-dimethylformamide), DMAC (N, N-dimethylacetamide), or NMP (N-methylpyrrolidone), or a combination thereof.
In another preferred embodiment, in the step (ii), the solid content of the prepared solution is 1-30 wt%.
In another preferred embodiment, the film formation comprises: coating a film on a glass plate or a plastic film and drying to form the cross-linked organic phosphonic acid high-temperature proton exchange membrane.
In another preferred embodiment, the coating method is a casting method.
In another preferred embodiment, the drying includes: after primary drying at 70-90 ℃, heating to 100-140 ℃ for secondary drying, and then heating to 160-300 ℃ for third drying.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a graph of proton conductivity as a function of temperature for organophosphonic acid high temperature proton exchange membranes and PBI membranes of examples 1,4, 5, 7, 13, 14 and 16.
FIG. 2 is a graph comparing the results of the high temperature proton exchange membrane phosphoric acid (phosphonic acid) run off rate tests prepared in examples 1, 13, and 14.
FIG. 3 is a graph of the single cell discharge of the high temperature PEM prepared in examples 1, 14 and 16.
FIG. 4 is a graph showing the cell operating stability test of the high temperature proton exchange membranes prepared in examples 7 and 14.
Detailed Description
The inventor of the invention has found through long-term and intensive research that the polybenzimidazole compound A, another acid-base organic phosphonic acid polymer B and an organic small molecular cross-linking agent C are adopted as raw materials to be compounded to prepare a solution and then form a film, so that the organic phosphonic acid high-temperature proton exchange membrane with high proton conductivity, high mechanical strength and low phosphonic acid loss rate can be prepared, and the high-temperature proton exchange membrane is very suitable for being used as a proton exchange membrane of a high-temperature proton conducting membrane fuel cell. Based on the above findings, the inventors have completed the present invention.
The crosslinking type organic phosphonic acid high-temperature proton exchange membrane of the invention adopts a composite mode of 'alkaline' polymer plus 'acid-alkali' type organic phosphonic acid polymer plus crosslinking agent to form a membrane, and compared with the reported organic phosphonic acid high-temperature proton exchange membrane and the preparation method, the crosslinking type organic phosphonic acid high-temperature proton exchange membrane has the following advantages:
1) the preparation method of the organic phosphonic acid polymer is simple and is suitable for large-scale batch production;
2) the film preparation process is simple and is suitable for large-scale batch preparation;
3) the content of organic phosphonic acid is accurate and controllable, and the proton conductivity can be accurately regulated and controlled;
4) the strength is high, and the swelling ratio is low;
therefore, the cross-linking type organic phosphonic acid high-temperature proton exchange membrane has high mechanical strength, accurate and controllable proton conductivity, low phosphonic acid loss rate, higher working stability and durability, and is beneficial to promoting the commercial development of high-temperature fuel cells.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Example 1
m-PBI and [ N-vinylimidazole-vinylphosphonic acid bis (trimethylsilyl) ester]Copolymer B1And preparation of 1, 4-bis (chloromethyl) benzene composite membrane
Figure BDA0001677180690000071
(1) N-vinylimidazole-vinylphosphonic acid bis (trimethylsilyl) ester copolymer B1(molar ratio 1: 6) preparation
N-vinylimidazole (188.2mg,2mmol) and bis (trimethylsilyl) vinylphosphonate (3028.7mg,12mmol) were added sequentially under nitrogen protection to a three-necked reaction flask, deionized water (200mL) was used as the solvent, and then the free radical chain initiator azobisisobutyronitrile (AIBN,24.63mg,0.15mmol) was added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B1。
(2) m-PBI and copolymer B1And preparation of 1, 4-bis (chloromethyl) benzene (molar ratio 1:3: 0.1) composite membrane
According to the following steps of 1:3: 0.1 molar ratio, dry m-PBI (154.2mg,0.5 mm) was weighedol) with copolymer B1(2412.6mg,1.5 mmol). Under the protection of nitrogen, dissolving the mixture of the two into dry DMAC (N, N-dimethylacetamide, 48.771g), heating and stirring to prepare a solution with the solid content of 5%, cooling to room temperature, adding 1, 4-bis (chloromethyl) benzene (8.8mg,0.05mmol), stirring for 2 hours, uniformly stirring, filtering to remove insoluble substances, degassing the filtrate, casting onto a glass plate with the thickness of 10cm × 10cm, drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 210 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 28 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 115MPa when the temperature is 309 ℃.
Example 2
O-PBI and [ 1-vinylpyrazole-1, 1-vinylphosphonic acid tetramethyl ester]Copolymer B2And preparation of 1, 4-bis (bromomethyl) benzene composite membrane
Figure BDA0001677180690000081
(1) Preparation of 1-vinylpyrazole-1, 1-vinylphosphonic acid tetramethylester copolymer B3 (molar ratio 1:5)
1-vinylpyrazole (94.1mg,1mmol) and 1, 1-vinylphosphonic acid tetramethyl ester (1220.6mg,5mmol) were added sequentially under nitrogen to a three-necked reaction flask, deionized water (200mL) was used as the solvent, followed by the addition of the free radical chain initiator azobisisobutyronitrile (AIBN,14.78mg,0.09 mmol). Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B2。
(2) O-PBI and copolymer B2And preparation of 1, 4-bis (bromomethyl) benzene (molar ratio 1:4: 0.5) composite membrane
According to the following steps of 1:4: 0.5 molar ratio, dry O-PBI (80.1mg,0.2mmol) is weighed out against copolymer B2(841.4mg,0.8mmol)。Under the protection of nitrogen, dissolving the mixture of the two into dry DMAC (N, N-dimethylacetamide, 14.437g), heating and stirring to prepare a solution with the solid content of 6%, cooling to room temperature, adding 1, 4-bis (bromomethyl) benzene (26.4mg,0.1mmol), stirring for 2 hours, uniformly stirring, filtering to remove insoluble substances, degassing the filtrate, casting the filtrate onto a glass plate with the thickness of 10cm × 10cm, drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 200 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 26 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength was 105MPa as shown by mechanical testing at 318 ℃.
Example 3
F6-PBI and [ 1-vinyl triazole-dimethyl vinylphosphonate]Copolymer B3And 2[ (4-chloromethyl) phenoxy group]Preparation of methyl ethylene oxide composite film
Figure BDA0001677180690000091
(1) 1-vinyl triazole-dimethyl vinylphosphonate copolymer B3Preparation of (molar ratio 1: 7):
under the protection of nitrogen, 1-vinyl triazole (95.1mg,1mmol) and dimethyl vinylphosphonate (952.6mg,7mmol) are added in sequence into a three-neck reaction flask, deionized water (200mL) is used as a solvent, and then a free radical chain initiator, namely azobisisobutyronitrile (AIBN,9.9mg,0.06mmol), is added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B3。
(2)F6-PBI and copolymer B3And 2[ (4-chloromethyl) phenoxy group]Preparation of composite membrane of methyl oxirane (molar ratio 1:4:2)
Weighing the dried F in a molar ratio of 1:4:26PBI (80.2mg,0.15mmol) and copolymer B3(628.6mg,0.6 mmol). Dissolving the mixture in dry NMP (N-methylpyrrolidone 9.417g) under nitrogen protection, heating and stirring to obtain solution with solid content of 7%, cooling to room temperature, adding 2[ (4-chloromethyl) phenoxy]Methyl ethylene oxide (59.6mg,0.3mmol) is stirred for 2 hours, the mixture is uniformly stirred and filtered, insoluble substances are filtered, the filtrate is subjected to degassing treatment and then is cast on a glass plate with the thickness of 10cm multiplied by 10cm, then the glass plate is placed in a blast oven to be dried for two hours at the temperature of 80 ℃, then the temperature is further raised to 120 ℃ to be dried for one hour, and finally the temperature is raised to 240 ℃ to be dried for one hour, so that the cross-linked organic phosphonic acid high-temperature proton exchange membrane is obtained. The film had a thickness of 32 μm (micrometers) and a DSC test showed a glass transition temperature Tg295 ℃, the tensile strength of which is 112MPa as shown by mechanical property tests.
Example 4
Py-O-PBI and [ N-vinyl-1, 3, 4-triazole-1, 1-vinyl diphosphonate tetraphenyl ester]Copolymer B7And 2[ (2-chloromethyl) phenoxy group]Preparation of methyl ethylene oxide composite film
Figure BDA0001677180690000101
(1) N-vinyl-1, 3, 4-triazole-1, 1-vinyl diphosphonite tetraphenyl ester copolymer B4(molar ratio 1:4) preparation
Under the protection of nitrogen, N-vinyl-1, 3, 4-triazole (95.1mg,1mmol) and 1, 1-vinyl diphosphotetetraphenyl ester (1968.3mg,4mmol) are sequentially added into a three-mouth reaction bottle, deionized water (200mL) is used as a solvent, and then a free radical chain initiator, namely azobisisobutyronitrile (AIBN,9.9mg,0.06mmol) is added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B4。
(2) Py-O-PBI and copolymer B4And 2[ (2-chloromethyl) phenoxy group]Preparation of composite membrane of methyl oxirane (molar ratio 1:0.1:0.2)
According to the molar ratio of 1:0.1:0.2,the dry Py-O-PBI (355.4mg,1mmol) was weighed out together with copolymer B4(206.3mg,0.1 mmol). Dissolving the mixture in dry DMAC (N, N-dimethylacetamide, 18.163g) under nitrogen protection, heating and stirring to obtain a solution with a solid content of 3%, cooling to room temperature, and adding 2[ (2-chloromethyl) phenoxy]Methyl ethylene oxide (39.7mg,0.2mmol) is stirred for 2 hours, the mixture is uniformly stirred and filtered, insoluble substances are filtered, the filtrate is subjected to degassing treatment and then is cast on a glass plate with the thickness of 10cm multiplied by 10cm, then the glass plate is placed in a blast oven to be dried for two hours at the temperature of 80 ℃, then the temperature is further raised to 120 ℃ to be dried for one hour, and finally the temperature is raised to 230 ℃ to be dried for one hour, so that the cross-linked organic phosphonic acid high-temperature proton exchange membrane is obtained. The film had a thickness of 30 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength was 117MPa as shown by mechanical property testing at 335 ℃.
Example 5
SO2-PBI and [ N-vinylbenzimidazole-vinylphosphonic acid bis (trimethylsilyl) ester]Copolymer B5And preparation of 1, 4-bis (oxacyclopropylmethoxy) benzene composite membrane
Figure BDA0001677180690000111
(1) N-vinylbenzimidazole-vinylphosphonic acid bis (trimethylsilyl) ester copolymer B5(molar ratio 1:8) preparation
N-vinylbenzimidazole (144.2mg,1mmol) and bis (trimethylsilyl) vinylphosphonate (2016.6mg,8mmol) were added sequentially under nitrogen atmosphere to a three-necked reaction flask, deionized water (250mL) was used as the solvent, and then the free radical chain initiator azobisisobutyronitrile (AIBN,29.6mg,0.18mmol) was added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B5
(2)SO2-PBI and copolymer B5And 1, 4-bis (oxetanylmethoxy) benzene (molar ratio 1: 0.3: 1) composite membranePrepare for
According to the weight ratio of 1: 0.3: 1 molar ratio, dry SO2PBI (494.6mg,1mmol) and copolymer B9(648.2mg,0.3 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMAC (N, N-dimethylacetamide, 21.713g), heating and stirring to prepare a solution with the solid content of 5%, cooling to room temperature, adding 1, 4-bis (oxacyclopropyl methoxy) benzene (222.2mg,1mmol), stirring for 2 hours, uniformly stirring, filtering to remove insoluble substances, degassing the filtrate, casting the filtrate on a 10cm × 10cm glass plate, drying at 80 ℃ for two hours in a blast oven, further heating to 120 ℃ for drying for one hour, and finally heating to 230 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 35 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 128MPa at 325 ℃.
Example 6
ABPBI and [ 5-vinyl triazole-1, 1-vinyl diphosphonic acid tetramethyl ester]Copolymer B6And preparation of 1, 3-bis [ (oxacyclopropylmethoxy) benzene composite membrane:
Figure BDA0001677180690000121
(1) 5-vinyl triazole-1, 1-vinyl diphosphonic acid tetramethyl ester copolymer B6(molar ratio 1:12) preparation
Under the protection of nitrogen, 5-vinyl triazole (95.1mg,1mmol) and 1, 1-vinyl diphosphonate tetramethyl ester (2929.4mg,12mmol) are added in sequence to a three-neck reaction flask, deionized water (250mL) is used as a solvent, and then a free radical chain initiator, namely azobisisobutyronitrile (AIBN,10.7mg,0.065mmol) is added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B6。
(2) ABPBI and copolymer B6And 1, 3-bis [ (oxetanylmethoxy) benzene(s) ((s))The molar ratio is 1:8: 2) preparing a composite membrane:
according to the ratio of 1:8: 2 molar ratio, dry ABPBI (11.6mg,0.1mmol) and copolymer B are weighed6(2418.7mg,0.8 mmol). Under the protection of nitrogen, dissolving the mixture of the two into dry DMAC (N, N-dimethylacetamide, 27.948g), heating and stirring to prepare a solution with the solid content of 8%, cooling to room temperature, adding 1, 3-bis [ (oxacyclopropyl methoxy) benzene (44.4mg,0.2mmol), stirring for 2 hours, uniformly stirring, filtering to remove insoluble substances, degassing the filtrate, casting to a glass plate with the thickness of 10cm × 10cm, drying for two hours in an air blast oven at 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 240 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 31 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength was 100MPa as shown by mechanical property test at 270 ℃.
Example 7
Poly [2,6- [4 ', 4' -methylene (diphenylmethane)]-benzodiimidazole]With [ 5-vinyltriazole-1, 1-vinylphosphonic acid]Copolymer B7And preparation of 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -bis [ (oxacyclopropylmethoxy) biphenyl composite membrane:
Figure BDA0001677180690000131
(1) 5-vinyl triazole-1, 1-vinyl diphosphonic acid copolymer B7(molar ratio 1:3) preparation
Under the protection of nitrogen, 5-vinyl triazole (95.1mg,1mmol) and 1, 1-vinyl diphosphonic acid (563.9mg,3mmol) are added in sequence into a three-mouth reaction bottle, deionized water (180mL) is used as a solvent, and then a free radical chain initiator, namely azobisisobutyronitrile (AIBN,8.2mg,0.05mmol) is added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B7。
(2)Poly [2,6- [4 ', 4' -methylene (diphenylmethane)]-benzodiimidazole]With copolymer B7And preparation of 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -bis [ (oxetanylmethoxy) biphenyl (molar ratio 1:2:1) composite membrane
The dried poly [2,6- [ 4', 4 "-methylene (diphenylmethane) was weighed in a molar ratio of 1:2:1]-benzodiimidazole](80.6mg,0.25mmol) with copolymer B7(329.5mg,0.5 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dried DMSO (dimethyl sulfoxide, 5.448g), heating and stirring to prepare a solution with the solid content of 7%, cooling to room temperature, adding 3,3 ', 5,5 ' -tetramethyl-4, 4 ' -bis [ (oxacyclopropyl methoxy) biphenyl (88.6mg,0.25mmol), stirring for 2 hours, uniformly stirring, filtering out insoluble substances, degassing the filtrate, casting onto a glass plate with the thickness of 10cm multiplied by 10cm, drying in a blast oven at 80 ℃ for two hours, further heating to 120 ℃ for drying for one hour, and finally heating to 200 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 25 μm (micrometers) and a DSC test showed a glass transition temperature Tg268 ℃, the tensile strength of which is 98MPa as shown by mechanical property tests.
Example 8
Poly [2,2 '- (2 ", 6" -pyridinylidene) -5, 5' -bis (benzimidazolyl) sulfone]And [ 1-vinyltriazole-allylphosphonic acid]Copolymer B8And preparation of 4, 4' -bis [ (oxacyclopropylmethoxy) diphenylmethane composite membrane
Figure BDA0001677180690000141
(1) 1-vinyl triazole-allyl phosphonic acid copolymer B8(molar ratio 1:9) preparation
1-vinylimidazole (95.1mg,1.0mmol) and allylphosphonic acid (1098.0mg,9mmol) were added sequentially to a three-necked reaction flask under nitrogen with deionized water (250mL) as the solvent, followed by the addition of the free radical chain initiator azobisisobutyronitrile (AIBN,19.7mg,0.12 mmol). Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous and stoppedReacting, and cooling to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B8。
(2) Poly [2,2 '- (2 ", 6" -pyridinylidene) -5, 5' -bis (benzimidazolyl) sulfone]With copolymer B8And preparation of 4, 4' -bis [ (oxacyclopropylmethoxy) diphenylmethane (molar ratio 1:3:0.4) composite membrane
Weighing dried poly [2,2 '- (2 ", 6" -pyridylidene) -5, 5' -bis (benzimidazolyl) sulfone in a molar ratio of 1:3:0.4](93.3mg,0.25mmol) with copolymer B8(894.8mg,0.75 mmol). Under the protection of nitrogen, dissolving the mixture of the two in dry DMSO (dimethyl sulfoxide, 18.774g), heating and stirring to prepare a solution with the solid content of 5%, cooling to room temperature, adding 4, 4' -bis [ (oxacyclopropyl methoxy) diphenylmethane (31.2mg,0.1mmol), stirring for 2 hours, uniformly stirring, filtering to remove insoluble substances, degassing the filtrate, casting onto a glass plate with the thickness of 10cm multiplied by 10cm, drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 180 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 28 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 99MPa as shown by a mechanical property test under the temperature of 271 ℃.
Example 9
Poly [2,6- [4 ', 4' -phenylene (diphenyl ether)]-benzodiimidazole]With (N-vinylimidazole-vinylphosphonic acid) copolymers B9And 2, 2-bis [ (4- (oxetanylmethoxy) phenyl)]Preparation of propane composite membrane
Figure BDA0001677180690000151
(1) N-vinylimidazole-vinylphosphonic acid copolymers B9(molar ratio 1:10) preparation
N-vinylimidazole (94.1mg,1.0mmol) and vinylphosphonic acid (1080.0mg,10mmol) were added sequentially to a three-necked reaction flask under nitrogen atmosphere with deionized water (250mL)As a solvent, azobisisobutyronitrile (AIBN,19.7mg,0.12mmol) was then added as a free radical chain initiator. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B9。
(2) Poly [2,6- [4 ', 4' -phenylene (diphenyl ether)]-benzodiimidazole]With copolymer B9And 2, 2-bis [ (4- (oxetanylmethoxy) phenyl)]Preparation of propane (molar ratio 1:2:0.5) composite membrane
Dried poly [2,6- (p-phenylene) -benzodiimidazole was weighed in a molar ratio of 1:2:0.5](129.7mg,0.4mmol) with copolymer B9(939.3mg,0.8 mmol). Dissolving the mixture in dry DMSO (dimethyl sulfoxide, 20.312g) under nitrogen protection, heating and stirring to obtain solution with solid content of 5%, cooling to room temperature, adding 2, 2-bis [ (4- (oxetanylmethoxy) phenyl ] methyl ] phenyl]And (2) stirring propane (68.1mg and 0.2mmol) for 2 hours, uniformly stirring, filtering to remove insoluble substances, degassing the filtrate, casting the solution onto a glass plate with the thickness of 10cm multiplied by 10cm, drying the glass plate in a blast oven at the temperature of 80 ℃ for two hours, further heating to 120 ℃ for drying for one hour, and finally heating to 170 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 29 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 104MPa according to the mechanical property test at 281 ℃.
Example 10
Poly [2,6- [4 ', 4' -phenylene (diphenylsulfone)]-benzodiimidazole]With (4-vinylpyridine-vinylphosphonic acid) copolymers B10And trimethoxy [ (3- (oxetanylmethoxy) propyl ] group]Preparation of silane composite film
Figure BDA0001677180690000161
(1) 4-vinylpyridine-vinylphosphonic acid copolymer B10(molar ratio 1:12) preparation
Under nitrogen4-vinylpyridine (105.0mg,1.0mmol) and vinylphosphonic acid (1296.0mg,12mmol) were added sequentially to a three-necked reaction flask with the protection of deionized water (250mL) as the solvent, followed by the addition of the free radical chain initiator azobisisobutyronitrile (AIBN,14.8mg,0.09 mmol). Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B10。
(2) Poly [2,6- [4 ', 4' -phenylene (diphenylsulfone)]-benzodiimidazole]With copolymer B10Trimethoxy [ (3- (Oxacyclopropylmethoxy) propyl ] methyl]Preparation of silane (molar ratio 1:5:1) composite membrane
The dried poly [2,6- (p-phenylene) -benzodiimidazole was weighed in a molar ratio of 1:5:1](55.8mg,0.15mmol) with copolymer B10(1050.8mg,0.75 mmol). Dissolving the mixture in dry DMSO (dimethyl sulfoxide, 21.025g) under nitrogen protection to obtain a solution with solid content of 5%, cooling to room temperature, adding trimethoxy [ (3- (oxetanylmethoxy) propyl ] group]Silane (35.4mg,0.15mmol) is stirred for 2 hours, the mixture is uniformly stirred and then filtered, insoluble substances are filtered, the filtrate is subjected to degassing treatment and then is cast on a glass plate with the thickness of 10cm multiplied by 10cm, then the glass plate is placed into a blast oven to be dried for two hours at the temperature of 80 ℃, then the temperature is further raised to 120 ℃ to be dried for one hour, and finally the temperature is raised to 170 ℃ to be dried for one hour, so that the cross-linked organic phosphonic acid high-temperature proton exchange membrane is obtained. The film had a thickness of 21 μm (micrometers) and a DSC test showed a glass transition temperature Tg279 ℃, the tensile strength of which is 105MPa as shown by mechanical property tests.
Example 11
Poly [2,6- (p-phenylene) -benzodiimidazole]With [ 5-vinylpyrimidin-2-propenyl [ 2-methylenephosphonic acid bis (trimethylsilyl) ester]Phosphonic acid bis (trimethylsilyl) ester]]Copolymer B11And preparation of 2, 2-dimethylpropylene glycol di (oxetanylmethyl) ether composite membrane
Figure BDA0001677180690000171
(1) 5-Vinylpyrimidine-2-propenyl [ 2-methylenephosphonic acid bis (trimethylsilyl) ester]Phosphonic acid bis (trimethylsilyl) ester]Copolymer B11Preparation of (molar ratio 1:14)
Under the protection of nitrogen, 5-vinyl pyrimidine (106.5mg,1.0mmol) and 2-propenyl [ 2-methylenephosphonic acid bis (trimethylsilyl) ester are added in sequence into a three-mouth reaction bottle]Bis (trimethylsilyl) phosphonate (7058.2mg,14mmol), deionized water (250mL) as solvent, followed by the addition of azobisisobutyronitrile (AIBN,14.0mg,0.085mmol), a free radical chain initiator. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B11。
(2) Poly [2,6- (p-phenylene) -benzodiimidazole]With copolymer B11And preparation of 2, 2-dimethylpropylene glycol di (oxetanylmethyl) ether (molar ratio 1:16:1) composite membrane
The dried poly [2,6- (p-phenylene) -benzodiimidazole was weighed in a molar ratio of 1:16:1](11.6mg,0.05mmol) with copolymer B11(5731.4mg,0.8 mmol). Under the protection of nitrogen, dissolving the mixture of the two into dry DMAC (N, N-dimethylacetamide, 22.972g), heating and stirring to prepare a solution with the solid content of 20%, cooling to room temperature, adding 2, 2-dimethylpropanediol di (oxetanylmethyl) ether (11.0mg,0.05mmol), stirring for 2 hours, uniformly stirring, filtering out insoluble substances, degassing the filtrate, casting onto a glass plate with the thickness of 10cm × 10cm, drying in a forced air oven at 80 ℃ for two hours, further heating to 120 ℃ for drying for one hour, and finally heating to 170 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 36 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 92MPa according to the mechanical property test at 258 ℃.
Example 12
S-PBI and [ 2-vinylbenzimidazole-allylphosphonic acid bis (triethylsilyl) ester]Copolymer B12And [ (4-chloromethyl) phenyl group]Preparation of ethyl trimethoxy silane composite film
Figure BDA0001677180690000181
(1) 2-Vinylbenzimidazole-allylphosphonic acid bis (triethylsilyl) ester copolymer B12(molar ratio 1:15) preparation
Under nitrogen protection, 2-vinylbenzimidazole (144.2mg,1mmol) and bis (trimethylsilyl) vinylphosphonate (5252.9mg,15mmol) were added sequentially to a three-necked reaction flask, deionized water (250mL) was used as a solvent, and then the free radical chain initiator azobisisobutyronitrile (AIBN,9.1mg,0.055mmol) was added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B12。
(2) S-PBI and copolymer B12And [ (4-chloromethyl) phenyl group]Preparation of ethyltrimethoxysilane (molar ratio of 1:8: 0.6) composite film
Dried S-PBI (41.6mg,0.1mmol) and copolymer B were weighed in a molar ratio of 1:8:0.612(4317.6mg,0.8 mmol). Under the protection of nitrogen, the mixture of the two was dissolved in dry DMAC (N, N-dimethylacetamide, 82.826g), heated and stirred to prepare a solution with a solid content of 5%, cooled to room temperature, and [ (4-chloromethyl) phenyl group was added]Ethyl trimethoxy silane (16.5mg,0.06mmol) is stirred for 2 hours, the mixture is uniformly stirred and filtered, insoluble substances are filtered, the filtrate is subjected to degassing treatment and then is cast on a glass plate with the thickness of 10cm multiplied by 10cm, the glass plate is then placed into a blast oven to be dried for two hours at the temperature of 80 ℃, then the temperature is further raised to 120 ℃ for drying for one hour, and finally the temperature is raised to 230 ℃ for drying for one hour, so that the cross-linked organic phosphonic acid high-temperature proton exchange membrane is obtained. The film had a thickness of 36 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the alloy is 132MPa according to the mechanical property test at 302 ℃.
Example 13
p-PBI [ sic ], [ alpha ], [ beta ] -a1-Vinyltriazole-2-propenyl [ 2-methylenephosphonic acid bis (trimethylsilyl) ester]Phosphonic acid bis (trimethylsilyl) ester]Copolymer B13And preparation of 1, 3-bis (chloromethyl) benzene composite membrane
Figure BDA0001677180690000191
(1) 1-Vinyltriazole-2-propenyl [ 2-methylenephosphonic acid bis (trimethylsilyl) ester]Phosphonic acid bis (trimethylsilyl) ester copolymer B13(molar ratio 1:2) preparation
Under the protection of nitrogen, 1-vinyl triazole (95.1mg,1mmol) and 2-propenyl [ 2-methylene phosphonic acid bis (trimethylsilyl) ester are sequentially added into a three-mouth reaction bottle]Bis (trimethylsilyl) phosphonate (1008.3mg,2mmol), deionized water (200mL) as solvent, followed by the addition of azobisisobutyronitrile (AIBN,9.9mg,0.06mmol), a free radical chain initiator. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B13。
(2) p-PBI and copolymer B13And preparation of 1, 3-bis (chloromethyl) benzene composite membrane (molar ratio 1:0.8:0.3)
Weigh dry p-PBI (308.4mg,1mmol) and copolymer B in a molar ratio of 1:0.8:0.38(882.7mg,0.8 mmol). Under the protection of nitrogen, dissolving the mixture of the two into dry DMAC (N, N-dimethylacetamide, 27.357g) to prepare a solution with a solid content of 4%, cooling to room temperature, adding 1, 3-bis (chloromethyl) benzene (52.5mg,0.3mmol), stirring for 2 hours, uniformly stirring, filtering out insoluble substances, degassing the filtrate, casting on a glass plate with the thickness of 10cm multiplied by 10cm, drying for two hours in a blast oven at the temperature of 80 ℃, further heating to 120 ℃ for drying for one hour, and finally heating to 240 ℃ for drying for one hour to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 29 μm (micrometers) and a DSC test showed a glass transition temperature TgThe tensile strength of the product is 126MP as shown by the mechanical property test at 310 DEG Ca。
Example 14
OO-PBI and [ 1-vinyl-1H-1, 2, 3-triazole-allylphosphonic acid bis (triisopropylsilyl) ester]Copolymer B14And 2[ (2-bromomethyl) phenoxy group]Preparation of methyl ethylene oxide composite film
Figure BDA0001677180690000201
(1) 1-vinyl-1H-1, 2, 3-triazole-allylphosphonic acid di (triisopropylsilyl) ester copolymer B14(molar ratio 1:8) preparation
Under the protection of nitrogen, 1-vinyl-1H-1, 2, 3-triazole (95.1mg,1mmol) and allyl phosphonic acid bis (triisopropylsilyl) ester (3590.1mg,8mmol) were added sequentially to a three-necked reaction flask, deionized water (200mL) was used as a solvent, and then a radical chain initiator azobisisobutyronitrile (AIBN,11.5mg,0.07mmol) was added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B14。
(2) OO-PBI and copolymer B14And 2[ (2-bromomethyl) phenoxy group]Preparation of methyl ethylene oxide (molar ratio 1:1:1) composite membrane
Weigh the dried OO-PBI (246.8mg,0.5mmol) and copolymer B in a molar ratio of 1:1:114(1842.6mg,0.5 mmol). Dissolving the mixture in dry NMP (N-methylpyrrolidone 32.734g) under nitrogen protection to obtain solution with solid content of 6%, cooling to room temperature, adding 2[ (2-bromomethyl) phenoxy group]Methyl ethylene oxide (121.5mg,0.5mmol) is stirred for 2 hours, the mixture is uniformly stirred and filtered, insoluble substances are filtered, the filtrate is subjected to degassing treatment and then is cast on a glass plate with the thickness of 10cm multiplied by 10cm, then the glass plate is placed in a blast oven to be dried for two hours at the temperature of 80 ℃, then the temperature is further raised to 120 ℃ for drying for one hour, and finally the temperature is raised to 220 ℃ for drying for one hour, so that the cross-linked organic phosphonic acid high-temperature proton exchange membrane is obtained. The film had a thickness of 25 μm (micrometers) and a DSC test showed a glass transition temperatureDegree TgThe mechanical property test shows that the tensile strength is 116MPa, 285 ℃.
Example 15
OSO2-PBI and [ N-vinylimidazole-2-propenyl (diethyl 2-methylenephosphonate) phosphonic acid diethyl ester]Copolymer B15And 2[ (4-bromomethyl) phenoxy group]Preparation of methyl ethylene oxide composite film
Figure BDA0001677180690000211
(1) N-vinylimidazole-2-propenyl (diethyl 2-methylenephosphonate) phosphonic acid diethyl ester copolymer B4(molar ratio 1:1) preparation
N-vinylimidazole (94.1mg,1mmol) and diethyl 2-propenyl (diethyl 2-methylenephosphonate) (366.2mg,1mmol) were added sequentially to a three-necked reaction flask under nitrogen, deionized water (180mL) was used as the solvent, and then the free radical chain initiator azobisisobutyronitrile (AIBN,8.2mg,0.05mmol) was added. Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B15。
(2)OSO2-PBI and copolymer B15And 2[ (4-bromomethyl) phenoxy group]Preparation of composite membrane of methyl oxirane (molar ratio 1:4:0.4)
The dry OSO was weighed in a molar ratio of 1:4:0.42PBI (92.8mg,0.2mmol) and copolymer B15(368.2mg,0.8 mmol). Under the protection of nitrogen, the mixture was dissolved in dry DMAC (N, N-dimethylacetamide, 8.759g) to prepare a solution with a solid content of 5%, and the solution was cooled to room temperature and added with 2[ (4-bromomethyl) phenoxy group]Methyl ethylene oxide (19.5mg,0.08mmol), stirring for 2 hr, stirring, filtering, removing insoluble substances, degassing, casting onto glass plate of 10cm × 10cm, drying at 80 deg.C for two hr in blast oven, further heating to 120 deg.C for one hr, and finally heating to 190 deg.C for one hrAnd obtaining the cross-linked organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 24 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 121MPa when the temperature is 307 ℃.
Example 16
Py-PBI and [ 2-vinylimidazole-allylphosphonic acid bis (triethylsilyl) ester]Copolymer B16And 2[ (2-chloromethyl) phenoxy group]Preparation of methyl ethylene oxide composite film
Figure BDA0001677180690000221
(1) 2-vinylimidazole-allylphosphonic acid bis (triethylsilicon) ester copolymer B16(molar ratio 1:3) preparation
2-vinylimidazole (282.3mg,3mmol) and allylphosphonic acid bis (triethylsilicon) ester (3155.2mg,9mmol) were added sequentially under nitrogen to a three-necked reaction flask, deionized water (200mL) was used as the solvent, followed by the addition of the free radical chain initiator azobisisobutyronitrile (AIBN,19.71mg,0.12 mmol). Stirring (mechanical stirring) and heating to 80 ℃ for reaction. After 24h reaction, the solution became viscous, the reaction was stopped and cooled to room temperature. Pouring the reaction solution into ethyl acetate, continuously stirring, separating out solid, filtering, and vacuum drying to obtain copolymer B16。
(2) Py-PBI and copolymer B16And 2[ (2-chloromethyl) phenoxy group]Preparation of methyl ethylene oxide (molar ratio 1:1:1) composite membrane
Weigh the dried Py-PBI (154.5mg,0.5mmol) and copolymer B in a 1:1:1 molar ratio16(572.3mg,0.5 mmol). Dissolving the mixture in dry DMF (N, N-dimethylformamide, 17.443g) under nitrogen protection to obtain solution with solid content of 4%, cooling to room temperature, adding 2[ (2-chloromethyl) phenoxy]Stirring methyl oxirane (99.32mg,0.5mmol) for 2 hr, stirring, filtering, removing insoluble substances, degassing, casting onto glass plate of 10cm × 10cm, drying in air oven at 80 deg.C for two hr, further heating to 120 deg.C, and drying for one hr to obtain final productTo a cross-linking type organic phosphonic acid high-temperature proton exchange membrane. The film had a thickness of 22 μm (micrometers) and a DSC test showed a glass transition temperature TgThe mechanical property test shows that the tensile strength is 115MPa when the temperature is 301 ℃.
Test examples
Proton conductivity test:
proton conductivity tests were conducted by a Membrane Test System 740 apparatus using a two-electrode method for testing the proton conductivity of the PBI Membrane and the membranes No. 1 (example 1), No. 4 (example 4), No. 5 (example 5), No. 7 (example 7), No. 13 (example 13), No. 14 (example 14), and No. 16 (example 16) in this patent.
The test method comprises the following steps:
(1) pretreatment in testing:
and (3) soaking the PBI membrane in 85% phosphoric acid at 60 ℃, taking out and drying after soaking for 48 hours, and testing.
Soaking the organic phosphonic acid film to be tested in 0.5mol/L diluted phosphoric acid for 48 hours, taking out, soaking by using deionized water, washing until the organic phosphonic acid film is neutral (the washing liquid is neutral), drying and testing.
(2) Formal Test (Test equipment Membrane Test System 740):
1. cutting a sample film to be detected into a shape of 1cm multiplied by 3 cm;
2. adhering a GDE with a Pt/C catalyst on the metal sheets of the two electrode clamps by using conductive adhesive, namely, gluing the GDE with the Pt/C catalyst on the metal sheets of the two electrode clamps, arranging the cut membrane to be tested in the middle of the GDE, and clamping the clamps;
3. the MTS740 was powered on and the fixture with the film to be tested was placed in the test chamber of the apparatus.
4. The testing program of the instrument is opened, and the pipeline connecting the gas cylinder and the instrument is connected. Regulating N2The pipeline pressure is 0.5MPa, H2The line pressure reaches 0.4MPa, the indication of each indicator lamp in the inspection program is normal, and the connection between the chemical workstation and the 740 operation cavity is inspected.
5. When the film sample is initially tested, N should be introduced first2Purging for 10min to remove air from the chamber at a rate of 500sccm/min when the instrument is in operation at a temperature and humidity (relatively wet)The degree is 2%, the relative humidity is set to 100% when the organic phosphonic acid film is tested), and the test can be started after the relative humidity reaches the set value and is stable.
6. An impedance spectrum is automatically obtained by using an MTS740 program, and a membrane resistance value R is obtained from the spectrum.
7. Data processing: the conductivity is calculated from ρ ═ L/(Rs × a).
L is the film thickness;
rs is membrane resistance for reading impedance spectrum
A is measured area
8. At the end of the test, N must be used2Purging for 15min to remove water vapor in the instrument, and finally turning off the power supply of the instrument and the program.
The test results are shown in fig. 1. The result shows that the conductivity of the composite organic phosphonic acid high-temperature proton exchange membrane for the fuel cell reaches the same order of magnitude as that of a PBI (poly (p-phenylene-imide)) membrane/inorganic phosphoric acid system, and the conductivity of some matching membranes is obviously higher than that of the PBI membrane. At present, the biggest problem of organic phosphonic acid membranes reported in a large number of reports is that proton conductivity is lower by 1 to 2 orders of magnitude than that of a PBI membrane/inorganic phosphoric acid system, and compared with the PBI membrane/inorganic phosphoric acid system, the organic phosphonic acid membrane prepared in the invention can reach the same order of magnitude and has extremely excellent effect.
Phosphoric acid (phosphonic acid) loss rate test:
we used the PBI membrane/inorganic phosphoric acid system, and the change in conductivity of the organic phosphonic acid membrane after soaking in deionized water to reflect the phosphoric acid (phosphonic acid) loss rate. We chose PBI membrane/inorganic phosphoric acid, and organophosphonic acid membrane No. 1 (example 1), No. 4 (example 4), No. 13 (example 13), No. 14 (example 14) for test comparison:
the test method comprises the following steps:
(1) preparation of test sample films:
soaking the PBI membrane in 85% phosphoric acid at 60 deg.c for 48 hr, and drying.
Soaking the organic phosphonic acid film to be tested in 0.5mol/L diluted phosphoric acid for 48 hours, taking out, soaking by using deionized water, washing until the organic phosphonic acid film is neutral (the washing liquid is neutral), and drying.
(2) Formal test
1. And soaking the prepared sample film in deionized water for 5 minutes, taking out and drying.
2. The proton conductivity of the dried sample membrane was measured at 160 ℃ according to the foregoing conductivity measurement method (test conditions: PBI membrane relative humidity 2%; organic phosphonic acid membrane relative humidity 100%)
3. The above operations 1 and 2 were cycled nine times.
As shown in fig. 2, the proton conductivity of the PBI membrane/inorganic phosphoric acid system decreased very rapidly, while the proton conductivity of the organic phosphoric acid membrane did not decrease almost at all. This result indicates that the inorganic phosphoric acid loss in the PBI film/inorganic phosphoric acid system is very severe, and the organic phosphonic acid of the organic phosphonic acid film hardly has the problem of loss, so that the organic phosphonic acid film of the present application can maintain good conductivity.
And (3) testing the discharge performance of the single battery:
the discharge performance of the cells assembled with film No. 1 (example 1), film No. 4 (example 4), and film No. 16 (example 16) in this patent was tested using a Fuel Cell Test System 850e apparatus.
(1) Preparation of test sample films:
soaking the organic phosphonic acid film to be tested in 0.5mol/L diluted phosphoric acid for 48 hours, taking out, soaking by using deionized water, washing until the organic phosphonic acid film is neutral (the washing liquid is neutral), and drying.
(2) Assembling single cells:
a) preparing a membrane electrode by using the membrane to be detected and the electrode, and assembling the membrane electrode in a single battery model for use to be detected;
b) the Cell is connected to a hydrogen Fuel Cell Test System 850 e. The hydrogen inlet end is connected with the negative electrode of the battery, the air inlet end is connected with the positive electrode of the battery, and the hydrogen and air inlet and outlet ends are respectively arranged at the same side in the graphite bipolar plate to ensure that one gas in the bipolar plate at one side is fed in and discharged out;
(3) single cell testing:
a) setting parameters of a test system:
and (3) testing temperature: 160 deg.C
Hydrogen gas inflow: 500cc/min, 1.6 metering ratio
Air intake amount: 1500cc/min, 1.3 of metering ratio
b) And (3) testing procedures:
test method adopting scanning potential
Voltage range: 0.25-1V, collecting one data point every 0.05V
c) Collecting data of parameters such as voltage, current density, energy density and the like, and setting a storage path;
the test results are shown in fig. 3, which shows that the organic phosphonic acid high-temperature proton exchange membrane has excellent discharge performance.
And testing the operating stability of the single cell:
we chose PBI membranes to assemble cells with membrane No. 7 (example 7) and membrane No. 14 (example 14), respectively, for the operating stability test.
1. Film treatment before testing:
a) soaking the PBI membrane in 85% phosphoric acid at 60 deg.c for 48 hr, and drying. Soaking the organic phosphonic acid film in 0.5mol/L diluted phosphoric acid for 48 hours, taking out, soaking by using deionized water, washing until the organic phosphonic acid film is neutral (the washing liquid is neutral), and drying.
b) Cutting the film to be measured into 6.5cm multiplied by 6.5 cm;
preparing MEA (membrane electrode);
a) cutting GDL with model number 29BC from SIGGRACET company into 5 × 5cm size for catalyst spraying;
b) spraying catalyst on the GDL pore layer, wherein the cathode catalyst loading is 2mg/cm2The loading of the anode catalyst is 3mg/cm2Preparing GDE;
c) placing the membrane to be tested in the middle, placing the cathode and anode of GDE on the upper and lower parts respectively, placing into a sandwich structure, and hot-pressing (hot-pressing conditions are 135 deg.C, 10MPa, 2min) to obtain MEA;
3. assembling the battery:
the prepared MEA was assembled in a cell model.
4. Single cell testing:
test apparatus Fuel Cell Test System 850e
Connecting the single battery with the testing equipment, and according to the set parameters: anode: hydrogen 500 ml/min; cathode: air 1500 ml/min; and (3) testing temperature: 160 ℃; PBI membrane relative humidity: 2%, relative humidity of organic phosphonic acid film 100%, constant scanning voltage 0.7v. The test results are shown in fig. 4.
From the test results, it can be seen that the PBI membrane assembled single cell can see a significant performance reduction after more than 1000 hours of testing, while the performance of the single cells assembled by the membrane No. 7 (example 7) and the membrane No. 14 (example 14) is always stable without significant reduction, which indicates that the single cells prepared by the organic phosphonic acid proton exchange membrane of the present application achieve better stability.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (9)

1. The cross-linked organic phosphonic acid high-temperature proton exchange membrane is characterized by being formed by compounding a polybenzimidazole compound A, another acid-base organic phosphonic acid polymer B and an organic micromolecule cross-linking agent C serving as raw materials, wherein the molar ratio nA to B is =1:0.01-99.99, and the molar ratio nA to C is =1: 0.01-5.00;
and the acid-base organic phosphonic acid polymer B is a copolymer formed by copolymerizing a basic olefin monomer D and an organic phosphonic acid monomer E, wherein the basic olefin monomer D is a monomer selected from the following group:
Figure 100778DEST_PATH_IMAGE001
the organic phosphonic acid monomer E is selected from the following group:
Figure 476395DEST_PATH_IMAGE002
R2selected from the group consisting of: H. substituted or unsubstituted C1-C9 alkyl, phenyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, triisopropylsilyl, tert-butyldiphenylsilyl; and the copolymerization molar ratio of the monomer D to the monomer E is nD: nE =1: 0.01-99.99;
the organic small molecule cross-linking agent C is selected from the following group:
Figure 897012DEST_PATH_IMAGE003
。
2. the cross-linked organophosphonic acid high-temperature proton exchange membrane according to claim 1, wherein the polybenzimidazole based polymer a is selected from the group consisting of:
Figure 556533DEST_PATH_IMAGE004
wherein n = 2-10000;
r is selected from the group consisting of: chemical bond, O, S, NH, C (O), S (O)2Unsubstituted or halogenated C1-C6 alkylene, unsubstituted or halogenated C2-C6 alkenylene;
R1selected from the group consisting of:
Figure 669982DEST_PATH_IMAGE003
。
3. the cross-linked organophosphonic acid high temperature proton exchange membrane according to claim 2 wherein the polybenzimidazole type compound a is selected from the group consisting of:
Figure 595213DEST_PATH_IMAGE005
。
4. the cross-linked organophosphonic acid high-temperature proton exchange membrane according to claim 1, wherein the molar ratio of monomer D to monomer E copolymerized in the "acid-base" organophosphonic acid polymer B is nD: nE =1: 1-20.
5. The crosslinked organophosphonic acid high temperature proton exchange membrane according to claim 1 wherein the "acid-base" organophosphonic acid polymer B is prepared by the following method: and (3) carrying out polymerization reaction on the monomer D and the organic phosphonic acid monomer E in deionized water to obtain the polymer B.
6. The cross-linked organophosphonic acid high temperature proton exchange membrane according to claim 1 wherein the molar ratio of a to B nA: nB =1: 0.1-40, and the molar ratio of A to C nC =1: 0.02-5.00.
7. The method for preparing the cross-linked organic phosphonic acid high-temperature proton exchange membrane according to claim 1, wherein the method for preparing the cross-linked organic phosphonic acid high-temperature proton exchange membrane comprises the following steps:
(i) providing a polybenzimidazole type compound A and an acid-base type organic phosphonic acid polymer B;
(ii) under the protection of inert gas, dissolving the mixture of the two in an organic solvent to prepare a mixed solution;
(iii) cooling to room temperature, adding the organic small molecular cross-linking agent C, and stirring until the mixture is uniformly mixed;
(iv) filtering to remove insoluble substances to obtain mixed filtrate;
(v) degassing the mixed filtrate;
(vi) and (3) forming a membrane from the mixed filtrate subjected to degassing treatment to obtain the cross-linked organic phosphonic acid high-temperature proton exchange membrane.
8. The process according to claim 7, wherein the molar ratio of polybenzimidazole-type compound A to "acid-base" organophosphonic acid polymer B is 1:0.1 to 40.
9. The process of claim 7, wherein in step (ii), the solution is prepared at a solids content of 1-30 wt%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926131A (en) * 2004-01-27 2007-03-07 美国丰田技术中心公司 Heterocycle grafted monomers and related polymers and hybrid inorganic-organic polymer membranes
CN104151587A (en) * 2013-05-15 2014-11-19 北京化工大学 Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane
CN107887626A (en) * 2017-11-09 2018-04-06 中国科学院上海有机化学研究所 One kind is crosslinked compound high temperature proton exchange film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1926131A (en) * 2004-01-27 2007-03-07 美国丰田技术中心公司 Heterocycle grafted monomers and related polymers and hybrid inorganic-organic polymer membranes
CN104151587A (en) * 2013-05-15 2014-11-19 北京化工大学 Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane
CN107887626A (en) * 2017-11-09 2018-04-06 中国科学院上海有机化学研究所 One kind is crosslinked compound high temperature proton exchange film and preparation method thereof

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