CN101205308B - Sulfonated polysulfonamide proton exchange membrane and preparation thereof - Google Patents
Sulfonated polysulfonamide proton exchange membrane and preparation thereof Download PDFInfo
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- CN101205308B CN101205308B CN200610105320A CN200610105320A CN101205308B CN 101205308 B CN101205308 B CN 101205308B CN 200610105320 A CN200610105320 A CN 200610105320A CN 200610105320 A CN200610105320 A CN 200610105320A CN 101205308 B CN101205308 B CN 101205308B
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Abstract
The invention discloses a sulfonated polysulfoneamide proton exchange membrane and a preparation method thereof. By selecting the new materials of the polysulfoneamide as raw materials, the inventionprepares the sulfonated membrane materials. The amide and the sulfonyl group in the PSA molecule are connected with each other on the para phenyl and form a linear macromolecule with the para phenyl;as the strong electro-withdrawing phenyl group exists on the macromolecular chain, the molecular structure is driven to have more excellent heat resistance, thermal stability and thermal oxidation resistance than the traditional acromatic polyamide through the double-bond conjugation of the benzene ring. The mixed acids comprising the concentrated sulfuric acids and oleums are selected as the sulfonating agents, thus lowering material viscosity and helping heat transfer and being beneficial to uniform and complete implementation of the sulfonation and reducing occurrence of the side reaction.The high activity of the oleums is helpful for enhancing the sulfonation degree of the sulfonated bodies. The introduction of the sulfonic group (-SO3H) in the main-chain structure of the polymer canremarkably enhance the proton conductivity and water content of the polymers. The invention has the advantages that the invention provides a proton exchange membrane which endures high temperature, has stable chemical performance, high proton conductivity, excellenet antioxidation property and thermal stability, etc., and has low cost and is suitale for fuel cells, and also can be used as variousultrafiltration membranes, nanofiltration membranes or reverse osmosis membranes and has wide application prospect.
Description
Technical field
The invention belongs to the polymer material science field, be specifically related to a kind of sulfonated polyphenyl sulfone terephthalamide proton exchange membrane and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells has advantages such as working temperature is low, startup is fast, specific power is high, simple in structure, easy to operate, noiselessness, zero pollution, be acknowledged as civil and military compact powers such as mobile phone, palm PC, notebook computer, Digital Video, CD player, small-sized communication power supply, various emergency source of electric power, robot power supply, and the first-selected energy of electric vehicle, stationary power generation station etc.Proton Exchange Membrane Fuel Cells partly is made up of anode, negative electrode, catalyzer and proton exchange membrane etc.Proton exchange membrane is Proton Exchange Membrane Fuel Cells " heart ", its effect in fuel cell is dual: the one, provide passage as ionogen for the migration and the conveying of proton, make proton arrive negative electrode from anode through film, constitute the loop with the transfer transport of external circuit, provide electric current to the external world; The 2nd, isolate polarization response gas as barrier film, prevent that them from directly having an effect.The quality of its performance directly affects the serviceability and the work-ing life of fuel cell, and therefore the research for proton exchange membrane material has become one of focus in the fuel cell studies work.
The Flemion film of the Aciplex film of the Dow film of the Nafion film of present mould material such as U.S. Du Pont company, U.S. Dow chemical company, Japanese Asahi company and Japanese Asahi Glass company is perfluoro sulfonic acid membrane, has the high and good advantage of chemical stability of proton conductivity, if but adopt above-mentioned film, the film expense accounts for 20%～30% of total cost, and therefore the exploitation mould material more cheap than existing perfluoro sulfonic acid membrane is the problem that people pay close attention to always.According to investigation, the organic prepared perfluoro sulfonic acid membrane in Chinese Academy of Sciences Shanghai, but stability is bad, and the life-span is short, and performance is also not ideal.The Dalian Chemistry and Physics Institute adopts home-made PTFE porous-film, injects the Nafion film resin liquid of Du Pont company, has prepared composite membrane, and the cost of ion-exchange membrane is reduced, but performance, work-ing life are not as the Nafion film of Du Pont company.Therefore the used PEM of domestic assembling PEMFC mainly relies on import.Proton Exchange Membrane Fuel Cells (PEMFC) adopts the Nafion film mostly at present, and still there is following shortcoming in this film: (1) makes difficulty, cost is high, and the market value of Nafion film is 1000 dollars/m at present
2, the synthetic and sulfonation of perfluor material is unusual difficulty all, and the hydrolysis in film process, sulfonation make polymkeric substance sex change, degraded easily, makes the film forming difficulty; (2) require high to temperature and water content, the optimal working temp of Nafion series membranes is 70～90 ℃, surpass this temperature its water content is sharply reduced, electroconductibility descends rapidly, has hindered by suitable raising working temperature and has improved an electrode reaction speed and a difficult problem that overcomes poisoning of catalyst; (3) some hydrocarbon polymer, as methyl alcohol etc., rate of permeation is higher, the methyl alcohol that sees through oxidation on negative electrode, not only make negative electrode produce mixed potential, make negative electrode Pt poisoning of catalyst simultaneously, cause battery performance to reduce, therefore be not suitable for use in the proton exchange membrane of direct methanol fuel cell (DMFC). at the problem of perfluorinated sulfonic acid type film existence, research at present mainly concentrates on two aspects: the one, existing perfluoro sulfonic acid membrane is improved, another is the mould material of development of new. on existing perfluorinated sulfonic acid type film basis, improves, comprise and reducing cost, improve use temperature, strengthen researchs such as alcohol-rejecting ability, yet the improvement of existing perfluoro sulfonic acid membrane is not fundamentally solved the problem of its existence, still rely on the content of perfluorinated resin such as the proton conductivity of film, working temperature also is difficult to improve a lot. and fluorine material is to the unfavorable people's attention that also more and more is subjected to of environment in addition. therefore, cast aside fluorine resin, the exploitation high-performance, novel cheaply proton exchange membrane material is the general orientation and the trend of future studies, many countries have all carried out the research of this respect. and the research of novel proton exchange membranes material at present mainly concentrates on the trial aspect of high-performance polymer being carried out chemical modification and blending and modifying. and the synthetic and preparation route of novel proton exchange membranes material roughly has sulfonation method, the direct polymerization method, the grafting method, doping method etc., wherein by sulfonation method sulfonic group being incorporated into the high-performance polymer main chain is the method for giving a kind of important and widespread use of polymer proton exchange capacity. and the developing direction of present novel proton exchange membranes has been changed into the sulfonation of polyfluoro or aromatic series fluorine free polymer by the sulfonation of (per) fluoropolymer, the various composite membranes of representational as poly-aromatic ring series: polybenzimidazole (PBI), polyether-ether-ketone, polyaryletherketone, polyethersulfone, polysulfones, polyarylsulphone, polyphenylene sulfide, polyphenylene oxide, the sulfonated membranes of polyimide etc. though the countries in the world investigator adopts different methods improving film properties at present, as the high temperature proton conductivity, some aspect such as methanol permeability has obtained certain progress, but its over-all properties is still not as traditional perfluoro sulfonic acid membrane, and preparation technology is still immature, from commercialization one segment distance is arranged still. therefore, development from proton exchange membrane, development of new, mould material is the problem that must at first solve in the proton exchange membrane development cheaply. in addition in the exploitation and research process of proton exchange membrane, should be when considering performance, take into account environmental factors, only in this way could guarantee promoting the use of of proton exchange membrane really, really realize the commercialization and the practicability of fuel cell.
Polyphenylene Sulfone terephthalamide (PSA) is a kind of novel high polymer material, belongs to aromatic polyamide class high temperature material, and commodity are called fragrant sulfone synthetic fibre, belong to p-aramid fiber series.Have good thermotolerance, thermostability, high temperature dimensional stability, flame retardant resistance, electrical insulating property and radioresistance, have good physical and mechanical properties and chemical stability simultaneously.Its decomposition temperature is about 420 ℃, and initial decomposition temperature Ti is 373.1 ℃; Rate of weight loss is 2.85% in the time of 400 ℃.The strength retention that it is handled in the warm air of 250 ℃ and 300 ℃ behind the 100h is respectively 90% and 80%.Its boiling water shrinkage only is 0.5%～1%, and the shrinking percentage in 300 ℃ of warm airs also only is 2%.Has stronger resistance to acid and stable preferably.Aspect anti-organic solvent, except several intensive polar solvents, all can keep satisfactory stability to various chemicals.These performances Proton Exchange Membrane Fuel Cells just require that proton exchange membrane possessed.Therefore, sulfonated polyphenyl sulfone terephthalamide (SPSA) is counted as a kind of proton exchange membrane material with applications well prospect.Still unmatchful its carries out the report of sulfonation modifying both at home and abroad at present.
Summary of the invention
The object of the present invention is to provide a kind of high temperature resistant, stable chemical performance, sulfonated polyphenyl sulfone terephthalamide (SPSA) proton exchange membrane that proton conductivity is high and preparation method thereof.
The present invention by sulfonation reaction with sulfonic group (SO
3H) be incorporated in the Polyphenylene Sulfone terephthalamide molecular backbone chain, under the prerequisite that continues premium propertiess such as maintenance its heat-resisting solvent resistance, electrical insulating property and high mechanical strength, improve the proton exchange ability of polymkeric substance, for fuel cell provides a kind of excellent combination property, the novel proton exchange membranes that raw material is cheap and easy to get.
A kind of sulfonated polyphenyl sulfone terephthalamide proton exchange membrane (SPSA), its repeated structural unit is suc as formula shown in (I):
N=50 in the formula～200, molecular weight are 10000～80000, and sulfonation degree is 0.1～2.0.
Sulfonation degree is the molar fraction of the contained sulfonic acid group of each repeated structural unit in the SPSA mould material molecular chain.
The sulfonated polyphenyl sulfone terephthalamide proton exchange membrane preparation method of a kind of formula (I),
N=50 in the formula～200, molecular weight are 10000～80000, and sulfonation degree is 0.1～2.0, it is characterized in that this method comprises following two steps successively:
The sulfonation of A, Polyphenylene Sulfone terephthalamide (PSA)
In reactor, add the Polyphenylene Sulfone terephthalamide, add the mixing acid of the vitriol oil and oleum then, feed nitrogen, after vigorous stirring reaches homogeneous phase solution, under 25～160 ℃ of conditions, reacted 1～45 hour; Reaction solution is poured in the mixture of ice and water, formed flocks, stir standing sedimentation, filter, use deionized water washing sediment, when the pH of filtrate is 6-8, take out throw out, drying makes sulfonation degree and is 0.1～2.0 sulfonated polyphenyl sulfone terephthalamide (SPSA);
The preparation of B, sulfonated polyphenyl sulfone terephthalamide (SPSA) proton exchange membrane
Sulfonated polyphenyl sulfone terephthalamide (SPSA) is dissolved in N, dinethylformamide (DMF), N, in the solvent of N-N,N-DIMETHYLACETAMIDE (DMAC), dimethyl sulfoxide (DMSO) (DMSO) or N-methyl arsenic pyrrolidone, form film-casting liquid, be tiled in sheet glass or the tetrafluoroethylene mould, predrying 24～48 hours 40～80 ℃ of normal pressures again, continue dry 24～60h down to remove residual solvent in 120～140 ℃ in vacuum, behind the cool to room temperature, immerse in the deionized water, take film off; Then at room temperature with film, soaking the back with dilute sulphuric acid takes out, repeatedly wash to remove residual sulfuric acid in the striping with deionized water again, be fully immersed in the deionized water to remove free acid, dry, be cooled to room temperature and take out, obtain sulfonated polyphenyl sulfone terephthalamide (SPSA) proton exchange membrane of homogeneous.
In the A step, 10～50 milliliters in the mixing acid of the 1 gram Polyphenylene Sulfone terephthalamide adding vitriol oil and oleum.
In the B step, the sulfonated polyphenyl sulfone terephthalamide of 3～20wt% is contained in the film-casting liquid the inside.
The thickness of the sulfonated polyphenyl sulfone terephthalamide proton exchange membrane of the present invention's preparation is 10～300 μ m.
It is feedstock production sulfonated membranes material that the present invention has selected Polyphenylene Sulfone terephthalamide novel material for use.Amide group in the PSA molecule and sulfuryl be interconnected on the contraposition phenyl and and contraposition phenyl formation linear macromolecule, owing to have strong electrophilic sulfuryl group on the macromolecular chain, by two key conjugations of phenyl ring, make this molecular structure have more excellent thermotolerance, thermostability and thermal oxidation resistance performance than conventional fragrant polyamide.And with sulfonic group (SO
3H) thermotolerance of introducing Polyphenylene Sulfone terephthalamide molecular backbone chain post polymerization thing improves, and sees Fig. 1.
The present invention has selected for use the mixing acid of the vitriol oil and oleum as sulphonating agent, wherein the vitriol oil is both as sulphonating agent, be homogeneous phase solution as solvent with dissolution of solid polymer again, can reduce material viscosity like this and help and conduct heat, help sulfonation reaction uniform and complete of carrying out and the generation that reduces side reaction.Oleum is active high, helps to improve the sulfonation degree of sulfonated bodies.Mixing acid with the oleum and the vitriol oil is easy to the control reaction.Feed nitrogen in the reaction and not only can prevent oxidation, reduce side reaction, and can take the water that reaction generates out of, help reaction and carry out thoroughly.With sulfonic group (SO
3H) be incorporated into the main polymer chain structure, can significantly improve its proton conduction performance and water content. because sulfonation reaction is the electrophilic substitution reaction that influenced by the functional group of the wetting ability of sulphonating agent and polymkeric substance, rule according to fragrant cationoid reaction is learnt: in the amido linkage, its carbonyl belongs to electron-withdrawing group, make the phenyl ring passivation, and amido belongs to electron-donating group, helping sulfonation reaction carries out, sulfuryl also belongs to strong electron-withdrawing group group, making the phenyl ring passivation. adjacency pair position effect has determined sulfonic access position in addition, and amido is an ortho-para directing group, and sulfuryl and carbonyl are meta-orienting group, so substitution reaction occurs in phenyl ring and-ortho position that NH-links to each other, promptly is positioned at-SO
2-between the position.And because sulfonic steric effect, each stupid ring only inserts a sulfonic group, sees Fig. 2.
The present invention is by regulating and control the ratio of Polyphenylene Sulfone terephthalamide and sulphonating agent, can prepare a series of SPSA with different sulfonation degree, ratio increase along with oleum, the raising of reaction times prolongation or temperature of reaction, the sulfonation degree of gained sulfonated polyphenyl sulfone terephthalamide (SPSA) raises.
Effect benefit of the present invention provides a kind of high temperature resistant, stable chemical performance, proton conductivity height, excellent property such as oxidation-resistance, thermostability, and cost is lower, be applicable to the proton exchange membrane of fuel cell, can also be used as various ultra-filtration membranes, nanofiltration membrane or reverse osmosis membrane, have broad application prospects.
Description of drawings
Fig. 1 is the TGA figure of the prepared SPSA of PSA and embodiment 2.
Fig. 2 is the prepared SPSA's of PSA and embodiment 2
1The H nmr spectrum
Embodiment
The equation of sulfonation reaction is as follows:
Embodiment 1:
With Polyphenylene Sulfone terephthalamide raw material at 100 ℃, dry 1h under the vacuum, it is standby to put into moisture eliminator then.Take by weighing the Polyphenylene Sulfone terephthalamide of 10g, pack into be furnished with thermometer, in the 250mL three-necked bottle of agitator, the mixing acid of the vitriol oil of adding 120mL and the oleum of 20mL, logical high pure nitrogen, after 25 ℃ of following vigorous stirring of room temperature reach homogeneous phase solution, be warming up to 30 ℃, behind the reaction 24h, reaction solution is slowly poured into thread in the mixture of ice and water of 800mL, formed flocks, after stirring 1h, standing sedimentation filters, with repeatedly washing precipitation of deionized water,, took out and be deposited in the following 60 ℃ of dry 48h of vacuum near 7 o'clock up to the pH of filtrate.The sulfonation degree of product is 0.26.
Embodiment 2
Raw material Processing Example 1.Take by weighing the Polyphenylene Sulfone terephthalamide of 10g, pack into be furnished with thermometer, in the 250mL three-necked bottle of agitator, the mixing acid of the vitriol oil of adding 100mL and the oleum of 40mL, logical high pure nitrogen, after 25 ℃ of following vigorous stirring of room temperature reach homogeneous phase solution, be warming up to 80 ℃, behind the reaction 8h, reaction solution is slowly poured into thread in the mixture of ice and water of 800mL, formed flocks, after stirring 1h, standing sedimentation filters, with repeatedly washing precipitation of deionized water,, took out and be deposited in the following 60 ℃ of dry 48h of vacuum near 7 o'clock up to the pH of filtrate.The sulfonation degree of product is 1.03.
Raw material Processing Example 1.Take by weighing the Polyphenylene Sulfone terephthalamide of 10g, pack into be furnished with thermometer, in the 250mL three-necked bottle of agitator, the mixing acid of the vitriol oil of adding 100mL and the oleum of 50mL, logical high pure nitrogen, after 25 ℃ of following vigorous stirring of room temperature reach homogeneous phase solution, be warming up to 100 ℃, behind the reaction 12h, reaction solution is slowly poured into thread in the mixture of ice and water of 800mL, formed flocks, after stirring 1h, standing sedimentation filters, with repeatedly washing precipitation of deionized water,, took out and be deposited in the following 60 ℃ of dry 48h of vacuum near 7 o'clock up to the pH of filtrate.The sulfonation degree of product is 1.91.
With sulfonation degree is that to be made into massfraction be 7% DMAC solution for 1.03 SPSA, after stirring, be tiled on the sheet glass, at 60 ℃ of predrying 24h of normal pressure, continue dry 48h down for 120 ℃ in vacuum again, behind the cool to room temperature, immerse in the deionized water, take off with sharp blade, the build that makes is 15 μ m.Then at room temperature, 1mol/L H with film
2SO
4Take out after soaking 24h in the aqueous solution, repeatedly wash with deionized water again and remove residual H
2SO
4After, be fully immersed in the deionized water at least that 24h soaks after 3 days to remove free acid, at 0.08MPa, under 80 ℃, vacuum-drying 2h takes out behind the cool to room temperature.Obtain described SPSA proton exchange membrane, its proton conductivity is 0.043S/cm.
Claims (4)
1. sulfonated polyphenyl sulfone terephthalamide proton exchange membrane, its repeated structural unit is suc as formula shown in (I):
N=50 in the formula～200, molecular weight are 10000～80000, and sulfonation degree is 0.1～2.0.
2. the sulfonated polyphenyl sulfone terephthalamide proton exchange membrane preparation method of a formula (I),
N=50 in the formula～200, molecular weight are 10000～80000, and sulfonation degree is 0.1～2.0, it is characterized in that this method comprises following two steps successively:
The sulfonation of A, Polyphenylene Sulfone terephthalamide
In reactor, add the Polyphenylene Sulfone terephthalamide, add the mixing acid of the vitriol oil and oleum then, feed nitrogen, after vigorous stirring reaches homogeneous phase solution, under 25～160 ℃ of conditions, reacted 1～45 hour; Reaction solution is poured in the mixture of ice and water, formed flocks, stir standing sedimentation, filter, use deionized water washing sediment, when the pH of filtrate is 6-8, take out throw out, drying makes sulfonation degree and is 0.1～2.0 sulfonated polyphenyl sulfone terephthalamide;
The preparation of B, sulfonated polyphenyl sulfone terephthalamide proton exchange membrane
Sulfonated polyphenyl sulfone terephthalamide is dissolved in N, dinethylformamide, N, in the solvent of N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) or N-methyl arsenic pyrrolidone, form film-casting liquid, be tiled in sheet glass or the tetrafluoroethylene mould, predrying 24～48 hours 40～80 ℃ of normal pressures again, continue dry 24～60h down to remove residual solvent in 120～140 ℃ in vacuum, behind the cool to room temperature, immerse in the deionized water, take film off; Then at room temperature, soak the back with dilute sulphuric acid and take out, repeatedly wash to remove residual sulfuric acid in the striping with deionized water again film, be fully immersed in the deionized water to remove free acid, drying is cooled to room temperature and takes out, and obtains the sulfonated polyphenyl sulfone terephthalamide proton exchange membrane of homogeneous.
3. method as claimed in claim 2 is characterized in that: in the A step, and 10～50 milliliters in the mixing acid of the 1 gram Polyphenylene Sulfone terephthalamide adding vitriol oil and oleum.
4. method as claimed in claim 2 is characterized in that: in the B step, the sulfonated polyphenyl sulfone terephthalamide of 3～20wt% is contained in the film-casting liquid the inside.
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| CN102405094A (en) * | 2009-02-19 | 2012-04-04 | 内盖夫研究与发展部本-古里安大学 | Chemically resistant membranes, coatings and films and methods for their preparation |
| CN108117640B (en) * | 2017-12-05 | 2020-06-09 | 宜宾天原集团股份有限公司 | Preparation method of chlorosulfonated polyether-ether-ketone composite material film |
| CN107894640A (en) * | 2017-12-28 | 2018-04-10 | 江苏亨通光电股份有限公司 | One kind limits Fracture Force and makes somebody a mere figurehead leading in cable |
| CN110229540B (en) * | 2019-04-25 | 2021-08-10 | 上海俪源科技有限公司 | Navy blue reactive dye and preparation process thereof |
| CN110128846B (en) * | 2019-04-25 | 2021-08-10 | 上海俪源科技有限公司 | Navy blue reactive dye and preparation method thereof |
| CN110157216B (en) * | 2019-04-25 | 2021-08-10 | 上海俪源科技有限公司 | Navy blue reactive dye and processing method thereof |
| CN113150344B (en) * | 2021-04-21 | 2022-05-31 | 常州大学 | Proton exchange membrane with main polymer chain of aromatic ring structure and preparation method thereof |
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| WO2001089654A2 (en) * | 2000-05-23 | 2001-11-29 | Osmonics Inc | Acid stable membranes for nanofiltration |
| CN1683059A (en) * | 2005-03-03 | 2005-10-19 | 上海一鸣过滤技术有限公司 | Reinforced hollow fiber super filter film and its preparing method |
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| WO2001089654A2 (en) * | 2000-05-23 | 2001-11-29 | Osmonics Inc | Acid stable membranes for nanofiltration |
| CN1683059A (en) * | 2005-03-03 | 2005-10-19 | 上海一鸣过滤技术有限公司 | Reinforced hollow fiber super filter film and its preparing method |
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