CN103560259A - POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as preparation method thereof - Google Patents
POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional high molecular materials and electrochemistry, and specifically relates to a POSS (Polyhedral Oligomeric Silsesquioxane) crosslinking type sulfonated polyimide proton exchange membrane as well as a preparation method thereof. The preparation method comprises the following steps: firstly, synthesizing a sulfonated polyimide polymer with a crosslinkable group imidazole group on a main chain, wherein the degree of sulfonation is controlled within 10-190%; and preparing a membrane forming liquid, adding a functional POSS crosslinking agent, carrying out reaction with the imidazole group, crosslinking the sulfonated polyimide polymer in a membrane forming process to form the crosslinking type sulfonated polyimide proton exchange membrane. The crosslinking membrane is endowed with good mechanical property and has higher hydrolytic stability and anti-oxidation stability. The method disclosed by the invention is good in controllability of the preparation process. Compared with conventional sulfonated polyimide membranes, the crosslinking type sulfonated polyimide proton exchange membrane is high in mechanical strength, strong in hydrolytic resistance and oxidation resistance, and good in dimensional stability, and has a broad application prospect in polymer electrolyte membrane fuel cells.
Description
Technical field
The invention belongs to functional high molecule material and technical field of electrochemistry, be specifically related to a kind of POSS crosslinked sulfonated polyimide proton exchange membrane and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFCs) is the current the most ripe a kind of technology that hydrogen and airborne oxygen can be combined to clean water and discharge electric energy in the world, has energy efficiency high, discharge low, eco-friendly advantage.Proton exchange membrane is the core component of PEMFC, has determined the performance and used life of whole battery.What in PEMFC, apply at present is mainly that perfluoro sulfonic acid membrane is (as Nafion
?), but expensive, the drawbacks limit such as mechanical strength is not high, poor dimensional stability and permeability height its extensive use.
Sulfonated polyimide proton membrane has several relatively outstanding features: (1) is to exterior temperature change insensitive (its vitrification point is high); (2) the hydrone number of each ion cluster does not rely on EW; (3) in proton conductivity and film a little less than water content correlation; (4) internal structure of the contained Ion Phase of monomer is not water droplet but the ion part of polymer chain; (5) micro-structural of film may be stratiform, rather than picture Nafion
?ellipsoid shape.Therefore, sulfonated polyimide is considered to get a good chance of obtaining a class membrane material of application.Yet, with Nafion
?compare, the Green Tea Extract oxidation stability of sulfonation hydrocarbon polymer film is all poor, thereby affects the useful life of fuel cell.
Sulfonated polyphenyl imidazoles have fabulous Green Tea Extract oxidation susceptibility, but due to interaction strong between basic imidazole base and acid sulfonic group, proton conduction is hindered, and make the proton conductivity of sulfonated polyphenyl imidazoles film very low.If adopt suitable method, benzimidazole structure is incorporated in polyimides, just both can learn from other's strong points to offset one's weaknesses.The present invention is in conjunction with feature and the performance of polyimides and polybenzimidazoles, in sulfonated polyimide main chain, introduce benzimidazolyl, and in film forming procedure, utilize the active N-H structure on imidazole radicals, add polyhedral oligomeric silsesquioxane (POSS) crosslinking agent of functionalization to make it form the proton exchange membrane material of cross-linking type, be expected when improving the Green Tea Extract oxidation susceptibility of film, increase substantially the hydrolytic stability energy of film, extend the useful life of film.
Summary of the invention
The object of this invention is to provide a kind of POSS crosslinked sulfonated polyimide proton exchange membrane and preparation method thereof.
The POSS crosslinked sulfonated polyimide proton exchange membrane that the present invention proposes, to introduce benzimidazolyl on sulfonated polyimide base polymer main chain, and in film forming procedure, utilize active N-H structure and polyhedral oligomeric silsesquioxane (POSS) crosslinking agent on imidazole radicals to react, make its crosslinked obtaining, its raw material forms and comprises:
1 part of sulfonated polyimide (molal quantity)
POSS crosslinking agent 0.025-0.5 part (accounting for the mass ratio of sulfonated polyimide)
Organic solvent 160-500 part (molal quantity);
Wherein, described sulfonated polyimide is that main chain contains benzimidazolyl.
In the present invention, the reinforced recently control of described sulfonated polyimide sulfonation degree (molal quantity of sulfonated diamine monomer is multiplied by two molal quantitys divided by dianhydride monomer) in building-up process.Wherein sulfonation degree is any one value in 10%-190%.
In the present invention, described POSS crosslinking agent for containing polyhedral oligomeric silsesquioxane (POSS) structure can with sulfonated polyimide in the compound that reacts of benzimidazolyl, the polyhedral oligomeric silsesquioxane replacing as the octa-epoxy of Hybrid Plastics company, the polyhedral oligomeric silsesquioxane that three epoxy radicals replace etc., but be not limited only to this.
In the present invention, described organic solvent is the mixed liquor of any one or two kinds in DMF, DMA, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE, metacresol.
The preparation method of the POSS crosslinked sulfonated polyimide proton exchange membrane that the present invention proposes, concrete steps are as follows:
(1) sulfonated polyimide is immersed in saturated NaCl solution, after 24h, takes out and dry.At 100 ℃, be dissolved in organic solvent wiring solution-forming.Wherein in every 50mL organic solvent, the addition of sulfonated polyimide is 0.5-2.5g;
(2) by polyhedral oligomeric silsesquioxane (POSS), normal-temperature dissolution is in organic solvent.Wherein in every 1mL organic solvent, the addition of POSS is 0.05-0.1g;
(3) under room temperature, the solution of step (1) and step (2) gained is mixed, after stirring, filter bubble removing.Wherein: the mass ratio of sulfonated polyimide and POSS crosslinking agent is 2:1～40:1;
(4) film liquid is cast on the glass plate of 10 cm * 10 cm, dry 4-6 h in 60-90 ℃ of vacuum drying oven, solvent volatilizees completely.Be warming up to 150-180 ℃ and continue heating 6-10h.Obtain sodium-salt type POSS crosslinked sulfonated polyimide proton exchange membrane;
5) proton exchange membrane of step (4) gained is soaked to 6-12 h in the methyl alcohol of 50-60 ℃, remove organic solvent residual in proton exchange membrane.Deionized water is immersed in proton exchange membrane in 1.0 mol/L hydrochloric acid and takes out after 48 h under normal temperature after cleaning, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain required product.
Feature of the present invention is to introduce imidazole group on sulfonated polyimide main polymer chain, then use POSS as crosslinking agent, itself and polyimides are cross-linked, can significantly improve thermal stability, antioxidative stabilizer, hydrolytic stability and the mechanical property of sulfonated polyimide proton exchange membrane and still there is higher proton conductivity.
Accompanying drawing explanation
?fig. 1 is that the mechanical property of the POSS crosslinked sulfonated polyimide proton exchange membrane that replaces of octa-epoxy is with the variation of sulfonated polyimide sulfonation degree, wherein the sulfonation degree of sulfonated polyimide is 80%, the mol ratio of 100%, 120%, POSS and sulfonated polyimide is 0.14:1.
Embodiment
Following examples are only for further illustrating the present invention, are not violating under purport of the present invention, and the present invention should be not limited to the content that following experimental example is specifically expressed.
Raw materials used as follows:
Sulfonated polyimide (containing benzimidazolyl and sulfonic acid group, SPIBI-X), according to methods Laboratory self-control described in document (Pan Haiyan etc., SCI. 2007,28 (1): 173), wherein X is sulfonation degree;
Octa-epoxy replaces, three epoxy radicals replace polyhedral oligomeric silsesquioxane (POSS), 99.5%, Hybrid Plastics company;
Methyl-sulfoxide (DMSO) ，99%， Chemical Reagent Co., Ltd., Sinopharm Group;
DMA (DMAc), chemical pure (>98%), Chemical Reagent Co., Ltd., Sinopharm Group;
DMF (DMF), chemical pure (>98%), Chemical Reagent Co., Ltd., Sinopharm Group;
1-METHYLPYRROLIDONE (NMP), chemical pure (>98%), Chemical Reagent Co., Ltd., Sinopharm Group;
Metacresol (
m-cresol), chemical pure (>98%), Chemical Reagent Co., Ltd., Sinopharm Group;
Embodiment 1
Raw materials used proportioning is as follows:
1 part of SPIBI-100 (repetitive molal quantity)
0.025 part of octa-epoxy polyhedral oligomeric silsesquioxane (POSS) (accounting for the mass number of SPIBI-100)
160 parts of methyl-sulfoxides (molal quantity)
(1) 0.6g SPIBI-100 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 13 mL methyl-sulfoxides (DMSO), form homogeneous solution.
(2) POSS normal-temperature dissolution 0.015g octa-epoxy being replaced, in 1mLDMSO solution, is stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 10h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 6 h, except residual DMSO solvent in striping.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain required POSS crosslinking proton exchange membrane.
The Mechanics Performance Testing of cross linking membrane:
Crosslinking proton exchange membrane is made to dumbbell shape film sample according to ASTM D882-02 standard, and in the upper hot strength of measuring cross linking membrane of DXLL-5000 type double lead electronic tensile machine (Shanghai De Jie instrument and equipment Co., Ltd), rate of extension is 50mm/min.The mechanical property of cross linking membrane as shown in Figure 1.
Embodiment 2
Raw materials used proportioning is as follows:
1 part of SPIBI-10 (repetitive molal quantity)
0.15 part of octa-epoxy polyhedral oligomeric silsesquioxane (POSS) (accounting for the mass number of SPIBI-10)
400 parts of methyl-sulfoxides (molal quantity)
(1) 0.6g SPIBI-100 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 30 mL methyl-sulfoxides (DMSO), form homogeneous solution.
(2) POSS normal-temperature dissolution 0.015g octa-epoxy being replaced, in 4mL DMSO solution, is stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 12h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 8 h, except residual DMSO solvent in striping.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain the crosslinked proton exchange membrane of required POSS.
Embodiment 3
Raw materials used proportioning is as follows:
1 part of SPIBI-190 (repetitive molal quantity)
0.50 part of octa-epoxy polyhedral oligomeric silsesquioxane (POSS) (with the mass ratio of SPIBI-190)
500 parts of 1-METHYLPYRROLIDONEs (NMP) (molal quantity)
(1) 0.6g SPIBI-190 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 30 mL 1-METHYLPYRROLIDONEs (NMP), form homogeneous solution.
(2) POSS normal-temperature dissolution 0.3g octa-epoxy being replaced, in 10mL nmp solution, is stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 8h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 10 h, except residual nmp solvent in striping.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain the crosslinked proton exchange membrane of required POSS.
Embodiment 4
Raw materials used proportioning is as follows:
1 part of SPIBI-20 (repetitive molal quantity)
Three 0.25 part of epoxy radicals polyhedral oligomeric silsesquioxane (POSS) (with the mass ratio of SPIBI-20)
360 parts of DMFs (DMF) (molal quantity)
(1) 0.6g SPIBI-20 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 25 mL DMFs (DMF), form homogeneous solution.
(2) 0.15g tri-epoxy radicals are replaced to POSS normal-temperature dissolution in 5mL DMF solution, be stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 8h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 6 h, except residual DMF solvent in striping.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain the crosslinked proton exchange membrane of required POSS.
Embodiment 5
Raw materials used proportioning is as follows:
1 part of SPIBI-120 (repetitive molal quantity)
Three epoxy radicals replace polyhedral oligomeric silsesquioxane (POSS) 0.5 part (with the mass ratio of SPIBI-120)
500 parts of methyl-sulfoxides (molal quantity)
(1) 0.6g SPIBI-120 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 30 mL methyl-sulfoxides (DMSO), form homogeneous solution.
(2) 0.3g tri-epoxy radicals are replaced to POSS normal-temperature dissolution in 10mL DMSO solution, be stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 8h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 8 h, except residual DMSO solvent in striping.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain the crosslinked proton exchange membrane of required POSS.
Embodiment 6
Raw materials used proportioning is as follows:
1 part of SPIBI-180 (repetitive molal quantity)
Three epoxy radicals replace polyhedral oligomeric silsesquioxane (POSS) 0.025 part (with the mass ratio of SPIBI-180)
400 parts of methyl-sulfoxides (molal quantity)
(1) 0.6g SPIBI-180 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 13 mL methyl-sulfoxides (DMSO), form homogeneous solution.
(2) 0.015g tri-epoxy radicals are replaced to POSS normal-temperature dissolution in 1mL DMSO solution, be stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 8h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 8 h, except residual DMSO solvent in striping.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain the crosslinked proton exchange membrane of required POSS.
Embodiment 7
Raw materials used proportioning is as follows:
1 part of SPIBI-80 (repetitive molal quantity)
0.30 part of octa-epoxy polyhedral oligomeric silsesquioxane (POSS) (with the mass ratio of SPIBI-80)
500 parts of DMAs (DMAc) (molal quantity)
(1) 0.6g SPIBI-80 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 30 mL DMAs (DMAc), form homogeneous solution.
(2) POSS normal-temperature dissolution 0.18g octa-epoxy being replaced, in 10mL DMAc solution, is stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 8h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 6 h, except residual DMAc solvent in striping.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain the crosslinked proton exchange membrane of required POSS.
Embodiment 8
Raw materials used proportioning is as follows:
1 part of SPIBI-60 (repetitive molal quantity)
Three 0.40 part of epoxy radicals polyhedral oligomeric silsesquioxane (POSS) (with the mass ratio of SPIBI-60)
Metacresol (
m-cresol) 360 parts (molal quantity)
(1) 0.6g SPIBI-60 is immersed in saturated NaCl solution, after 24 hours, takes out and dry.Then at 100 ℃, be dissolved in 25 mL metacresols (
m-cresol), in, form homogeneous solution.
(2) 0.24g tri-epoxy radicals are replaced to POSS normal-temperature dissolution in 5mL
min-cresol solution, be stirred to homogeneous solution.Under room temperature, mix with (1) formed solution, filter bubble removing.
(3) mixed liquor of step (2) gained is cast on the glass plate of 10 cm * 10 cm, dry 6 h in 80 ℃ of vacuum drying ovens, solvent volatilizees completely.Be warming up to 150 ℃ and continue heating 8h, cross-linking reaction is carried out completely.
(4) film of step (3) gained is put into 60 ℃ of methyl alcohol and soak 12 h, except residual in striping
m-cresol solvent.Then, normal temperature is immersed in film in 1.0 mol/L hydrochloric acid, carries out 48 h proton exchange.Film is taken out, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain the crosslinked proton exchange membrane of required POSS.
In above-described embodiment, the parameter of each component raw material and consumption and preparation process, is only the representative of choosing in order to describe invention.In fact a large amount of experiments show, in summary of the invention part limited range, all can obtain the similar POSS crosslinked sulfonated polyimide proton exchange membrane of above-described embodiment.
Claims (5)
1. a POSS crosslinked sulfonated polyimide proton exchange membrane, it is characterized in that this cross linking membrane is to introduce benzimidazolyl on polyimide main polymer chain, and in film forming procedure, utilize active N-H structure and polyhedral oligomeric silsesquioxane POSS crosslinking agent on imidazole radicals to react and crosslinked obtaining, its raw material forms and comprises:
1 part of sulfonated polyimide (molal quantity)
Polyhedral oligomeric silsesquioxane crosslinking agent 0.025-0.5 part (accounting for the mass ratio of sulfonated polyimide)
Organic solvent 160-500 part (molal quantity);
Wherein, described sulfonated polyimide is that main chain contains benzimidazole based structures.
2. POSS crosslinked sulfonated polyimide proton exchange membrane according to claim 1, the sulfonation degree that it is characterized in that described sulfonated polyimide any one value from 10%-190%.
3. POSS crosslinked sulfonated polyimide proton exchange membrane according to claim 1, it is characterized in that POSS crosslinking agent be the polyhedral oligomeric silsesquioxane that replaces of octa-epoxy, in the polyhedral oligomeric silsesquioxane that three epoxy radicals replace any, but be not limited only to this.
4. POSS crosslinked sulfonated polyimide proton exchange membrane according to claim 1, it is characterized in that described organic solvent is N, the mixed liquor of any one or two kinds in dinethylformamide, DMA, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE.
5. a preparation method for POSS crosslinked sulfonated polyimide proton exchange membrane as claimed in claim 1, is characterized in that concrete steps are as follows:
(1) sulfonated polyimide is immersed in saturated NaCl solution, after 24h, takes out and dry; At 100 ℃, be dissolved in organic solvent wiring solution-forming; Wherein in every 50mL organic solvent, the addition of sulfonated polyimide is 0.5-2.5g;
(2) by polyhedral oligomeric silsesquioxane crosslinking agent, normal-temperature dissolution is in organic solvent; Wherein in every 1mL organic solvent, the addition of polyhedral oligomeric silsesquioxane is 0.05-0.1g;
(3) under room temperature, the solution of step (1) and step (2) gained is mixed, after stirring, filter bubble removing; Wherein: the mass ratio of sulfonated polyimide and polyhedral oligomeric silsesquioxane crosslinking agent is 2:1～40:1;
(4) film liquid step (3) being obtained is cast on the glass plate of 10 cm * 10 cm, dry 4-6 h in 60-90 ℃ of vacuum drying oven, and solvent volatilizees completely; Be warming up to 150-180 ℃ and continue heating 6-10h; Obtain sodium-salt type POSS crosslinked sulfonated polyimide proton exchange membrane;
(5) the quality proton exchange of step (4) gained is soaked to 6-12 h in the methyl alcohol of 50-60 ℃, remove organic solvent residual in proton exchange membrane; Deionized water is immersed in film in 1.0 mol/L hydrochloric acid and takes out after 48 h under normal temperature after cleaning, and with deionized water cyclic washing, to neutral, in 150 ℃ of vacuum drying ovens, dry 24 h, obtain required product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110041552A (en) * | 2019-04-23 | 2019-07-23 | 吉林大学 | Compound high temperature proton exchange film and preparation method thereof based on sulfonation aryl oxide type polybenzimidazoles Yu sulfonation polysilsesquioxane |
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