CN104098896A - Aromatic sulfonated polybenzimidazole proton exchange membrane for fuel cell and preparation method thereof - Google Patents
Aromatic sulfonated polybenzimidazole proton exchange membrane for fuel cell and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2287—After-treatment
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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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1086—After-treatment of the membrane other than by polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- 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
Abstract
The invention discloses a preparation method for fast microwave synthesis of an aromatic sulfonated polybenzimidazole proton exchange membrane material. The aromatic sulfonated polybenzimidazole proton exchange membrane material comprises repeated structural units shown in the figure and has a sulfonation degree controllable in a range of 20-100%. The preparation method has simple processes and a low cost, utilizes a solution casting or tape casting method to realize preparation of the corresponding proton exchange membrane, and realizes acid doping treatment on the membrane thereby preparing the high temperature-resistant acid-doped aromatic sulfonated polybenzimidazole proton exchange membrane. The aromatic sulfonated polybenzimidazole proton exchange membrane has high proton conductivity and excellent chemical and thermostability, has uniform thickness of 40-150 microns, an acid doping amount of 3.57-17.49mol/RPU, a wide use temperature range of 25-160 DEG C and a wide application prospect, is especially suitable for a high-temperature proton exchange membrane fuel cell and can be normally used without external humidification.
Description
Technical field
The present invention relates to a kind of sulfonated aromatic polybenzimidazole proton exchange membrane and preparation method thereof, belong to fuel cell material technical field, particularly proton exchange membrane technical field.
Background technology
Proton exchange membrane is one of critical material technology determining proton exchange film fuel battery performance.At present, mould material used in Proton Exchange Membrane Fuel Cells more than 80% is all perfluoro sulfonic acid membrane and adopt modified membrane or the composite membrane that perfluoro sulfonic acid membrane is substrate.Yet, when this class proton exchange membrane is used for Proton Exchange Membrane Fuel Cells, exist various problems, as: (1) proton conduction seriously relies on water molecules, and this service temperature that has just limited fuel cell can not be over 100 ℃; (2) under low temperature, the easy CO of catalyzer is poisoning, can have a strong impact on fuel battery performance; (3) film is expensive.
In order to overcome the shortcoming of this class proton exchange membrane, at present, a large amount of research work is just concentrating on exploitation high-temperature resistant proton exchange membrane, improve the service temperature of fuel cell, this brings a series of advantage to Proton Exchange Membrane Fuel Cells, main manifestations is: (1) is conducive to CO at oxidation and the desorption of galvanic anode, thereby improves CO tolerant ability; (2) reduce the redox overpotential of cell cathode, improve the activity of catalyzer; (3) simplify the heat management system of battery, can effectively utilize used heat, reduce the usage quantity of reforming system water vapour.Along with the intensification of investigators to high temperature proton exchange film fuel cell understanding, the resistant to elevated temperatures proton exchange membrane of development of new is paid attention to by increasing investigators.
Polybenzimidazole, as a kind of novel engineering plastics, still has very good mechanical property and chemical property above at 400 ℃, is considered to the representative of high strength of new generation, high-modulus, high temperature resistance diaphragm material; Meanwhile, it also has the premium propertiess such as wear-resisting, fire-retardant, radiation hardness and acid and alkali-resistance.Aerospace field, microelectronic, fiber manufacture field, fuel cell field and catalyst field etc. have been widely used at present.
Research is found, although there is good resistance to elevated temperatures with the aromatic series polybenzimidazole that aromatic dicarboxylic acids and fragrant quaternary amine polycondensation obtain, but due to its structural high degree of rigidity and the strong interaction of interchain, cause its poorly soluble and infusibility, molecular weight is wayward, workability is poor, has limited its application in fuel cell field.
Sulfonated aromatic polybenzimidazole is exactly the class high-temperature resistant proton exchange membrane material arising at the historic moment under this background, introduces sulfonic acid group to obtaining higher proton conductivity in polybenzimidazole.Conventional method of sulfonating mainly contains following three kinds: (1) Direct Sulfonation polybenzimidazole main chain, the method also claims rear sulfonation method, i.e. sulfonation after first polymerization.But the shortcoming of this sulfonation method is: under hot conditions, polybenzimidazole main chain is very easily degraded, and sulfonation degree is wayward; (2) method that adopts chemical graft by the small molecules such as Isosorbide-5-Nitrae-butyl sultone and PS respectively reaction chain receive polybenzimidazole molecular backbone chain, generate side chain with sulfonic sulfonated polyphenyl imidazoles.This class graft type sulfonated polyphenyl imidazoles film all have good chemical property under low temperature or high temperature (160 ℃) condition, yet adopt the method for this grafting, the more difficult control of not only long reaction time, and sulfonation degree; (3) by sulfonated aromatic di-carboxylic acid and non-sulfonated aromatic di-carboxylic acid and fragrant quaternary amine or its hydrochloride direct condensation, make.Adopt and can effectively avoid in this way the loaded down with trivial details technique of chemical graft process and the problem such as the sulfonation degree of rear sulfonation method is wayward, the method designability is strong simultaneously, can effectively improve by the di-carboxylic acid monomer of choice structure uniqueness solvability and the workability of sulfonated aromatic polybenzimidazole.
At present, prepare the method that sulfonated aromatic polybenzimidazole mainly adopts and have melt-polycondensation and solution polycondensation.Wherein, the synthesis technique of melt-polycondensation is complicated, temperature control is required strict, be not easy to control, can not guarantee that reactant fully mixes in whole reaction process, end group may can not be contacted by embedding, the by product (as water, phenol etc.) of reaction is included in reaction system, affect the raising of polymericular weight, unreacted monomer is difficult to be removed in molten state, makes synthetic polymkeric substance purity drop.Although and solution polycondensation has been avoided these shortcomings of melt-polycondensation to a certain extent, it exists, and a maximum drawback---reaction time is long, solution polycondensation generally need to react more than 20 hours.Therefore, when adopting solution polycondensation method, utilizing the novel type of heating that can improve speed of reaction has been extremely urgent.The preparation method of a kind of synthetic aroma family sulfonated polyphenyl fast imidazoles and the sulfonated aromatic polybenzimidazole of preparing by the method are provided, and make high-temperature resistant proton exchange membrane just becomes the technical barrier that this technical field is badly in need of solution simultaneously.
Summary of the invention
One of object of the present invention is to provide a kind of sulfonated aromatic polybenzimidazole proton exchange membrane and method thereof for fuel cell, described proton exchange membrane has wider working temperature (25 ~ 160 ℃), especially at high temperature (120 ~ 160 ℃), still have higher proton conductivity, preparation method is simple.
Above-mentioned purpose of the present invention is achieved through the following technical solutions, sulfonated aromatic polybenzimidazole proton exchange membrane for a kind of fuel cell, it is characterized in that: this mould material is homemade sulfonated aromatic polybenzimidazole (sPBI), when introducing sulfonic acid group in polybenzimidazole molecular chain, also introduced the flexible group of hexichol ehter bond, both guaranteed the proton conductivity of proton exchange membrane, can solve the problem of the frangible indissoluble of film again, sulfonation degree controlled (20 ~ 100%), the thickness of film is 40 ~ 150 μ m.
Homemade mould material sPBI, it has following repeated structural unit:
Wherein x is not less than 0 integer; Y is not less than 0 integer, and x, y are 0 when different;
Another object of the present invention is to provide the preparation method of above-mentioned sulfonated aromatic polybenzimidazole proton exchange membrane, comprises following steps:
(1) microwave of sPBI mould material is synthetic fast
(
) polyphosphoric acid and Vanadium Pentoxide in FLAKES are joined in container, put into microwave reactor, under nitrogen atmosphere, heat, stir deoxidation, until Vanadium Pentoxide in FLAKES dissolves completely, be cooled to room temperature, obtain polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution;
(
) by 3,3 '-diaminobenzidine and 5-sodium sulfo isophthalate and 4,4 '-phenyl ether dioctyl phthalate joins in described polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, adopts microwave heating to carry out temperature reaction, first at 40 ~ 140 ℃, slowly stir 5 ~ 15min; Then at 170 ~ 200 ℃, react 70 ~ 150min, obtain henna viscous solution;
(
) described henna viscous solution is poured into water while hot, separate out the thread polymkeric substance of red-brown, by products therefrom soaking flushing repeatedly in deionized water, join subsequently in sodium hydrogen carbonate solution, remove residual acid, finally again with deionized water, ethanol repetitive scrubbing to remove inorganic salt impurity, decompress filter, vacuum-drying obtains sPBI to constant weight;
(2) preparation of sPBI proton exchange membrane
The proton exchange membrane material sPBI that step (1) is made is dissolved in fast the N of 1 ~ 5 times of quality under microwave heating condition, dinethylformamide (DMF) or N, N-N,N-DIMETHYLACETAMIDE (DMAc) or N, in N-dimethyl sulfoxide (DMSO) (DMSO) solvent, add solubility promoter triethylamine 100 ~ 500 μ L, microwave heating power is 300W ~ 600W, the mechanical stirring time is 60 ~ 150min, with the rotating speed separation 10 ~ 30min of 7000 ~ 9000 revs/min, get supernatant liquor and be poured on cast or casting film-forming in glass membrane cisterna.Be placed in air dry oven, at 40 ~ 60 ℃ dry 12 hours, and then at 100 ℃, keep 3 hours in the vacuum drying oven that is 0.09 ~ 0.1MPa in vacuum tightness; Dried film is immersed in deionized water, from membrane cisterna, take off.Under room temperature, in methyl alcohol, soak after 12 ~ 24 hours and take out, except the triethylamine in striping, with deionized water, repeatedly wash to remove residual methyl alcohol in striping, wipe subsequently the deionized water of film remained on surface, film is placed at 100 ℃ of the vacuum drying ovens that vacuum tightness is 0.09 ~ 0.1MPa and is kept 1 hour, it is that 10 ~ 90%(is preferably 60 ~ 85% that dry high-temperature polymer film is immersed to excessive mass concentration) in phosphoric acid and/or sulphuric acid soln, under room temperature standing 24 hours, after taking out film, wipe the remaining attached acid in its surface, obtain required high-temperature resistant aromatic sulfonated polyphenyl imidazoles proton exchange membrane, the even thickness of film (40 ~ 150 μ m), acid doping is contained sour amount of substance in every mole of sPBI repeating unit of 3 ~ 18mol/RPU().
The present invention has compared obvious advantage with technology with existing material:
(1) proton conductivity of film is strong.The object that phosphoric acid and/or sulfuric acid are immersed in the present invention is to improve the proton conductivity of film, to reaching proton exchange membrane, at high temperature still has the requirement of certain proton conductivity; Utilize film prepared by preparation method proposed by the invention under normal temperature and high temperature, to have excellent proton conductivity;
(2) good stability of film.The membrane structure of utilizing method proposed by the invention to prepare is stable, has good chemical stability and thermostability;
(3) preparation technology is simple, and cost is low.The microwave that the present invention proposes the fast preparation method of synthetic sPBI can shorten the polycondensation cycle widely, simplifies its preparation technology, obtains sPBI mould material high temperature resistant, favorable solubility.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of sulfonated aromatic polybenzimidazole proton exchange membrane.(a) and (b), (c) have shown respectively the micromorphology of the sPBI film of different sulfonation degree, as can be seen from the figure, increase along with sPBI sulfonation degree, the microcosmic surface of sPBI film is just more coarse, be owing to having introduced wetting ability sulfonic acid group in polymer architecture, make sPBI in water, have certain swelling to cause.
Fig. 2 is proton conductivity and the sour doping relation of sulfonated aromatic polybenzimidazole proton exchange membrane.Ordinate zou is proton conductivity (Scm
-1), X-coordinate is sulfonation degree; Trigonometric curve represents the proton conductivity of sPBI proton exchange membrane when different sulfonation degree; Square, circular, trigpoint represents the proton conductivity of Nafion112 film under same test condition.
Fig. 3 is proton conductivity and the sour doping relation of sulfonated aromatic polybenzimidazole proton exchange membrane.Ordinate zou is proton conductivity (Scm
-1), X-coordinate be actual probe temperature (℃); The electrochemical workstation (IM6ex) that the German ZAHNER ENNIUM of proton conductivity test employing company produces, test condition is: range of frequency: 0.1 ~ 1MHz, voltage amplitude: 5mV, temperature: 25 ~ 160 ℃, relative humidity: 0%, respectively sPBI film and Nafion112 film are tested, shown in result Fig. 2 and Fig. 3, under same test condition, the proton conductivity of sPBI film is suitable with Nafion112 film; When sulfonation degree or probe temperature are when higher, its proton conductivity is even better than Nafion112 film, proves that sPBI film has good chemical property, can meet the chemical property requirement of fuel cell completely.
Embodiment
Embodiment 1
The preparation of the sulfonated aromatic polybenzimidazole proton exchange membrane of sulfonation degree 20%
(1) microwave of sPBI mould material is synthetic fast
The sulfonated aromatic polybenzimidazole of preparation, structure is as follows:
50.7g polyphosphoric acid and 8.2g Vanadium Pentoxide in FLAKES are joined in the 100mL four-hole round-bottomed flask that agitator and airway are housed, put it in microwave reactor, under nitrogen atmosphere in heating, at 120 ℃, stir deoxidation, until Vanadium Pentoxide in FLAKES white powder dissolves completely, obtain a kind of transparent, clarification homogeneous solution, after it is cooled to room temperature, obtain polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, take 1.8mmol(0.3857g) 3,5-sodium sulfo isophthalate and the 7.2mmol(1.8589g of 3 '-diaminobenzidine, 1.8mmol (0.4827g)) 4,4 '-phenyl ether dioctyl phthalate once feeds intake before joining in prepared polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, the temperature reaction stage adopts microwave procedure to heat up: microwave heating power is 300W, in 40 ℃ of abundant 15min that stir, reaction monomers is fully mixed, in 170 ℃ of reaction 150min, solution becomes sticky thick gradually, stopped reaction, red-brown viscous solution is poured into while hot and in a large amount of deionized waters (frozen water), separated out brown thread polymkeric substance, by products therefrom soaking flushing repeatedly in deionized water, remove unnecessary acid, be immersed in subsequently in 5% sodium hydrogen carbonate solution, be placed in 45 ℃ of baking ovens 48 hours to remove remaining acid, until washing fluid pH value is neutrality, again at deionized water (boiling water), in dehydrated alcohol repeatedly washing by soaking to remove inorganic salt impurity, decompress filter, then vacuum-drying at 120 ℃, to constant weight, be ground into powder, obtain based on 5-sodium sulfo isophthalate containing hexichol ether sulfonated aromatic polybenzimidazole mould material 1, its reaction yield is 97.5%, sulfonation degree is 20%,
(2) preparation of sPBI proton exchange membrane
The proton exchange membrane material making 1 is dissolved in fast under microwave heating condition in the DMF solvent of 1 times of quality, add solubility promoter triethylamine 100 μ L, microwave heating power is 300W, the mechanical stirring time is 60min, with the separated 30min of the rotating speeds of 7000 revs/min, get supernatant liquor and be poured on cast or casting film-forming in glass membrane cisterna.Be placed in air dry oven, at 40 ℃ dry 12 hours, and then at 100 ℃, keep 3 hours in the vacuum drying oven that is 0.1MPa in vacuum tightness; Dried film is immersed in deionized water, from membrane cisterna, take off.Under room temperature, in methyl alcohol, soak after 12 hours and take out, except the triethylamine in striping, with deionized water, repeatedly wash to remove residual methyl alcohol in striping, wipe subsequently the deionized water of film remained on surface, film is placed at 100 ℃ of the vacuum drying ovens that vacuum tightness is 0.1MPa and is kept 1 hour, it is in 60% phosphoric acid solution that dry high-temperature polymer film is immersed to excessive mass concentration, under room temperature standing 24 hours, after taking out film, wipe the remaining attached acid in its surface, obtain required high-temperature resistant aromatic polybenzimidazole proton exchange membrane, the even thickness of film (60 μ m), acid doping is 6.97mol/RPU.
Embodiment 2
The preparation of the sulfonated aromatic polybenzimidazole proton exchange membrane of sulfonation degree 60%
(1) microwave of sPBI mould material is synthetic fast
The sulfonated aromatic polybenzimidazole of preparation, structure is as follows:
51.2g polyphosphoric acid and 24.6g Vanadium Pentoxide in FLAKES are joined in the 100mL four-hole round-bottomed flask that agitator and airway are housed, put it in microwave reactor, under nitrogen atmosphere in heating, at 140 ℃, stir deoxidation, until Vanadium Pentoxide in FLAKES white powder dissolves completely, obtain a kind of transparent, clarification homogeneous solution, after it is cooled to room temperature, obtain polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, take 1.8mmol(0.3857g) 3,5-sodium sulfo isophthalate and the 3.6mmol(0.9296g of 3 '-diaminobenzidine, 5.4mmol (1.4482g)) 4,4 '-phenyl ether dioctyl phthalate once feeds intake before joining in prepared polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, the temperature reaction stage adopts microwave procedure to heat up: microwave heating power is 400W, in 70 ℃ of abundant 10min that stir, reaction monomers is fully mixed, in 180 ℃ of reaction 110min, solution becomes sticky thick gradually, stopped reaction, red-brown viscous solution is poured into while hot and in a large amount of deionized waters (frozen water), separated out brown thread polymkeric substance, by products therefrom soaking flushing repeatedly in deionized water, remove unnecessary acid, be immersed in subsequently in 5% sodium hydrogen carbonate solution, be placed in 45 ℃ of baking ovens 48 hours to remove remaining acid, until washing fluid pH value is neutrality, again at deionized water (boiling water), in dehydrated alcohol repeatedly washing by soaking to remove inorganic salt impurity, decompress filter, then vacuum-drying at 120 ℃, to constant weight, be ground into powder, obtain based on 5-sodium sulfo isophthalate containing hexichol ether sulfonated aromatic polybenzimidazole mould material 2, its reaction yield is 98.5%, sulfonation degree is 60%,
(2) preparation of sPBI proton exchange membrane
The proton exchange membrane material making 2 is dissolved in fast under microwave heating condition in the DMAc solvent of 2.5 times of quality, add solubility promoter triethylamine 250 μ L, microwave heating power is 450W, the mechanical stirring time is 60 ~ 150min, with the separated 15min of the rotating speeds of 8000 revs/min, get supernatant liquor and be poured on cast or casting film-forming in glass membrane cisterna.Be placed in air dry oven, at 50 ℃ dry 12 hours, and then at 100 ℃, keep 3 hours in the vacuum drying oven that is 0.1MPa in vacuum tightness; Dried film is immersed in deionized water, from membrane cisterna, take off.Under room temperature, in methyl alcohol, soak after 18 hours and take out, except the triethylamine in striping, with deionized water, repeatedly wash to remove residual methyl alcohol in striping, wipe subsequently the deionized water of film remained on surface, film is placed at 100 ℃ of the vacuum drying ovens that vacuum tightness is 0.1MPa and is kept 1 hour, it is in 75% sulphuric acid soln that dry high-temperature polymer film is immersed to excessive mass concentration, under room temperature standing 24 hours, after taking out film, wipe the remaining attached acid in its surface, obtain required high-temperature resistant aromatic polybenzimidazole proton exchange membrane, the even thickness of film (87 μ m), acid doping is 9.84mol/RPU.
Embodiment 3
The preparation of the sulfonated aromatic polybenzimidazole proton exchange membrane of sulfonation degree 100%
(1) microwave of sPBI mould material is synthetic fast
The sulfonated aromatic polybenzimidazole of preparation, has following repeated structural unit:
53.8g polyphosphoric acid and 16.7g Vanadium Pentoxide in FLAKES are joined in the 100mL four-hole round-bottomed flask that agitator and airway are housed, put it in microwave reactor, under nitrogen atmosphere, heat, at 160 ℃, stir deoxidation, until Vanadium Pentoxide in FLAKES white powder dissolves completely, obtain a kind of transparent, clarification homogeneous solution, after it is cooled to room temperature, obtain polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, take 1.8mmol(0.3857g) 3, the 5-sodium sulfo isophthalate of 3 '-diaminobenzidine and 9mmol (2.4136g) once feeds intake before joining in prepared polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, entering temperature reaction stage employing microwave procedure heats up: microwave heating power is 600W, in 120 ℃ of abundant 5min that stir, reaction monomers is fully mixed, in 200 ℃ of reaction 70min, solution becomes sticky thick gradually, stopped reaction, red-brown viscous solution is poured into while hot and in a large amount of deionized waters (frozen water), separated out brown thread polymkeric substance, by products therefrom soaking flushing repeatedly in deionized water, remove unnecessary acid, be immersed in subsequently in 5% sodium hydrogen carbonate solution, be placed in 45 ℃ of baking ovens 48 hours to remove remaining acid, until washing fluid pH value is neutrality, again at deionized water (boiling water), in dehydrated alcohol repeatedly washing by soaking to remove inorganic salt impurity, decompress filter, then vacuum-drying at 120 ℃, to constant weight, obtain the sulfonated aromatic polybenzimidazole mould material 3 based on terephthalic acid-2-sodium sulfonate, reaction yield is 98.4%, sulfonation degree is 79.6%,
(2) preparation of sPBI proton exchange membrane
The proton exchange membrane material making 3 is dissolved in fast under microwave heating condition in the DMSO solvent of 5 times of quality, add solubility promoter triethylamine 500 μ L, microwave heating power is 600W, the mechanical stirring time is 150min, with the separated 10min of the rotating speeds of 9000 revs/min, get supernatant liquor and be poured on cast or casting film-forming in glass membrane cisterna.Be placed in air dry oven, at 60 ℃ dry 12 hours, and then at 100 ℃, keep 3 hours in the vacuum drying oven that is 0.1MPa in vacuum tightness; Dried film is immersed in deionized water, from membrane cisterna, take off.Under room temperature, in methyl alcohol, soak after 24 hours and take out, except the triethylamine in striping, with deionized water, repeatedly wash to remove residual methyl alcohol in striping, wipe subsequently the deionized water of film remained on surface, film is placed at 100 ℃ of the vacuum drying ovens that vacuum tightness is 0.1MPa and is kept 1 hour, it is in 85% phosphoric acid and 85% sulfuric acid mixed solution that dry high-temperature polymer film is immersed to excessive mass concentration, under room temperature standing 24 hours, after taking out film, wipe the remaining attached acid in its surface, obtain required high-temperature resistant aromatic polybenzimidazole proton exchange membrane, the even thickness of film (147 μ m), acid doping is contained sour amount of substance in every mole of sPBI repeating unit of 17.49mol/RPU().
Above embodiments of the invention are explained in detail, all embodiment implement take technical solution of the present invention under prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention are not limited to the above embodiments.
Claims (9)
1. a sulfonated aromatic polybenzimidazole mould material, it has following repeated structural unit:
Wherein x is not less than 0 integer; Y is not less than 0 integer, and x, y are 0 when different.
2. a preparation method for sulfonated aromatic polybenzimidazole proton exchange membrane, comprises the steps:
(1) microwave of sPBI mould material is synthetic fast
(
) polyphosphoric acid and Vanadium Pentoxide in FLAKES are joined in container, put into microwave reactor, under nitrogen atmosphere, heat, stir deoxidation, until Vanadium Pentoxide in FLAKES dissolves completely, be cooled to room temperature, obtain polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution;
(
) by 3,3 '-diaminobenzidine and 5-sodium sulfo isophthalate and 4,4 '-phenyl ether dioctyl phthalate joins in described polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, adopts microwave heating to carry out temperature reaction, first at 40 ~ 140 ℃, slowly stir 5 ~ 15min; Then at 170 ~ 200 ℃, react 70 ~ 150min, obtain henna viscous solution;
(
) described henna viscous solution is poured into water while hot, separate out the thread polymkeric substance of red-brown, by products therefrom soaking flushing repeatedly in deionized water, join subsequently in sodium hydrogen carbonate solution, remove residual acid, finally again with deionized water, ethanol repetitive scrubbing to remove inorganic salt impurity, decompress filter, vacuum-drying obtains sPBI mould material to constant weight;
(2) preparation of sPBI proton exchange membrane
The proton exchange membrane material sPBI that step (1) is made is dissolved in fast in the organic solvent of 1-5 times of quality under microwave heating condition, add solubility promoter triethylamine 100 ~ 500 μ L, microwave heating power is 300W ~ 600W, the mechanical stirring time is 60 ~ 150min, with the resulting solution of rotating speed separation 10 ~ 30min of 7000 ~ 9000 revs/min, get supernatant liquor and be poured on cast or casting film-forming in glass membrane cisterna, be placed in air dry oven, at 40 ~ 60 ℃ dry 12 hours, and then at 100 ℃, keep 3 hours in the vacuum drying oven that is 0.09 ~ 0.1MPa in vacuum tightness, dried film is immersed in deionized water, from membrane cisterna, take off, under room temperature, in methyl alcohol, soak after 12 ~ 24 hours and take out, except the triethylamine in striping, with deionized water, repeatedly wash to remove residual methyl alcohol in striping, wipe subsequently the deionized water of film remained on surface, film is placed at 100 ℃ of the vacuum drying ovens that vacuum tightness is 0.09 ~ 0.1MPa and is kept 1 hour, it is that 10 ~ 90%(is preferably 60 ~ 85% that dry high-temperature polymer film is immersed to excessive mass concentration) in phosphoric acid and/or sulphuric acid soln, under room temperature standing 24 hours, after taking out film, wipe the remaining attached acid in its surface, obtain required high-temperature resistant aromatic polybenzimidazole proton exchange membrane, the even thickness of film (40 ~ 150 μ m), acid doping is contained sour amount of substance in every mole of sPBI repeating unit of 3 ~ 18mol/RPU().
3. the preparation method of sulfonated aromatic polybenzimidazole proton exchange membrane according to claim 2, is characterized in that: in described polyphosphoric acid/Vanadium Pentoxide in FLAKES homogeneous solution, the mass content of Vanadium Pentoxide in FLAKES is 14% ~ 33%.
4. the preparation method of sulfonated aromatic polybenzimidazole proton exchange membrane according to claim 2, is characterized in that: the described temperature heating under nitrogen atmosphere is 120 ~ 160 ℃.
5. the preparation method of sulfonated aromatic polybenzimidazole proton exchange membrane according to claim 2, is characterized in that: the molar content of sulfonated aromatic di-carboxylic acid in sulfonated aromatic di-carboxylic acid and non-sulfonated aromatic di-carboxylic acid total amount is 20 ~ 100%.
6. the preparation method of sulfonated aromatic polybenzimidazole proton exchange membrane according to claim 2, is characterized in that: fragrant quaternary amine and total aromatic dicarboxylic acids's molar ratio is 1:5.
7. the preparation method of sulfonated aromatic polybenzimidazole proton exchange membrane according to claim 2, is characterized in that: the power of described microwave heating is 300 ~ 600W.
8. the preparation method of sulfonated aromatic polybenzimidazole proton exchange membrane according to claim 2, it is characterized in that: the method film forming organic solvent used is selected from N, dinethylformamide (DMF), N, N-N,N-DIMETHYLACETAMIDE (DMAc) or N, one or more mixing solutionss in N-dimethyl sulfoxide (DMSO) (DMSO).
9. the preparation method of sulfonated aromatic polybenzimidazole proton exchange membrane according to claim 2, is characterized in that: the method sour doped solution used is to be made by 85% strong phosphoric acid and/or 98% diluting concentrated sulfuric acid.
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