CN108598533B - Coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane and preparation method thereof - Google Patents

Coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane and preparation method thereof Download PDF

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CN108598533B
CN108598533B CN201810379557.9A CN201810379557A CN108598533B CN 108598533 B CN108598533 B CN 108598533B CN 201810379557 A CN201810379557 A CN 201810379557A CN 108598533 B CN108598533 B CN 108598533B
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sulfonated polyimide
coumarin
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CN108598533A (en
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潘海燕
陈思琦
金明
常志宏
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Tongji University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane and a preparation method thereof, wherein the proton exchange membrane comprises the following components in parts by weight: 1 part of sulfonated polyimide containing photosensitive groups, 0.005-0.05 part of photoinitiator aid and 20-100 parts of organic solvent; the photosensitive sulfonated polyimide comprises the following components in parts by mole: 1 part of dianhydride, 0.2-2 parts of sulfonated diamine, 0.8-1.2 parts of catalyst and 0.2-10 parts of photosensitizer. Compared with the prior art, the coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane has the advantages of high proton conductivity, high mechanical strength, good hydrolysis and chemical stability, wide raw material source, good preparation process controllability, effective saving of production cost and good application prospect.

Description

Coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of functional polymer materials and electrochemistry, and relates to a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are fuel cells in which a proton exchange membrane is used as an electrolyte, and are one of five types of fuel cells. The technology is the most mature technology in the world at present, which can enable hydrogen and oxygen in the air to generate chemical reaction to generate water and release electric energy, and has the advantages of high energy efficiency, low emission, environmental friendliness and the like. At the heart of a fuel cell, the properties of the electrolyte are directly related to key performances of the fuel cell, such as power generation efficiency, service life, and the like. The proton conductivity, mechanical properties, and dimensional stability of Proton Exchange Membranes (PEM) have a direct impact on the performance of PEMFCs.
Currently, perfluorinated proton exchange membranes (e.g., proton exchange membranes)
Figure BDA0001640739670000011
) Is the main body of the proton exchange membrane on the market, but the proton exchange membrane has the defects of high price, complex preparation process, excessive dependence on water for proton conduction in the membrane, low conductivity at high temperature or low humidity, serious methanol leakage, low fuel utilization rate, large fluorine content, harmful substances generated during degradation, poor mechanical strength and dimensional stability, and the like, and the wide range of the proton exchange membrane is limited by the defects of the proton exchange membrane, the likeThe method is widely applied.
Polyimide has excellent heat resistance and chemical stability as a high-performance engineering plastic, and recently, a researcher uses Sulfonated Polyimide (SPI) as a proton exchange membrane for a fuel cell, so that the sulfonated polyimide has good conductivity and alcohol resistance, has attracted extensive attention in many industrial fields such as microelectronics and membrane separation, and the like, and the advantages are expected to be obtained in the proton exchange membrane fuel cell and have a great application prospect, so that in related reports, such as patents CN 107722271 a, CN 107417915A and CN 107383404 a, the sulfonated polyimide has been mentioned to be applied as the proton exchange membrane with excellent properties. When the sulfonation degree of the sulfonated polyimide is low, the proton conductivity is low, and when the sulfonation degree reaches a certain value, the dimensional stability and the mechanical strength of the sulfonated polyimide are seriously reduced, so that the application potential of the sulfonated polyimide is also reduced. The sulfonated polyimide is crosslinked, so that the mechanical property, the thermodynamic property and the chemical property of the proton exchange membrane can be effectively improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane with high mechanical strength, good dimensional stability and high proton conductivity and a preparation method thereof.
The design idea of the technical scheme of the invention is to introduce photosensitive groups into a main chain of sulfonated polyimide, and to perform a crosslinking reaction by illumination in the film forming process or the using process of the sulfonated polyimide so as to obtain the coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane material.
The purpose of the invention can be realized by the following technical scheme:
a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane comprises the following components in parts by weight: 1 part of sulfonated polyimide containing photosensitive groups, 0.005-0.05 part of photoinitiator assistant and 20-100 parts of organic solvent.
The photoinitiator includes but is not limited to 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, methyl benzoylformate, methyl acetate, and mixtures thereof, 4-phenylbenzophenone, 4-chlorobenzophenone, benzoin dimethyl ether, methyl o-benzoylbenzoate, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, alpha-dimethoxy-alpha-phenylacetophenone, alpha-diethoxyacetophenone, alpha-hydroxyalkylphenone, alpha-aminoalkylbenzophenone, bis-benzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxybenzophenone, Michler's ketone, thiopropoxyphenyl thioxanthone, isopropyl thioxanthone, and the like.
The photoinitiator aid comprises one or more of triethylamine, N-dimethyl diethanolamine, tris (3-mercaptopropionic acid) trimethylolpropane, diaryl iodonium salt and the like.
The organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.
The sulfonated polyimide containing photosensitive groups comprises the following components in parts by mole: 1 part of dianhydride, 0.2-2 parts of sulfonated diamine, 0.2-2 parts of non-sulfonated diamine, 0.2-10 parts of halogenated photosensitizer and 0.8-1.2 parts of catalyst.
The dianhydrides include, but are not limited to, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9, 10-perylene tetracarboxylic anhydride, 4,4' - (hexafluoroisopropylene) diphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 1,6,7, 12-tetrachloro-3, 4,9, 10-perylene tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 1,2,3, 4-cyclopentyltetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 1,2,3, 4-butanetetracarboxylic dianhydride or 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride.
The sulfonated diamines include, but are not limited to, 2' -bis (3-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2' -bis (3-sulfo4-methylbenzenesulfonyl) -4,4' -diaminobiphenyl, 2' -bis (2,4' -disulfonated biphenyl-4-sulfonyl) -4,4' -diaminobiphenyl, 2' -bis (4- (4-sulfophenoxy) -3-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2' -bis (4- (4-sulfophenylthio) -3-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2,2' -bis (4- (4-sulfobenzenesulfonyl) -5-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2' -bis (3- (3-sulfobenzenesulfonyl) -5-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2' -bis (4- (methylene-4-sulfophenyl) -3-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2' -bis (4- (isopropylidene-4-sulfophenyl) -3-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2' -bis (4- (hexafluoroisopropylidene-4-sulfophenyl) -3-sulfobenzenesulfonyl) -4, one or more of 4' -diaminobiphenyl.
The non-sulfonated diamine has a functionality of 4 or more, and includes, but is not limited to, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (4-aminophenyl) propane, 2-bis (3-amino-4-methylphenyl) propane, one or more of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-aminophenyl) hexafluoropropane and 2, 2-bis (3-amino-4-methylphenyl) hexafluoropropane.
The catalyst includes but is not limited to one or more of triethylamine, acetic anhydride or benzoic acid.
Such halogenated photosensitizers include, but are not limited to, 3-chlorocoumarin, 6-bromocoumarin, 6-chloro-4-hydroxycoumarin, 3- (bromoacetyl) coumarin, 6-bromocoumarin-3-carboxylic acid, 6-chloro-4-hydroxycoumarin, 3- (bromoacetyl) coumarin, 6-bromo-4-hydroxycoumarin, or bishydroxycoumarin, coumarin 2, coumarin 6, 4-hydroxycoumarin, 6-hydroxycoumarin, 3-aminocoumarin, coumarin 343, 3-hydroxycoumarin, 6-hydroxycoumarin, 3-aminocoumarin, coumarin-3-carboxylic acid, 7-hydroxycoumarin, 6, 7-dihydroxycoumarin, 5, 7-dihydroxycoumarin, dihydrocoumarin, substituted coumarin, or unsubstituted coumarin, 4, 6-dihydroxycoumarin, 6-hydroxy-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 4-hydroxy-6-methylcoumarin, 7-hydroxycoumarin-4-acetic acid, 4-hydroxy-3-nitrocoumarin, 4-hydroxy-6-methylcoumarin, and the like.
The invention also provides a preparation method of the coumarin-based photo-cyclized cross-linked sulfonated polyimide proton exchange membrane, which comprises the following steps:
preparing sulfonated polyimide in step (1):
preparing the following components in parts by mole: 1 part of dianhydride, 0.2-2 parts of sulfonated diamine, 0.2-2 parts of non-sulfonated diamine and 0.8-1.2 parts of catalyst; adding 1-10 parts of reaction solvent and sulfonated diamine into a reaction container, introducing inert gas, stirring, adding non-sulfonated diamine, dianhydride and catalyst after the sulfonated diamine is completely dissolved, carrying out polymerization reaction, slowly adding the product into acetone for precipitation after the reaction is finished, carrying out soxhlet extraction on the precipitate by using acetone, removing residual solvent, catalyst and low molecular weight substances, and carrying out vacuum drying on the product to obtain sulfonated polyimide;
preparing a halogenated photosensitizer in step (2):
the photosensitizer without functional groups capable of reacting with the main chain of the sulfonated polyimide reacts with molecules with functional groups capable of reacting with the main chain of the sulfonated polyimide, after the reaction is finished, the raw materials and the solvent are removed, and the product is dried in vacuum to prepare the halogenated photosensitizer. This step is not required if the photosensitizer itself contains functional groups that can react with the sulfonated polyimide backbone.
Step (3) preparing sulfonated polyimide containing photosensitive groups:
preparing the sulfonated polyimide prepared in the step (1), the halogenated photosensitizer prepared in the step (2) and an organic solvent according to the following weight parts: 1 part of sulfonated polyimide, 0.2-10 parts of halogenated photosensitizer and 20-100 parts of organic solvent; adding an organic solvent and the sulfonated polyimide prepared in the step (1) into a reaction container, introducing inert gas, stirring, adding the halogenated photosensitizer prepared in the step (2) for reaction after the polyimide is completely dissolved, slowly adding the product into acetone for precipitation after the reaction is finished, performing soxhlet extraction on the precipitate by using acetone, removing residual solvent, catalyst and low molecular weight substances, and performing vacuum drying on the product to obtain the sulfonated polyimide containing photosensitive groups;
step (4) preparing a membrane solution:
preparing the sulfonated polyimide containing the photosensitive group prepared in the step (3), a photoinitiator and an organic solvent according to the following weight parts: 1 part of polyimide, 0.005-0.05 part of photoinitiator assistant and 20-100 parts of organic solvent; dissolving sulfonated polyimide containing photosensitive groups in an organic solvent, mixing the sulfonated polyimide with a photoinitiator and a photoinitiator aid at room temperature, and uniformly stirring to prepare a film forming solution;
step (5) preparing a coumarin-based photo-cyclized cross-linked sulfonated polyimide proton exchange membrane:
and (3) casting the membrane solution obtained in the step (4) in a membrane frame at 75-90 ℃, irradiating for 15min by using a 365nm LED light source, preserving heat for 4-8 hours to ensure that a crosslinking reaction is completed, cooling, sequentially soaking the formed membrane in deionized water and alcohol, then soaking the membrane in dilute hydrochloric acid for 24 hours at normal temperature, carrying out proton exchange, washing with deionized water to be neutral, and drying at 50-70 ℃ to obtain the coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane.
Wherein:
the reaction conditions in the step (1) are as follows: heating to 75-85 deg.C, reacting for 3-5 hr, heating to 160-200 deg.C, reacting for 12-20 hr, and cooling to 95-115 deg.C after reaction;
the reaction conditions in the step (2) are as follows: heating to reflux the solvent, reacting for 20-30h, and cooling to room temperature after the reaction is finished;
the molecules having a functional group reactive with the sulfonated polyimide main chain in the step (2) include, but are not limited to, one or more of methylene chloride, methylene bromide, 1, 2-dichloroethane, 1, 2-dibromoethane, 1, 2-dichloropropane, 1, 3-dichloropropane, 2-dichloropropane, 1-dichloropropane, 2-dimethyl-1, 3-dichloropropane, 1, 2-dibromopropane, 1, 3-dibromopropane, 2-dibromopropane, 1-dibromopropane, 2-dimethyl-1, 3-dibromopropane;
the reaction conditions in the step (3) are as follows: heating to 90-110 ℃, reacting for 20-30h, and cooling to 95-115 ℃ after the reaction is finished;
the dosage relation of the sulfonated polyimide containing photosensitive groups and the organic solvent in the step (4) is as follows: the mass percentage of the sulfonated polyimide containing photosensitive groups in the organic solvent is 2-5 percent;
and (5) the dilute hydrochloric acid solution is 8-10% by mass.
Compared with the prior art, the invention has the following characteristics:
1) photosensitive groups are introduced into a main chain of the sulfonated polyimide, and the sulfonated polyimide is subjected to a crosslinking reaction by illumination in a film forming process or a using process to obtain a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane material, so that the mechanical property of the proton exchange membrane can be remarkably improved, and the proton exchange membrane material still has high proton conductivity;
2) the prepared photocyclization crosslinking sulfonated polyimide proton exchange membrane material has high mechanical strength and good size stability while keeping higher proton conductivity, and has wide application prospect in polymer electrolyte membrane fuel cells;
3) the preparation process has good controllability, wide raw material source and mild process conditions, can effectively save the production cost and has good application prospect.
Drawings
FIG. 1 is the proton conductivity of the coumarin-based photocrosslinked sulfonated polyimide proton exchange membranes C-SPI-140, C-SPI-120, C-SPI-100 of examples 2,3,4, and the uncrosslinked sulfonated polyimides SPI-140, SPI-120, SPI-100 of comparative examples 2,3, 4.
FIG. 2 is the tensile strength of the coumarin-based photocrosslinked sulfonated polyimide proton exchange membranes C-SPI-140, C-SPI-120, C-SPI-100 of examples 2,3,4, and the uncrosslinked sulfonated polyimides SPI-140, SPI-120, SPI-100 of comparative examples 2,3, 4.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1:
step (1): synthesizing sulfonated polyimide containing hydroxyl with sulfonation degree of 80%:
0.6957g (4mmol) of 2,2' -benzidine disulfonic acid (BDSA) were weighed into a 250mL three-necked flask, 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of 1,4,5, 8-Naphthalene Tetracarboxylic Dianhydride (NTDA), 2.9898g (6mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP) and 2.4547g (20mmol) of benzoic acid are weighed, added into a three-necked flask in turn, and added with 25mL of m-cresol to make the solid content between 16% and 17%, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in a vacuum oven at 50 deg.C to constant weight;
step (2): synthesizing a brominated photosensitizer:
4.9635g (30mmol) of 7-hydroxycoumarin were weighed into a 250mL single-neck flask, 56.9273g (300mmol) of 1, 2-dibromoethane, 12.4389g (90mmol) of potassium carbonate and 0.2490g (1.5mmol) of potassium iodide were added, and 100mL of acetone was added. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and after oxygen is removed, the single-mouth bottle is heated in an oil bath until the temperature is reached to acetone reflux. Reacting for 24 hours, cooling to room temperature after plate counting and judging that the reaction is stopped, extracting for 3 times by using ethyl acetate to obtain an organic layer, evaporating most of liquid by rotation, then distilling under reduced pressure to remove 1, 2-dibromoethane, and drying in a vacuum oven at 50 ℃ to constant weight for later use;
and (3): synthesis of sulfonated polyimide containing photosensitive group:
firstly, 0.4996g (1eq) of sulfonated polyimide containing hydroxyl group and having a sulfonation degree of 80% synthesized in the step (1) are weighed into a 100mL single-neck flask, 10mL of DMF is added, and the mixture is heated to about 100 ℃. After the solid was completely dissolved, 1.4864g (10eq) of the brominated photosensitizer synthesized in step (2), 0.2300g (3eq) of potassium carbonate and 0.0046g (0.05eq) of potassium iodide were weighed out, followed by addition of 5mL of DMF. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and oxygen is removed. Heating in oil bath at 100 deg.c. The reaction is carried out for 24 hours, and the reaction is protected from light. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in a vacuum oven at 50 deg.C to constant weight;
and (4): synthesis of sulfonated polyimide membrane solution:
dissolving the sulfonated polyimide containing photosensitive groups and having a sulfonation degree of 80% synthesized in the step (3) in NMP to form a 2% -5% solution, adding a photoinitiator Benzophenone (BP) with a mass fraction of 5% and a photoinitiator auxiliary Triethylamine (TEA) with a mass fraction of 5%, and continuously stirring the mixture to prepare a film forming solution;
and (5): preparing a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane:
and (4) pouring the uniform membrane solution obtained in the step (4) into a membrane frame of 10cm multiplied by 10 cm. The solvent was evaporated in a vacuum oven at 70 ℃ for 3 days, and then the dry film was irradiated with 365nm for 15 min. Keeping the glass plate in the oven horizontal to ensure the uniform thickness of the film, naturally cooling, and then soaking the film in methanol at 80 ℃ for 3h to remove impurities such as residual solvent. The membrane is soaked in 1.0mol/L hydrochloric acid for 24h under the condition of normal temperature, and proton exchange is carried out. Then washing the membrane with deionized water to be neutral, and drying the membrane to be constant weight to obtain the photocyclization crosslinking sulfonated polyimide proton exchange membrane C-SPI-80 with the sulfonation degree of 80 percent.
Example 2:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 100%:
0.6957g (5mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (5mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in 50 deg.C vacuum oven to constant weight;
step (2): synthesizing a brominated photosensitizer:
4.9635g (30mmol) of 7-hydroxycoumarin were weighed into a 250mL single-neck flask, 56.9273g (300mmol) of 1, 2-dibromoethane, 12.4389g (90mmol) of potassium carbonate and 0.2490g (1.5mmol) of potassium iodide were added, and 100mL of acetone was added. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and after oxygen is removed, the single-mouth bottle is heated in an oil bath until the temperature is reached to acetone reflux. Reacting for 24 hours, cooling to room temperature after plate counting and judging that the reaction is stopped, extracting for 3 times by using ethyl acetate to obtain an organic layer, evaporating most of liquid by rotation, then distilling under reduced pressure to remove 1, 2-dibromoethane, and drying in a vacuum oven at 50 ℃ to constant weight for later use;
and (3): synthesis of sulfonated polyimide containing photosensitive group:
0.4996g (1eq) of the sulfonated polyimide containing hydroxyl groups and having a sulfonation degree of 100% synthesized in step (1) were weighed in a 100mL single-neck flask, 10mL of DMF was added, and the mixture was heated at about 100 ℃. After the solid was completely dissolved, 1.4864g (10eq) of the brominated photosensitizer synthesized in step (20), 0.2300g (3eq) of potassium carbonate and 0.0046g (0.05eq) of potassium iodide were weighed out, followed by addition of 5mL of DMF. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and oxygen is removed. Heating in oil bath at 100 deg.c. The reaction is carried out for 24 hours, and the reaction is protected from light. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in a vacuum oven at 50 deg.C to constant weight;
and (4): synthesis of sulfonated polyimide membrane solution:
dissolving the sulfonated polyimide containing photosensitive groups and having a sulfonation degree of 100% synthesized in the step (3) in NMP to form a 2% -5% solution, adding a photoinitiator Benzophenone (BP) with a mass fraction of 5% and a photoinitiator auxiliary Triethylamine (TEA) with a mass fraction of 5%, and continuously stirring the mixture to prepare a film forming solution;
and (5): preparing a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane:
and (4) pouring the uniform membrane solution obtained in the step (4) into a membrane frame of 10cm multiplied by 10 cm. The solvent was evaporated in a vacuum oven at 70 ℃ for 3 days, and then the dry film was irradiated with 365nm for 15 min. Keeping the glass plate in the oven horizontal to ensure the uniform thickness of the film, naturally cooling, and then soaking the film in methanol at 80 ℃ for 3h to remove impurities such as residual solvent. The membrane is soaked in 1.0mol/L hydrochloric acid for 24h under the condition of normal temperature, and proton exchange is carried out. Then washing the membrane with deionized water to be neutral, and drying the membrane to be constant weight to obtain the photocyclization crosslinking sulfonated polyimide proton exchange membrane C-SPI-100 with the sulfonation degree of 100 percent.
Example 3:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 120%:
0.6957g (6mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (4mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight;
step (2): synthesizing a brominated photosensitizer:
4.9635g (30mmol) of 7-hydroxycoumarin were weighed into a 250mL single-neck flask, 56.9273g (300mmol) of 1, 2-dibromoethane, 12.4389g (90mmol) of potassium carbonate and 0.2490g (1.5mmol) of potassium iodide were added, and 100mL of acetone was added. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and after oxygen is removed, the single-mouth bottle is heated in an oil bath until the temperature is reached to acetone reflux. Reacting for 24 hours, cooling to room temperature after plate counting and judging that the reaction is stopped, extracting for 3 times by using ethyl acetate to obtain an organic layer, evaporating most of liquid by rotation, then distilling under reduced pressure to remove 1, 2-dibromoethane, and drying in a vacuum oven at 50 ℃ to constant weight for later use;
and (3): synthesis of sulfonated polyimide containing photosensitive group:
firstly, 0.4996g (1eq) of sulfonated polyimide containing hydroxyl group and having a sulfonation degree of 120% synthesized in the step (1) are weighed into a 100mL single-neck flask, 10mL of DMF is added, and the mixture is heated to about 100 ℃. After the solid was completely dissolved, 1.4864g (10eq) of the brominated photosensitizer synthesized in step (2), 0.2300g (3eq) of potassium carbonate and 0.0046g (0.05eq) of potassium iodide were weighed out, followed by addition of 5mL of DMF. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and oxygen is removed. Heating in oil bath at 100 deg.c. The reaction is carried out for 24 hours, and the reaction is protected from light. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in a vacuum oven at 50 deg.C to constant weight;
and (4): synthesis of sulfonated polyimide membrane solution:
dissolving the sulfonated polyimide containing photosensitive groups and having a sulfonation degree of 120% synthesized in the step (3) in NMP to form a 2% -5% solution, adding a photoinitiator Benzophenone (BP) with a mass fraction of 5% and a photoinitiator auxiliary Triethylamine (TEA) with a mass fraction of 5%, and continuously stirring the mixture to prepare a film forming solution;
and (5): preparing a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane:
and (4) pouring the uniform membrane solution obtained in the step (4) into a membrane frame of 10cm multiplied by 10 cm. The solvent was evaporated in a vacuum oven at 70 ℃ for 3 days, and then the dry film was irradiated with 365nm for 15 min. Keeping the glass plate in the oven horizontal to ensure the uniform thickness of the film, naturally cooling, and then soaking the film in methanol at 80 ℃ for 3h to remove impurities such as residual solvent. The membrane is soaked in 1.0mol/L hydrochloric acid for 24h under the condition of normal temperature, and proton exchange is carried out. Then washing the membrane with deionized water to be neutral, and drying the membrane to be constant weight to obtain the photocyclization crosslinking sulfonated polyimide proton exchange membrane C-SPI-120 with the sulfonation degree of 120 percent.
Example 4:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 140%:
0.6957g (7mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (3mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in sequence, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight;
step (2): synthesizing a brominated photosensitizer:
4.9635g (30mmol) of 7-hydroxycoumarin were weighed into a 250mL single-neck flask, 56.9273g (300mmol) of 1, 2-dibromoethane, 12.4389g (90mmol) of potassium carbonate and 0.2490g (1.5mmol) of potassium iodide were added, and 100mL of acetone was added. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and after oxygen is removed, the single-mouth bottle is heated in an oil bath until the temperature is reached to acetone reflux. Reacting for 24 hours, cooling to room temperature after plate counting and judging that the reaction is stopped, extracting for 3 times by using ethyl acetate to obtain an organic layer, evaporating most of liquid by rotation, then distilling under reduced pressure to remove 1, 2-dibromoethane, and drying in a vacuum oven at 50 ℃ to constant weight for later use;
and (3): synthesis of sulfonated polyimide containing photosensitive group:
0.4996g (1eq) of sulfonated polyimide containing a hydroxyl group and having a sulfonation degree of 140% synthesized in step (1) were weighed in a 100mL single-neck flask, 10mL of DMF was added, and the mixture was heated at about 100 ℃. After the solid was completely dissolved, 1.4864g (10eq) of the brominated photosensitizer synthesized in step (2), 0.2300g (3eq) of potassium carbonate and 0.0046g (0.05eq) of potassium iodide were weighed out, followed by addition of 5mL of DMF. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and oxygen is removed. Heating in oil bath at 100 deg.c. The reaction is carried out for 24 hours, and the reaction is protected from light. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in a vacuum oven at 50 deg.C to constant weight;
and (4): synthesis of sulfonated polyimide membrane solution:
dissolving the sulfonated polyimide containing photosensitive groups and having a sulfonation degree of 140% synthesized in the step (3) in NMP to form a 2% -5% solution, adding a photoinitiator Benzophenone (BP) with a mass fraction of 5% and a photoinitiator auxiliary Triethylamine (TEA) with a mass fraction of 5%, and continuously stirring the mixture to prepare a film forming solution;
and (5): preparing a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane;
and (4) pouring the uniform membrane solution obtained in the step (4) into a membrane frame of 10cm multiplied by 10 cm. The solvent was evaporated in a vacuum oven at 70 ℃ for 3 days, and then the dry film was irradiated with 365nm for 15 min. Keeping the glass plate in the oven horizontal to ensure the uniform thickness of the film, naturally cooling, and then soaking the film in methanol at 80 ℃ for 3h to remove impurities such as residual solvent. The membrane is soaked in 1.0mol/L hydrochloric acid for 24h under the condition of normal temperature, and proton exchange is carried out. Then washing the membrane with deionized water to be neutral, and drying the membrane to be constant weight to obtain the photocyclization crosslinking sulfonated polyimide proton exchange membrane C-SPI-140 with the sulfonation degree of 140 percent.
Example 5:
step (1): synthesizing sulfonated polyimide containing hydroxyl with sulfonation degree of 160%:
0.6957g (8mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (2mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight;
step (2): synthesizing a brominated photosensitizer:
4.9635g (30mmol) of 7-hydroxycoumarin were weighed into a 250mL single-neck flask, 56.9273g (300mmol) of 1, 2-dibromoethane, 12.4389g (90mmol) of potassium carbonate and 0.2490g (1.5mmol) of potassium iodide were added, and 100mL of acetone was added. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and after oxygen is removed, the single-mouth bottle is heated in an oil bath until the temperature is reached to acetone reflux. Reacting for 24 hours, cooling to room temperature after plate counting and judging that the reaction is stopped, extracting for 3 times by using ethyl acetate to obtain an organic layer, evaporating most of liquid by rotation, then distilling under reduced pressure to remove 1, 2-dibromoethane, and drying in a vacuum oven at 50 ℃ to constant weight for later use;
and (3): synthesis of sulfonated polyimide containing photosensitive group:
0.4996g (1eq) of the sulfonated polyimide containing hydroxyl groups and having a sulfonation degree of 160% synthesized in step (1) were weighed in a 100mL single-neck flask, 10mL of DMF was added, and the mixture was heated at about 100 ℃. After the solid was completely dissolved, 1.4864g (10eq) of the brominated photosensitizer synthesized in step (2), 0.2300g (3eq) of potassium carbonate and 0.0046g (0.05eq) of potassium iodide were weighed out, followed by addition of 5mL of DMF. The upper end of the single-mouth bottle is connected with a reflux condenser tube, and oxygen is removed. Heating in oil bath at 100 deg.c. The reaction is carried out for 24 hours, and the reaction is protected from light. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in a vacuum oven at 50 deg.C to constant weight;
and (4): synthesis of sulfonated polyimide membrane solution:
dissolving the sulfonated polyimide containing photosensitive groups and having a sulfonation degree of 160% synthesized in the step (3) in NMP to form a 2% -5% solution, adding a photoinitiator Benzophenone (BP) with a mass fraction of 5% and a photoinitiator auxiliary Triethylamine (TEA) with a mass fraction of 5%, and continuously stirring the mixture to prepare a film forming solution;
and (5): preparing a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane:
and (4) pouring the uniform membrane solution obtained in the step (4) into a membrane frame of 10cm multiplied by 10 cm. The solvent was evaporated in a vacuum oven at 70 ℃ for 3 days, and then the dry film was irradiated with 365nm for 15 min. Keeping the glass plate in the oven horizontal to ensure the uniform thickness of the film, naturally cooling, and then soaking the film in methanol at 80 ℃ for 3h to remove impurities such as residual solvent. The membrane is soaked in 1.0mol/L hydrochloric acid for 24h under the condition of normal temperature, and proton exchange is carried out. Then washing the membrane with deionized water to be neutral, and drying the membrane to be constant weight to obtain the photocyclization crosslinking sulfonated polyimide proton exchange membrane C-SPI-160 with the sulfonation degree of 160 percent.
Example 6:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 100%:
0.6957g (5mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (5mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in 50 deg.C vacuum oven to constant weight;
step (2): synthesis of sulfonated polyimide containing photosensitive group:
0.4996g (1eq) of the sulfonated polyimide containing hydroxyl groups and having a sulfonation degree of 100% synthesized in step (1) were weighed in a 100mL single-neck flask, 10mL of DMF was added, and the mixture was heated at about 100 ℃. After the solid was completely dissolved, 1.2620g (10eq) of 6-bromocoumarin, 0.2300g (3eq) of potassium carbonate and 0.0046g (0.05eq) of potassium iodide were weighed out as bromophotosensitizer, and 5ml of DMF was added. The upper end of the single-mouth bottle is connected with a reflux condenser pipe and then connected with a tee joint, and one mouth of the tee joint is connected with a balloon for isolating oxygen. Then pumping for about 3min by a water pump to remove oxygen in the air. Heating in oil bath at 100 deg.c. The reaction is carried out for 24 hours, and the reaction is protected from light. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight.
And (3): synthesis of sulfonated polyimide membrane solution:
dissolving the sulfonated polyimide containing photosensitive groups and having a sulfonation degree of 40% synthesized in the step (2) in NMP to form a 2% -5% solution, adding a photoinitiator Benzophenone (BP) with a mass fraction of 5% and a photoinitiator auxiliary Triethylamine (TEA) with a mass fraction of 5%, and continuously stirring the mixture to prepare a film forming solution;
and (4): preparing a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane:
and (4) pouring the uniform membrane solution obtained in the step (3) into a membrane frame of 10cm multiplied by 10 cm. The solvent was evaporated in a vacuum oven at 70 ℃ for 3 days, and then the dry film was irradiated with 365nm for 15 min. Keeping the glass plate in the oven horizontal to ensure the uniform thickness of the film, naturally cooling, and then soaking the film in methanol at 80 ℃ for 3h to remove impurities such as residual solvent. The membrane is soaked in 1.0mol/L hydrochloric acid for 24h under the condition of normal temperature, and proton exchange is carried out. Then washing the membrane with deionized water to be neutral, and drying the membrane to be constant weight to obtain the photocyclization crosslinking sulfonated polyimide proton exchange membrane C-SPI-100 with the sulfonation degree of 100 percent.
Example 7:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 100%:
0.6957g (5mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (5mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in 50 deg.C vacuum oven to constant weight;
step (2): synthesis of sulfonated polyimide containing photosensitive group:
firstly, 0.4996g (1eq) of sulfonated polyimide containing hydroxyl group and having a sulfonation degree of 100% synthesized in the step (1) are weighed into a 100mL single-neck flask, 10mL of DMF is added, and the mixture is heated to about 100 ℃. After the solid was completely dissolved, 1.0124g (10eq) of 3-chlorocoumarin, 0.2300g (3eq) of potassium carbonate and 0.0046g (0.05eq) of potassium iodide were weighed out as bromophotosensitizer, and 5mL of DMF was added. The upper end of the single-mouth bottle is connected with a reflux condenser pipe and then connected with a tee joint, and one mouth of the tee joint is connected with a balloon for isolating oxygen. Then pumping for about 3min by a water pump to remove oxygen in the air. Heating in oil bath at 100 deg.c. The reaction is carried out for 24 hours, and the reaction is protected from light. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight.
And (3): synthesis of sulfonated polyimide membrane solution:
dissolving the sulfonated polyimide containing photosensitive groups and having a sulfonation degree of 100% synthesized in the step (2) in NMP to form a 2% -5% solution, adding a photoinitiator Benzophenone (BP) with a mass fraction of 5% and a photoinitiator auxiliary Triethylamine (TEA) with a mass fraction of 5%, and continuously stirring the mixture to prepare a film forming solution;
and (4): preparing a coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane:
and (4) pouring the uniform membrane solution obtained in the step (3) into a membrane frame of 10cm multiplied by 10 cm. The solvent was evaporated in a vacuum oven at 70 ℃ for 3 days, and then the dry film was irradiated with 365nm for 15 min. Keeping the glass plate in the oven horizontal to ensure the uniform thickness of the film, naturally cooling, and then soaking the film in methanol at 80 ℃ for 3h to remove impurities such as residual solvent. The membrane is soaked in 1.0mol/L hydrochloric acid for 24h under the condition of normal temperature, and proton exchange is carried out. Then washing the membrane with deionized water to be neutral, and drying the membrane to be constant weight to obtain the photocyclization crosslinking sulfonated polyimide proton exchange membrane C-SPI-100 with the sulfonation degree of 100 percent.
Example 8: proton conductivity tests of examples 2,3,4 and comparative examples 2,3, 4.
Measurement was performed by an AC impedance method using an electrochemical analyzer model CHI600B (Shanghai Chenghua instruments Co.). The measurement of the membrane is carried out under water-gas conditions, the vessel can humidify the environment by heating the injected water, the measured conductivity is practically the conductivity under the full-wet condition, the temperature is controlled by adding a sand bath or an oil bath, the magnitude of the conductivity is related to the thickness of the membrane and the distance between the electrodes, and the proton conductivity can be calculated according to the following formula.
Figure BDA0001640739670000151
Where σ is proton conductivity in units of S, L is the electrode spacing in units of mm, S is the cross-sectional area of the membrane in units of mm2, and Ω is the bulk resistance in units of Ω.
Proton conductivity of the coumarin-based photocrosslinked sulfonated polyimide proton exchange membranes C-SPI-140, C-SPI-120, C-SPI-100 of examples 2,3,4, and the uncrosslinked sulfonated polyimides SPI-140, SPI-120, SPI-100 of comparative examples 2,3,4 are shown in FIG. 1. The conductivity of the crosslinked proton exchange membrane decreased slightly compared to the uncrosslinked sample, but still reached a very high value. For example, the sample C-SPI-100 with the worst conductivity has the room-temperature conductivity (sigma) exceeding 0.01S/cm.
Example 9: tensile strength tests of examples 2,3,4 and comparative examples 2,3, 4.
According to the GB/T1040.2-2006 standard, the film is cut into sample strips with the width of 6mm, the length of 50m, the thickness of about 0.5mm and the distance between the sample lines of 25 mm. A stretching experiment is carried out on a UTM2502 universal material testing machine (Shenzhen Sansi longitudinal and transverse science and technology Co., Ltd.), and the stretching speed is 50 mm/min. Tensile strength is the tensile strength per cross-sectional area and is calculated by the following formula:
Figure BDA0001640739670000152
wherein Ts is a tensile strength (MPa); f is the maximum tension (N) to which the film sample is subjected when breaking; s is the cross-sectional area (m) of the film sample2)。
The tensile strength of the coumarin-based photocrosslinked sulfonated polyimide proton exchange membranes C-SPI-140, C-SPI-120, C-SPI-100 of examples 2,3,4, and the uncrosslinked sulfonated polyimides SPI-140, SPI-120, SPI-100 of comparative examples 2,3,4 are shown in FIG. 2. It is clear that the tensile strength of each corresponding sample after crosslinking is significantly improved over the uncrosslinked sample.
Comparative example 1:
step (1): synthesizing sulfonated polyimide containing hydroxyl with sulfonation degree of 80%:
0.6957g (4mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (6mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight;
step (2): preparing a film forming solution:
and (2) dissolving the hydroxyl-containing sulfonated polyimide with the sulfonation degree of 80% synthesized in the step (1) in DMSO, and heating and dissolving to prepare a membrane liquid with the mass fraction of 2% -5%.
And (3): preparation of uncrosslinked sulfonated polyimide proton exchange membranes:
and (3) pouring the film forming solution obtained in the step (2) into a film frame of 10cm multiplied by 10cm, and keeping the temperature of a film forming oven at 80 ℃ for 12 hours to completely volatilize the solvent. The glass plate was kept horizontal in the oven to ensure uniform film thickness. Then naturally cooling. Soaking the film in deionized water for stripping, and soaking the film in methanol at 80 deg.C for 3 hr to remove impurities such as residual solvent. And then soaking the membrane in 1.0mol/L hydrochloric acid for 24h at normal temperature, performing proton exchange, washing with deionized water to neutrality, and drying to constant weight to obtain the non-crosslinked sulfonated polyimide proton exchange membrane SPI-80 with the sulfonation degree of 80%.
Comparative example 2:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 100%:
0.6957g (5mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (5mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight; (ii) a
Step (2): preparing a film forming solution:
and (2) dissolving the hydroxyl-containing sulfonated polyimide with the sulfonation degree of 100% synthesized in the step (1) in DMSO, and heating and dissolving to prepare a membrane liquid with the mass fraction of 2% -5%.
And (3): preparation of uncrosslinked sulfonated polyimide proton exchange membranes:
and (3) pouring the film forming solution obtained in the step (2) into a film frame of 10cm multiplied by 10cm, and keeping the temperature of a film forming oven at 80 ℃ for 12 hours to completely volatilize the solvent. The glass plate was kept horizontal in the oven to ensure uniform film thickness. Then naturally cooling. Soaking the film in deionized water for stripping, and soaking the film in methanol at 80 deg.C for 3 hr to remove impurities such as residual solvent. And then soaking the membrane in 1.0mol/L hydrochloric acid for 24h at normal temperature, performing proton exchange, washing with deionized water to neutrality, and drying to constant weight to obtain the non-crosslinked sulfonated polyimide proton exchange membrane SPI-100 with the sulfonation degree of 100%.
Comparative example 3:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 120%:
0.6957g (6mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (4mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight;
step (2): preparing a film forming solution:
and (2) dissolving the hydroxyl-containing sulfonated polyimide with the sulfonation degree of 120% synthesized in the step (1) in DMSO, and heating and dissolving to prepare a membrane liquid with the mass fraction of 2% -5%.
And (3): preparation of uncrosslinked sulfonated polyimide proton exchange membranes:
and (3) pouring the film forming solution obtained in the step (2) into a film frame of 10cm multiplied by 10cm, and keeping the temperature of a film forming oven at 80 ℃ for 12 hours to completely volatilize the solvent. The glass plate was kept horizontal in the oven to ensure uniform film thickness. Then naturally cooling. Soaking the film in deionized water for stripping, and soaking the film in methanol at 80 deg.C for 3 hr to remove impurities such as residual solvent. And then soaking the membrane in 1.0mol/L hydrochloric acid for 24h at normal temperature, performing proton exchange, washing with deionized water to neutrality, and drying to constant weight to obtain the non-crosslinked sulfonated polyimide proton exchange membrane SPI-120 with the sulfonation degree of 120%.
Comparative example 4:
step (1): synthesizing sulfonated polyimide containing hydroxyl with a sulfonation degree of 140%:
0.6957g (7mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (3mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in sequence, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight;
step (2): preparing a film forming solution:
and (2) dissolving the hydroxyl-containing sulfonated polyimide with the sulfonation degree of 140% synthesized in the step (1) in DMSO, and heating and dissolving to prepare a membrane liquid with the mass fraction of 2% -5%.
And (3): preparation of uncrosslinked sulfonated polyimide proton exchange membranes:
and (3) pouring the film forming solution obtained in the step (2) into a film frame of 10cm multiplied by 10cm, and keeping the temperature of a film forming oven at 80 ℃ for 12 hours to completely volatilize the solvent. The glass plate was kept horizontal in the oven to ensure uniform film thickness. Then naturally cooling. Soaking the film in deionized water for stripping, and soaking the film in methanol at 80 deg.C for 3 hr to remove impurities such as residual solvent. And then soaking the membrane in 1.0mol/L hydrochloric acid for 24h at normal temperature, performing proton exchange, washing with deionized water to neutrality, and drying to constant weight to obtain the non-crosslinked sulfonated polyimide proton exchange membrane SPI-140 with the sulfonation degree of 140%.
Comparative example 5:
step (1): synthesizing sulfonated polyimide containing hydroxyl with sulfonation degree of 160%:
0.6957g (8mmol) of BDSA were weighed into a 250mL three-necked flask, and 20mL of m-cresol and 1.67mL (12mmol) of triethylamine were added. The right end of the three-mouth bottle is connected with a reflux condenser pipe through a bent connecting pipe, and then is connected with a conical flask filled with water through a drying pipe for testing the nitrogen flow rate, and the middle mouth is connected with a mechanical stirring device. The rotating speed is adjusted to 100r/min, and the temperature is increased to 80 ℃. After about 30min BDSA dissolved to give a yellow transparent liquid which was allowed to cool naturally to room temperature. 2.7936g (10mmol) of NTDA, 2.9898g (2mmol) of 6FAP and 2.4547g (20mmol) of benzoic acid are weighed out, added into a three-necked flask in turn, and added with 25mL of m-cresol to ensure that the solid content is 16-17 percent, and stirred for 30 min. The temperature is increased to 80 ℃ and the temperature is kept for 4 h. Then the temperature is increased to 180 ℃ and the temperature is kept for 20 h. After the reaction was stopped, it was cooled to 110 ℃ and then poured into 200mL of acetone to form a polymer strand. Filtering with Buchner funnel, Soxhlet extracting with acetone for 24 hr, and drying in vacuum oven at 50 deg.C to constant weight;
step (2): preparing a film forming solution:
and (2) dissolving the hydroxyl-containing sulfonated polyimide with the sulfonation degree of 160% synthesized in the step (1) in DMSO, and heating and dissolving to prepare a membrane liquid with the mass fraction of 2% -5%.
And (3): preparation of uncrosslinked sulfonated polyimide proton exchange membranes:
and (3) pouring the film forming solution obtained in the step (2) into a film frame of 10cm multiplied by 10cm, and keeping the temperature of a film forming oven at 80 ℃ for 12 hours to completely volatilize the solvent. The glass plate was kept horizontal in the oven to ensure uniform film thickness. Then naturally cooling. Soaking the film in deionized water for stripping, and soaking the film in methanol at 80 deg.C for 3 hr to remove impurities such as residual solvent. And then soaking the membrane in 1.0mol/L hydrochloric acid for 24h at normal temperature, performing proton exchange, washing with deionized water to neutrality, and drying to constant weight to obtain the non-crosslinked sulfonated polyimide proton exchange membrane SPI-160 with the sulfonation degree of 160%.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (8)

1. A coumarin-based photocyclization crosslinking sulfonated polyimide proton exchange membrane is characterized by comprising the following components in parts by weight: 1 part of sulfonated polyimide containing photosensitive groups, 0.005-0.05 part of photoinitiator assistant and 20-100 parts of organic solvent.
2. The coumarin-based photocrosslinked sulfonated polyimide proton exchange membrane according to claim 1, wherein the sulfonated polyimide containing photosensitive groups comprises the following components in parts by mole: 1 part of dianhydride, 0.2-2 parts of sulfonated diamine, 0.2-2 parts of non-sulfonated diamine, 0.2-10 parts of halogenated photosensitizer and 0.8-1.2 parts of catalyst.
3. The coumarin-based photocrosslinked sulfonated polyimide proton exchange membrane according to claim 2, wherein the dianhydrides include 1,3,5, 8-naphthalene tetracarboxylic dianhydride, pyromellitic dianhydride, 3,4,9, 10-perylene tetracarboxylic anhydride, 4,4' - (hexafluoroisopropylene) diphthalic anhydride, bicyclo [2.2.2] oct-7-ene-2, 3,5, 6-tetracarboxylic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, 1,6,7, 12-tetrachloro-3, 4,9, 10-perylene tetracarboxylic dianhydride, bisphenol a type diether dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 1,2,3, 4-butane tetracarboxylic dianhydride or 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride.
4. The coumarin-based photo-cyclized cross-linked sulfonated polyimide proton exchange membrane according to claim 2, wherein the sulfonated diamine comprises 2,2 '-bis (3-sulfobenzenesulfonyl) -4,4' -diaminobiphenyl, 2 '-bis (3-sulfo4-methylbenzenesulfonyl) -4,4' -diaminobiphenyl, 2 '-bis (2,4' -disulfonated biphenyl-4-sulfonyl) -4,4 '-diaminobiphenyl, 2' -bis (4- (4-sulfophenoxy) -3-sulfobenzenesulfonyl) -4,4 '-diaminobiphenyl, 2' -bis (4- (4-sulfophenylthio) -3-sulfobenzenesulfonyl) -4,4 '-diaminobiphenyl, 2' -bis (4- (4-sulfobenzenesulfonyl) -5-sulfobenzenesulfonyl) -4,4 '-diaminobiphenyl, 2' -bis (3- (3-sulfobenzenesulfonyl) -5-sulfobenzenesulfonyl) -4,4 '-diaminobiphenyl, 2' -bis (4- (methylene-4-sulfophenyl) -3-sulfobenzenesulfonyl) -4,4 '-diaminobiphenyl, 2' -bis (4- (isopropylidene-4-sulfophenyl) -3-sulfobenzenesulfonyl) -4,4 '-diaminobiphenyl, 2' -bis (4- (hexafluoroisopropylidene-4-sulfophenyl) -3-sulfobiphenyl One or more of acyloxy benzenesulfonyl) -4,4' -diaminobiphenyl.
5. The coumarin-based photocyclized crosslinked sulfonated polyimide proton exchange membrane of claim 2, the sulfonated diamine is characterized in that the non-sulfonated diamine has a functionality of more than or equal to 4 and comprises one or more of 2, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (4-aminophenyl) propane, 2-bis (3-amino-4-methylphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-aminophenyl) hexafluoropropane and 2, 2-bis (3-amino-4-methylphenyl) hexafluoropropane.
6. The coumarin-based photocrosslinked sulfonated polyimide proton exchange membrane according to claim 2, wherein the catalyst comprises one or more of triethylamine, acetic anhydride or benzoic acid.
7. The coumarin-based photocyclized crosslinked sulfonated polyimide proton exchange membrane of claim 2, wherein the halogenated photosensitizer comprises 3-chlorocoumarin, 6-bromocoumarin, 6-chloro-4-hydroxycoumarin, 3- (bromoacetyl) coumarin, 6-bromocoumarin-3-carboxylic acid, 6-chloro-4-hydroxycoumarin, or coumarin 2, coumarin 6, 4-hydroxycoumarin, 6-hydroxycoumarin, 3-aminocoumarin, coumarin 343, 3-hydroxycoumarin, coumarin-3-carboxylic acid, 7-hydroxycoumarin, 6, 7-dihydroxycoumarin, 5, 7-dihydroxycoumarin, or a mixture thereof, One or more of halogenated products of 4, 6-dihydroxycoumarin, 6-hydroxy-4-methylcoumarin, 7-hydroxy-4-methylcoumarin, 4-hydroxy-6-methylcoumarin, 7-hydroxycoumarin-4-acetic acid and 4-hydroxy-3-nitrocoumarin.
8. The coumarin-based photocyclized crosslinked sulfonated polyimide proton exchange membrane as claimed in claim 1, wherein the photoinitiator comprises 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, 2-dimethylamino-2-benzyl-1- [4- (4-morpholinyl) phenyl ] -1-butanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1- One or more of acetone, methyl benzoylformate, 4-phenylbenzophenone, 4-chlorobenzophenone, benzoin dimethyl ether, methyl o-benzoylbenzoate, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, diphenylethanone, alpha-hydroxyalkylphenone, alpha-aminoalkylphenone, bisbenzoylphenylphosphine oxide, benzophenone, 2, 4-dihydroxybenzophenone, Michler's ketone, thiopropoxythioxanone, and isopropyl thioxanthone;
the photoinitiation auxiliary agent comprises one or more of triethylamine, N-dimethyl diethanol amine, tris (3-mercaptopropionic acid) trimethylolpropane and diaryl iodonium salt;
the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.
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