CN104629081A - Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base - Google Patents
Preparation method of pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as base Download PDFInfo
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Abstract
The invention belongs to the technical fields of functional polymer materials and electrochemistry and in particular relates to a preparation method of a pore-filing type proton exchange membrane taking double ether crosslinked porous polybenzimidazole imide as a base. The preparation method of the pore-filing type proton exchange membrane taking the double ether crosslinked porous polybenzimidazole imide as the base comprises the following steps: firstly synthesizing polybenzimidazole imide provided with a cross-linkable imidazole group on a main chain, preparing the synthesized polybenzimidazole imide into a membrane solution, adding a double ether crosslinking agent, reacting with the imidazole group, a crosslinking sulfonated polyimide polymer in a membrane forming process, adding a pore-forming agent at the same time to form a crosslinked porous polybenzimidazole imide membrane, and finally compounding the crosslinked porous polybenzimidazole imide membrane with perfluorosulfonate resin, so that the pore-filling type proton exchange membrane is obtained. A basement membrane gives good mechanical properties to the pore-filling type membrane, and the pore-filling type membrane has high dimensional stability; meanwhile, the proton conductivity of a perfluorosulfonate membrane is not greatly reduced. The preparation method of the pore-filing type proton exchange membrane taking the double ether crosslinked porous polybenzimidazole imide as the base has the advantages that the preparation technology controllability is good; and compared with the traditional perfluorosulfonate membrane, the obtained pore-filling type proton exchange membrane has high mechanical strength and good dimensional stability and has broad application prospect in a polymer electrolyte membrane fuel cell.
Description
Technical field
The invention belongs to functional high molecule material and technical field of electrochemistry, be specifically related to a kind of with the preparation method of the bis ether cross-linking type porous polybenzimidazole imide Pore-Filling Type Proton Exchange Membrane that is substrate.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFCs) is electrolytical fuel cell with proton exchange membrane, is the one in five kinds of fuel cells.A kind of oxygen generation chemical reaction that can make in hydrogen and air that its is at present the most ripe in the world, generation water also discharges the technology of electric energy, has energy efficiency high, discharges low, eco-friendly advantage.As the core of fuel cell, electrolytical character is directly connected to the key property such as generating efficiency, work-ing life of fuel cell.And the proton conductivity of proton exchange membrane (PEM), mechanical property, the performance of dimensional stability on PEMFC have directly important impact.At present, perfluor type proton exchange membrane is (as Nafion
?) be the main body of proton exchange membrane on market, but the costliness of its price, physical strength and poor dimensional stability and shortcoming limits its widespread use such as fuel permeability is high.
Pore-Filling Type Proton Exchange Membrane a kind ofly ionogen is filled into the novel proton exchange membranes formed in the basilar membrane of porous.Compared with traditional perfluoro sulfonic acid membrane, Pore-Filling Type Proton Exchange Membrane tool has the following advantages: (1) limits the swelling property of film; (2) fuel permeability is reduced; (3) its proton conductivity and fuel permeability can be regulated by the aperture of film and porosity; (4) the swelling of film is avoided and the peeling off of the not swelling film that causes of catalyzer and catalyst layer; (5) cheap.This just requires that the basement membrane material of Pore-Filling Type Proton Exchange Membrane self has excellent mechanical property and dimensional stability and low gas and penetration by liquid rate, simultaneously also cheap.
Polyimide has superior heat, chemistry and mechanical stability and low gas permeability, obtained at many industrial circles such as microelectronics, membrane sepn and paid close attention to widely, and these advantages to be also us to be obtained for mid-term at Proton Exchange Membrane Fuel Cells.But its Green Tea Extract oxidisability is poorer than perfluoro sulfonic acid membrane.
Polybenzimidazole is the base polymer that main chain contains repetition benzoglyoxaline ring, has excellent performance, is the best resin of current thermotolerance and flame retardancy.Benzimidazolyl-is incorporated in polyimide main chain, not only can improve the antioxidative stabilizer of polyimide, the film-forming properties of polybenzimidazole, but also the use temperature of proton exchange membrane material can be improved, make it can have excellent performance under low humidity high temperature.Utilize the active N-H key in benzimidazolyl-simultaneously, add linking agent, in film process, make it be cross-linked, thus improve the mechanical property, reduction gas permeability, raising hydrolysis resistance to oxidation stability etc. of medlin proton exchange film.
Summary of the invention
The object of this invention is to provide a kind of with the preparation method of the bis ether cross-linking type porous polybenzimidazole imide film proton exchange membrane that is substrate.
The proton exchange membrane being substrate with bis ether cross-linking type porous polybenzimidazole imide film that the present invention proposes, introduce benzimidazole structure on polyimide-based polymer main chain, and in film process, utilize the active N-H structure on imidazolyl and bis ether linking agent to react, make it be cross-linked, add water soluble pore formers simultaneously, after water infiltration, obtain vesicular structure, finally perfluorinated sulfonic acid base polymer solution-cast evaporating solvent on this porous-film is obtained Pore-Filling Type Proton Exchange Membrane.Its raw material composition comprises: polybenzimidazole imide, bis ether linking agent (mol ratio of its crosslinkable group and benzoglyoxaline group is between 0-0.8), pore-creating agent (be 0-70% with the mass ratio of polymkeric substance) and perfluorinated sulfonic resin.
Propose in the present invention with the preparation method of the bis ether cross-linking type porous polybenzimidazole imide film proton exchange membrane that is substrate, concrete steps are as follows:
(1) in the there-necked flask of complete drying, add organic solvent and the diamines containing benzimidazole structure, connect gas inlet, drying tube, pneumatic outlet, reflux condensing tube and mechanical stirrer, pass into rare gas element and start to stir, after diamines dissolves completely, add diacid and the catalyzer of equivalent.Be warming up to 80 DEG C of reaction 4h, heat up afterwards and make solvent refluxing, reaction 20h.Be cooled to 100 DEG C after reaction terminates, product slowly poured in acetone and precipitates, precipitation acetone is carried out soxhlet extraction removing residual solvent, catalyzer and small molecular weight material, afterwards product is dried standby in vacuum drying oven under 60 DEG C of conditions;
(2) by the polymer dissolution of gained in (1) in organic solvent, the massfraction of solution is 2%-5%; After thing to be polymerized dissolves completely, add diether type linking agent, in the imidazole ring in its crosslinkable groups and macromolecular chain, the mol ratio of hydrogen bound to nitrogen is 0-0.8.Add pore-creating agent, its massfraction is the 0%-70% of polymkeric substance simultaneously.Stirring at room temperature makes linking agent and pore-creating agent dissolve completely and be uniformly dispersed.Film liquid is cast in the film frame of 10cm × 10cm 80 DEG C time, insulation 6h, being warming up to 150 DEG C again makes crosslinking reaction carry out completely, again obtained film deionized water is soaked 24h, 24h is soaked with methyl alcohol again after taking-up, finally film is dried under 60 DEG C of conditions, obtained crosslinked polybenzimidazole imide porous-film;
(3) be dissolved in organic solvent by perfluorinated sulfonic resin, liquid quality fraction is 2%-5%; First add part film liquid in the film frame of 10cm × 10cm, again the cross-linked porous film in (2) is joined above film liquid, again residue film liquid is joined above cross-linked porous film, complete wetting, dry under 80 DEG C of conditions, afterwards obtained film deionized water is soaked 24h, after taking-up, soak 24h with methyl alcohol again, finally film is dried under 60 DEG C of conditions, the proton exchange membrane that to obtain with bis ether cross-linking type porous polybenzimidazole imide film be substrate.
In the present invention, bis ether linking agent is the linking agent with epoxide group and bis ether structure, and its epoxide group can with the H-H reaction on hydrogen bound to nitrogen on benzoglyoxaline group.Such as 3,3 ', 5,5 '-tetramethyl biphenyl diphenol diglycidylether (TMBP).
In the present invention, described organic solvent is the mixed solution of any one or two kinds in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
Beneficial effect of the present invention is:
Benzoglyoxaline group is introduced in polyimide molecule chain, makes intermolecular being cross-linked by diether type linking agent, and add pore-creating agent and prepare the crosslinked porous polybenzimidazole imide film of bis ether, and in this, as the substrate of Pore-Filling Type Proton Exchange Membrane.Because there is crosslinking structure in the molecular structure of this substrate, basilar membrane is made to have outstanding thermostability, antioxidative stabilizer, stability to hydrolysis and mechanical property.After obtaining Pore-Filling Type Proton Exchange Membrane with perfluorinated sulfonic resin compound, physical strength and the shortcoming such as poor dimensional stability and fuel permeability height of perfluorinated sulfonic resin can be improved.Meanwhile, the appearance of vesicular structure makes perfluorinated sulfonic resin can be through, the electrical property of Pore-Filling Type Proton Exchange Membrane will be caused to occur huge decline because basilar membrane cannot carry out proton exchange.
Accompanying drawing explanation
Fig. 1 is that cross-linking type porous polybenzimidazole imide CPIBI-60-Y is when fixing dosage of crosslinking agent, the figure that the change of the tensile strength of cross-linked porous film changes with the change of the massfraction Y of pore-creating agent, wherein pore-creating agent massfraction is 10 % respectively, 30%, 50%, 70%.
Fig. 2 is that cross-linking type porous polybenzimidazole imide CPIBI-X-50 is when fixing pore-creating agent massfraction, the change of the tensile strength of cross-linked porous film is with the change of the mol ratio X of crosslinked group in linking agent and benzoglyoxaline group and the figure changed, wherein mol ratio is 0 respectively, 1:5,2:5,3:5,4:5.
Fig. 3 is with the variation diagram of specific conductivity under the cross-linking type porous polybenzimidazole imide filling perforation type perfluorinated sulfonic resin proton exchange membrane that is substrate at different temperatures 100% humidity condition.Wherein adopted substrate is CPIBI-60-30.
Embodiment
Following examples are merely and further illustrate the present invention, and do not violating under purport of the present invention, the present invention should be not limited to the content that following experimental example is specifically expressed.
Embodiment 1
Prepared by the CPIBI-20-50-Nafion of the filling perforation type Nafion resin molding being substrate with the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 1:5, pore-creating agent 50% massfraction.
(1) preparation process of polybenzimidazole polyimide PI BI is as follows, 3mmol (0.6796g is added in the 100mL there-necked flask of complete drying, 99%) 2-(4-aminophenyl) N-Methyl pyrrolidone (NMP) of-5 aminobenzimidazoles (APBIA) and 10mL, connect gas inlet, drying tube, pneumatic outlet, reflux condensing tube and mechanical stirrer, pass into rare gas element and start to stir, after APBIA dissolves completely, add 3mmol (1.3599g, 98%) 4, the catalyzer isoquinoline 99.9 of 4 '-hexafluoroisopropyli,ene-Tetra hydro Phthalic anhydride (6FDA) and 0.78mL, after question response thing dissolves completely, be warming up to 80 DEG C and keep this thermotonus 4h, being warming up to 215 DEG C afterwards makes solvent NMP reflux, reaction 20h, after reaction terminates, be cooled to about 100 DEG C, product is poured in acetone and precipitates, and repeatedly rinse with acetone, again with acetone to product soxhlet extraction 24h, afterwards product is placed in 60 DEG C of baking ovens to dry, obtain polybenzimidazole polyimide PI BI,
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-20-50 is as follows, weigh 0.3g(1) in the PIBI that obtains, be dissolved in the NMP of 10mL, after dissolving completely, at room temperature add 0.017g linking agent 3, 3 ', 5, 5 '-tetramethyl biphenyl diphenol diglycidylether (TMBP) and 0.15g pore-creating agent dibutyl phthalate (DBP), stirring at room temperature, afterwards film liquid is cast in the film frame of 10cm × 10cm 80 DEG C time, insulation 6h, being warming up to 150 DEG C again makes crosslinking reaction carry out completely, again obtained film deionized water is soaked 24h, 24h is soaked with methyl alcohol again after taking-up, finally film is dried under 60 DEG C of conditions, obtained crosslinked polybenzimidazole imide porous-film CPIBI-20-50,
(3) preparation process of Nafion filling perforation film is as follows, weighs 0.6gNafion resin, is dissolved in the NMP of 12mL, filters configuration film forming liquid.Be cast in by 6mL film liquid on the sheet glass of 10 cm × 10 cm, CPIBI-20-50 is positioned over above the film liquid of sheet glass, casts on CPIBI-20-50 by remaining 6mL film liquid simultaneously, and dry in 80 DEG C of baking ovens, solvent volatilizees completely.Film is peeled off from sheet glass, puts into methyl alcohol and soak 24 h, except the residual nmp solvent in striping.Film is taken out, use deionized water repetitive scrubbing, dry 24 h in 150 DEG C of vacuum drying ovens, obtain with the CPIBI-20-50-Nafion of the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 1:5, the pore-creating agent 50% massfraction filling perforation type Nafion resin molding that is substrate.
Embodiment 2
Prepared by the CPIBI-40-50-Nafion of the filling perforation type Nafion resin molding being substrate with the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 2:5, pore-creating agent 50% massfraction.
(1) preparation process of polybenzimidazole polyimide PI BI is with the step (1) in embodiment 1;
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-40-50, except the quality of TMBP is become except 0.034g, other steps and the kind of reagent added and quality identical with the step (2) in embodiment 1;
(3) preparation process of Nafion filling perforation film, except basilar membrane is become except CPIBI-40-50, other steps and the reagent type added and quality identical with the step (3) in embodiment 1.
Embodiment 3
Prepared by the CPIBI-60-50-Nafion of the filling perforation type Nafion resin molding being substrate with the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 3:5, pore-creating agent 50% massfraction.
(1) preparation process of polybenzimidazole polyimide PI BI is with the step (1) in embodiment 1;
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-60-50, except the quality of TMBP is become except 0.051g, other steps and the kind of reagent added and quality identical with the step (2) in embodiment 1;
(3) preparation process of Nafion filling perforation film, except basilar membrane is become except CPIBI-60-50, other steps and the reagent type added and quality identical with the step (3) in embodiment 1.
Embodiment 4
Prepared by the CPIBI-80-50-Nafion of the filling perforation type Nafion resin molding being substrate with the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 4:5, pore-creating agent 50% massfraction.
(1) preparation process of polybenzimidazole polyimide PI BI is with the step (1) in embodiment 1;
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-80-50, except the quality of TMBP is become except 0.068g, other steps and the kind of reagent added and quality identical with the step (2) in embodiment 1;
(3) preparation process of Nafion filling perforation film, except basilar membrane is become except CPIBI-60-50, other steps and the reagent type added and quality identical with the step (3) in embodiment 1.
Embodiment 5
Prepared by the CPIBI-60-10-Nafion of the filling perforation type Nafion resin molding being substrate with the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 3:5, pore-creating agent 10% massfraction.
(1) preparation process of polybenzimidazole polyimide PI BI is with the step (1) in embodiment 3;
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-60-10, except the quality of DBP is become except 0.03g, other steps and the kind of reagent added and quality identical with the step (2) in embodiment 3;
(3) preparation process of Nafion filling perforation film, except basilar membrane is become except CPIBI-60-10, other steps and the reagent type added and quality identical with the step (3) in embodiment 3.
Embodiment 6
Prepared by the CPIBI-60-30-Nafion of the filling perforation type Nafion resin molding being substrate with the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 3:5, pore-creating agent 30% massfraction.
(1) preparation process of polybenzimidazole polyimide PI BI is with the step (1) in embodiment 3;
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-60-10, except the quality of DBP is become except 0.09g, other steps and the kind of reagent added and quality identical with the step (2) in embodiment 3;
(3) preparation process of Nafion filling perforation film, except basilar membrane is become except CPIBI-60-30, other steps and the reagent type added and quality identical with the step (3) in embodiment 3.
Embodiment 7
Prepared by the CPIBI-60-70-Nafion of the filling perforation type Nafion resin molding being substrate with the cross-linking type porous polybenzimidazole imide of crosslinked group and benzoglyoxaline group mol ratio 3:5, pore-creating agent 70% massfraction.
(1) preparation process of polybenzimidazole polyimide PI BI is with the step (1) in embodiment 3;
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-60-10, except the quality of DBP is become except 0.21g, other steps and the kind of reagent added and quality identical with the step (2) in embodiment 3;
(3) preparation process of Nafion filling perforation film, except basilar membrane is become except CPIBI-60-70, other steps and the reagent type added and quality identical with the step (3) in embodiment 3.
Embodiment 8
The CPIBI-60-70-Nafion preparation of the filling perforation type Nafion resin molding being substrate with the porous polybenzimidazole imide of pore-creating agent 70% massfraction.(blank)
(1) preparation process of polybenzimidazole polyimide PI BI is with the step (1) in embodiment 3;
(2) preparation process of cross-linking type polybenzimidazole imide film substrate CPIBI-60-10, do not add except the quality of DBP is become 0.21g outside linking agent TMBP, other steps and the kind of reagent added and quality identical with the step (2) in embodiment 3;
(3) preparation process of Nafion filling perforation film, except basilar membrane is become except CPIBI-60-70, other steps and the reagent type added and quality identical with the step (3) in embodiment 3.
In above-described embodiment, the parameter of each component raw material and consumption and preparation process is only the representative chosen to describe invention.In fact a large amount of experiments shows, in summary of the invention part limited range, all can obtain above-described embodiment similar, the proton exchange membrane being substrate with bis ether cross-linking type porous polybenzimidazole imide film.
Claims (4)
1. the preparation method of the proton exchange membrane that is substrate with bis ether cross-linking type porous polybenzimidazole imide film, it is characterized in that described proton exchange membrane introduces benzimidazole structure on polyimide-based polymer main chain, and in film process, utilize the active N-H structure on imidazolyl and bis ether linking agent to react, make it be cross-linked, add water soluble pore formers simultaneously, after water infiltration, obtain vesicular structure, finally perfluorinated sulfonic acid base polymer solution-cast evaporating solvent on this porous-film is obtained Pore-Filling Type Proton Exchange Membrane; Concrete steps are as follows:
(1) in the there-necked flask of complete drying, add organic solvent and the diamines containing benzimidazole structure, connect gas inlet, drying tube, pneumatic outlet, reflux condensing tube and mechanical stirrer, pass into rare gas element and start to stir, after diamines dissolves completely, add diacid and the catalyzer of equivalent; Be warming up to 80 DEG C of reaction 4h, heat up afterwards and make solvent refluxing, reaction 20h; Be cooled to 100 DEG C after reaction terminates, product slowly poured in acetone and precipitates, precipitation acetone is carried out soxhlet extraction removing residual solvent, catalyzer and small molecular weight material, afterwards product is dried standby in vacuum drying oven under 60 DEG C of conditions;
(2) by the polymer dissolution of gained in (1) in organic solvent, the massfraction of solution is 2%-5%; After thing to be polymerized dissolves completely, add diether type linking agent, in the imidazole ring in its crosslinkable groups and macromolecular chain, the mol ratio of hydrogen bound to nitrogen is 0-0.8; Add pore-creating agent, its massfraction is the 0%-70% of polymkeric substance simultaneously; Stirring at room temperature makes linking agent and pore-creating agent dissolve completely and be uniformly dispersed; Film liquid is cast in the film frame of 10cm × 10cm 80 DEG C time, insulation 6h, being warming up to 150 DEG C again makes crosslinking reaction carry out completely, again obtained film deionized water is soaked 24h, 24h is soaked with methyl alcohol again after taking-up, finally film is dried under 60 DEG C of conditions, obtained crosslinked polybenzimidazole imide porous-film;
(3) be dissolved in organic solvent by perfluorinated sulfonic resin, liquid quality fraction is 2%-5%; First add part film liquid in the film frame of 10cm × 10cm, again the cross-linked porous film in (2) is joined above film liquid, again residue film liquid is joined above cross-linked porous film, complete wetting, dry under 80 DEG C of conditions, afterwards obtained film deionized water is soaked 24h, after taking-up, soak 24h with methyl alcohol again, finally film is dried under 60 DEG C of conditions, the proton exchange membrane that to obtain with bis ether cross-linking type porous polybenzimidazole imide film be substrate.
2. method according to claim 1, can state linking agent described in it is characterized in that is 3,3 ', 5,5 '-tetramethyl biphenyl diphenol diglycidylether, but be not limited thereto.
3. method according to claim 1, can state pore-creating agent described in it is characterized in that is dibutyl phthalate, but is not limited thereto.
4. method according to claim 1, is characterized in that described organic solvent is any one or two kinds of mixed solution in DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
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| CN117276611A (en) * | 2023-11-22 | 2023-12-22 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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| WO2018155598A1 (en) | 2017-02-23 | 2018-08-30 | 旭化成株式会社 | Composition, composite film and membrane electrode assembly |
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| CN109251446A (en) * | 2018-08-24 | 2019-01-22 | 海信（山东）空调有限公司 | A kind of high water absorption is low to be swollen anti-condensation thin-film material and its preparation method and application |
| CN110739476A (en) * | 2019-10-22 | 2020-01-31 | 山东东岳未来氢能材料有限公司 | PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof |
| CN110739476B (en) * | 2019-10-22 | 2020-09-22 | 山东东岳未来氢能材料有限公司 | PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and preparation method thereof |
| CN111073283A (en) * | 2019-11-28 | 2020-04-28 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
| CN111073282A (en) * | 2019-11-28 | 2020-04-28 | 李南文 | Solvent-resistant colorless transparent cross-linked polyimide film and preparation method thereof |
| CN111073283B (en) * | 2019-11-28 | 2022-05-31 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
| CN111073282B (en) * | 2019-11-28 | 2022-05-31 | 李南文 | Solvent-resistant colorless transparent cross-linked polyimide film and preparation method thereof |
| CN117276611A (en) * | 2023-11-22 | 2023-12-22 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
| CN117276611B (en) * | 2023-11-22 | 2024-02-23 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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