CN1621431A - Sulfonated fluorine-containing poly-arylether (arone) and its preparing method and use - Google Patents
Sulfonated fluorine-containing poly-arylether (arone) and its preparing method and use Download PDFInfo
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- CN1621431A CN1621431A CNA2004100518619A CN200410051861A CN1621431A CN 1621431 A CN1621431 A CN 1621431A CN A2004100518619 A CNA2004100518619 A CN A2004100518619A CN 200410051861 A CN200410051861 A CN 200410051861A CN 1621431 A CN1621431 A CN 1621431A
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The present invention relates to one kind of sulfonated fluorene-containing polyaryl ether (ketone) and its application in preparing proton exchanging film. The sulfonated fluorine-containing polyaryl ether (ketone) may be prepared through polymerization of 9, 9-(4, 4-dihydroxyphenyl) fluorene and chloric or fluorous arone (arene) to form polyaryl ether (ketone); and the subsequent sulfonation with chlorosulfonic acid in the controlled consumption for controlled product sulfonation degree. The sulfonated fluorine-containing polyaryl ether (ketone) may be dissolved in different polar solvents before being cast to form single-component film, or be mixed with other polymer material for preparing composite film, or be mixed with heteropoly acid and other inorganic matter for preparing hetero film; and all these kinds of film have the advantages of low cost, high stability, high water absorption, small equivalent molecular weight, etc. and are expected to find use in fuel cell.
Description
Technical field
The present invention relates to class sulfonated fluorene-containing polyarylether (ketone) and preparation method thereof and their application in the preparation proton exchange membrane.
Background technology
Fuel cell has the effciency of energy transfer height, environmental friendliness, and the advantage that noiselessness etc. are outstanding is considered to the energy of 21 century first-selection, in fields such as space flight, military affairs, the energy, traffic wide application prospect is arranged.Proton Exchange Membrane Fuel Cells (PEMFC) be called as the 5th generation fuel cell, it starts but also have room temperature fast except possessing the advantage part of general fuel cell, no electrolyte loss, water is easily discharged, the life-span is long, outstanding features such as specific power and specific energy height.Proton exchange membrane (PEM) is one of core component of PEMFC, and its performance is directly connected to whole fuel cell overall performance.
General in the world proton exchange membrane is a perfluorinated sulfonic acid type proton exchange membrane at present, and wherein the most representative is the Nafion series perfluorinated sulfonic acid type proton exchange membrane that du pont company is produced.The Nafion series membranes has advantages such as electric conductivity height, stable chemical performance, life-span be long, but also has many shortcomings, and one of them significant disadvantage costs an arm and a leg exactly.At present the price of Nafion series proton exchange membrane be the 600-800 dollar/square metre.Market survey shows, if PEMFC will obtain business-like application on electromobile, wherein the cost of proton exchange membrane material must be controlled at the 50-150 dollar/square metre.Therefore, use the parts of expensive Nafion battery that film acts as a fuel, seriously restricting the commercialization process of PEM fuel cell, become the PEM fuel cell and move towards business-like key so research and develop cheaply proton exchange membrane.
Because fluorine-containing raw-material price is generally than higher, the R﹠D work of PEM mainly concentrates on the proton exchange membrane of development research free-floride and half fluorine.Wherein aspect floride-free proton exchange membrane research, sulfonated poly aryl ether ketone is one of research object that has potentiality to be exploited.But discover the sulfonated poly aryl ether ketone of general sulfonation on the polyaryletherketone main chain, owing to be subjected to sulfonic the influence, the ehter bond on the polyaryletherketone main chain ruptures easily, has reduced its chemical stability and work-ing life.If polyaryletherketone is sulfonated on side chain, then might effectively reduces the influence of sulfonic group, thereby improve its chemical stability and work-ing life the main chain ehter bond.
Sometimes mechanical strength or the anti-permeability performance in order to improve proton exchange membrane also prepares composite membrane to sulfonated poly aryl ether ketone and other superpolymer blend.
Sometimes electric conductivity or the chemical stability in order to improve proton exchange membrane also mixed up inorganicss such as some heteropolyacids or some metal oxides in sulfonated poly aryl ether ketone, the preparation hybrid film.
Summary of the invention
The object of the present invention is to provide class sulfonated fluorene-containing polyarylether (ketone) and preparation method thereof, and the application of this compounds in the preparation proton exchange membrane.
The present invention carries out sulfonation by the polyarylether (ketone) of choosing a class and containing fluorenes with chlorsulfonic acid, and the sulfonic group of sulfonated products is prepared required sulfonated fluorene-containing polyarylether (ketone) on the side chain of fluorenyl unit.
The present invention also by selecting the prepared sulfonated polyether (ketone) of different solvents dissolving for use, is cast into single component film then, or is cast into composite membrane with other superpolymer blend, or is cast into hybrid film with inorganics blend such as heteropolyacid.
Sulfonated fluorene-containing polyarylether provided by the invention (ketone) has as shown in the formula the structure shown in (I):
N=50 in the following formula～150, X
1=0.1～1, when X1 less than 1 the time, X
2=0; Work as X
1Equal at 1 o'clock, X
2=0～0.5;
Sulfonated fluorene-containing polyarylether of the present invention (ketone) can prepare by the following method: select polyarylether containing fluorene (ketone) for use (II), make dissolution with solvents with methylene dichloride or trichloromethane, strength of solution is 0.5～5% (wt), dripping concentration is the methylene dichloride or the chloroform soln of the chlorsulfonic acid of 0.1～10% (wt), the fluorenyl structural unit of polyarylether containing fluorene in the reactant (ketone) and the mol ratio of chlorsulfonic acid are 1: (2～10), at room temperature carrying out sulfonation handles, the sulfonic group of proton is led in introducing, methylene dichloride or the trichloromethane as solvent removed in reaction end hypsokinesis, obtain the brown precipitate product, be sulfonated fluorene-containing polyarylether (ketone) (I); Reaction process is shown below:
N=50 in the following formula～150, X
1=0.1～1, works as X
1Less than 1 o'clock, X
2=0; Work as X
1Equal at 1 o'clock, X
2=0～0.5;
Or
As stated above, by the fluorenyl structural unit of polyarylether containing fluorene (ketone) and the mol ratio of chlorsulfonic acid in the control reactant, can obtain different sulfonation degree (is X among the structural formula I
1+ X
2The value difference) sulfonated fluorene-containing polyarylether (ketone).
Above-mentioned prepared sulfonated fluorene-containing polyarylether (ketone) product can also be remake and be further purified processing, concrete grammar is: give a baby a bath on the third day after its birth time with normal hexane, dissolve with polar aprotic solvent, with among the 3%wt NaOH and 4～10 hours, the NaOH consumption equals 1～3 times of amount of substance of reactant chlorsulfonic acid, and then with 5%v/v HCl solution acidifying 4～10 hours, the consumption of HCl was 1～4 times of amount of substance of NaOH consumption; Product after the acidifying changes dialysis in the semi-permeable membranes dialysis bag over to, removes small molecular weight impurity, changes water every day one time, and the water until the dialysis bag outside is neutral; The product of dialysis changes in the distilling flask, uses the Rotary Evaporators evaporate to dryness, obtains being more suitable for being used to preparing the sulfonated fluorene-containing polyarylether (ketone) of the purifying of proton exchange membrane.
Sulfonated fluorene-containing polyarylether of the present invention (ketone) can be used for preparing proton exchange membrane (PEM), and the PEM of gained is suitable for as fuel battery proton exchange film.
The method for preparing proton exchange membrane with sulfonated fluorene-containing polyarylether of the present invention (ketone) is: the invention described above (preferably purified) sulfonated fluorene-containing polyarylether (ketone) is fully dissolved with polar aprotic solvent, remove by filter insoluble impurity, solution is concentrated at 50～65 ℃ and is poured over can not flow out sheet glass on the sheet glass time, be poured over casting film-forming on the clean sheet glass, put into vacuum drying oven, vacuum volatilization solvent under 40～60 ℃ of temperature gets dry finished product single component proton exchange membrane (single component film); Used polar aprotic solvent can be N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), methyl-sulphoxide (DMSO), N-Methyl pyrrolidone (NMP) or oil of mirbane.
Sulfonated fluorene-containing polyarylether (ketone) and other superpolymer blend of the purifying that makes can also be prepared compound proton exchange membrane (composite membrane), perhaps sulfonated fluorene-containing polyarylether (ketone) and the inorganics blend with purifying prepares hybridization proton exchange membrane (hybrid film), and the technology of preparation is identical with above-mentioned preparation single component film with condition.Described other superpolymer is generally tetrafluoroethylene, poly(vinylidene fluoride), vinylidene fluoride or/and styrol copolymer etc.; Described inorganics is generally phospho-wolframic acid, phosphorus aluminic acid, silicon-dioxide, aluminium sesquioxide or/and titanium oxide etc.
Utilize sulfonated fluorene-containing polyarylether of the present invention (ketone) preparation proton exchange membrane to have following characteristics:
1, the raw material that is adopted is except that the IIc part is fluorine-containing and is not fluorine-containing superpolymer, and with respect to the perfluor superpolymer, price much lower (IIc also be comparatively cheap) can effectively reduce the cost of proton exchange membrane.
2, polyarylether containing fluorene (ketone) resin has excellent chemical physics performance and mechanical property such as high temperature resistant, creep resistance, high strength, obdurability, is widely used at aspects such as polymeric membrane, aerospace and electronic industries.With its polyarylether skeleton, can satisfy PEMFC to the physical chemistry of proton exchange membrane and the requirement of mechanical property as proton exchange membrane material.
3, the present invention carries out sulfonation with polyarylether containing fluorene (ketone), sulfonic group in the product molecule is positioned on the fluorenes ring that contains fluorene structural units, is on the side chain of macromolecular structure, can effectively avoid the influence of sulfonic group to the molecular backbone chain ehter bond, thereby improve its chemical stability, prolong its work-ing life.
4, since polyarylether containing fluorene (ketone) (II) the fluorenes ring element in the structure have two positions can introduce the sulfonate functional base, so its equivalent weight (EW, film weight mg/ sulfonic acid base unit weight meq) lower, between 300-600, suitable with the BAM3G third generation proton exchange membrane of Canadian Ba Lade company.The water-intake rate of equivalent weight and resin and to lead the proton performance closely related.The equivalent weight of institute's synthetic sulfonated fluorene-containing polyarylether (ketone) can be regulated by the consumption and the sulfonation condition of regulating sulphonating agent.Make it to have higher water-intake rate and higher proton conductivity.
Embodiment:
One, the sulfonation embodiment of polyarylether containing fluorene (ketone)
The sulfonation of embodiment 1-1 polyarylether containing fluorene ketone IIa:
Under the room temperature, the polyarylether containing fluorene ketone IIa of 0.25mmol is added in the single port flask of 100mL, add the 25mL methylene dichloride, induction stirring is fully dissolved it, by containing the ratio of fluorene structural units with the chlorsulfonic acid molecule in the polyarylether containing fluorene ketone IIa molecule is that 1: 4 amount is measured 0.0665ml (1mmol, 0.117g) chlorsulfonic acid, add the 3mL methylene dichloride and be mixed with solution solution, slowly dropwise splash into, stirring reaction 5 hours has brown precipitate to generate, and inclining methylene dichloride, each with 5mL normal hexane washing three times, add 5mLDMAc, stirs and it was fully dissolved in 1-2 hour, the sodium hydroxide solution of adding 10mL 3wt%, stirred 6 hours, the HCl solution that adds 100mL 5wt% again reacted 5 hours, and reaction product changes in the dialysis bag, with deionized water dialysis to the water outside the dialysis bag is neutral, and evaporate to dryness promptly gets sulfonated fluorene-containing polyaryletherketone Ia then.It (is X that ultimate analysis records sulfonation degree
1+ X
2Value) be 0.73.Confirm that through IR spectrum and HNMR spectrum sulfonic group is positioned on the side chain that contains fluorene structural units.
Embodiment 1-2,1-3,1-4,1-5,1-6,1-7,1-8,1-9,1-10 is respectively the sulfonation of polyarylether containing fluorene (ketone) IIb～IIj, its method of sulfonating is identical with embodiment 1-1 with step, and raw material ratio that different is (ratio that contains fluorene structural units and chlorsulfonic acid molecule in polyarylether containing fluorene (ketone) molecule) is different, and the sulfonation degree of products therefrom (is X
1+ X
2Value) difference, as shown in table 1:
Table 1
| Embodiment | ?1-2 | ??1-3 | ??1-4 | ??1-5 | ??1-6 | ??1-7 | ??1-8 | ??1-9 | ??1-10 |
| Polyarylether containing fluorene (ketone) | ?IIb | ??IIc | ??IId | ??IIe | ??IIf | ??IIg | ??IIh | ??IIi | ??IIj |
| Raw material ratio | ?1∶5 | ??1∶8 | ??1∶5 | ??1∶4 | ??1∶4 | ??1∶4 | ??1∶5 | ??1∶5 | ??1∶6 |
| The sulfonation degree of sulfonated products | ?0.92 | ??1.53 | ??0.89 | ??0.76 | ??0.74 | ??0.77 | ??0.93 | ??0.96 | ??1.12 |
Two, the preparation of film
Embodiment 2-1 prepares single component film by sulfonated fluorene-containing polyaryletherketone Ia:
Get the sulfonated fluorene-containing polyaryletherketone Ia1g that makes by embodiment 1-1, add 20mL DMAc, stirring 3h dissolves it fully, filter, filtrate is concentrated at 65 ℃ to be estimated to be poured over can not flow out sheet glass on the sheet glass time, is poured over casting film-forming on the clean sheet glass then, puts into vacuum drying oven, vacuum volatilization solvent under 40 ℃ of temperature gets dry finished product single component film.
The film that makes is measured its antioxidant property with Fenton reagent, and method is the H 30%
2O
2The FeSO that adds 30ppm in the solution
4, in the time of 25 ℃, put into 1cm
2Membrane sample, recording film begins to split the broken time.
The film that makes is measured its specific conductivity with the alternating-current impedance determinator with sulfuric acid acidifying under 80 ℃ of temperature of 1M after 24 hours.
Embodiment 2-2,2-3,2-4,2-5,2-6,2-7,2-8,2-9,2-10 are respectively by sulfonated fluorene-containing polyarylether (ketone) Ib～Ij and prepare single component film, and its preparation method is identical with embodiment 2-1 with step.The film that makes in Fenton reagent split the broken time and specific conductivity has nothing in common with each other, as shown in table 2.
Table 2
| Embodiment | ??2-1 | ???2-2 | ??2-3 | ??2-4 | ??2-5 | ??2-6 | ??2-7 | ??2-8 | ??2-9 | ??2-10 |
| Sulfonated fluorene-containing polyarylether (ketone) | ??Ia | ???Ib | ??Ic | ??Id | ??Ie | ??If | ??Ig | ??Ih | ??Ii | ??Ij |
| Film splits the broken time (h:m) | ??4:44 | ???4:23 | ??6:08 | ??4:53 | ??4:02 | ??3:38 | ??3:42 | ??5:06 | ??4:56 | ??5:11 |
| Membrane conductivity (S.cm -1) | ??8.27 ??×10 -3 | ???7.36 ???×10 -3 | ??8.42 ??×10 -3 | ??5.23 ??×10 -3 | ??3.16 ??×10 -3 | ??2.89 ??×10 -3 | ??3.53 ??×10 -3 | ??5.47 ??×10 -3 | ??5.31 ??×10 -3 | ??6.22× ???10 -3 |
The preparation of embodiment 2-11 composite membrane:
Get the sulfonated fluorene-containing polyaryletherketone Ia1g that makes by embodiment (1-1), be dissolved in 20mLDMAc altogether with the 0.5g tetrafluoroethylene, stirring 3h dissolves it fully, filter, filtrate is concentrated at 65 ℃ to be estimated to be poured over can not flow out sheet glass on the sheet glass time, is poured over casting film-forming on the clean sheet glass then, puts into vacuum drying oven, vacuum volatilization solvent under 40 ℃ of temperature gets dry finished product composite membrane.
The preparation of embodiment 2-12 hybrid film:
Make the DMAc solution (filtrate) of sulfonated fluorene-containing polyaryletherketone Ia by embodiment (2-1), add 0.1g phospho-wolframic acid (H therein
3[P (W
3O
10)
4] .14H
2O), vigorous stirring is uniformly dispersed it, is concentrated at 65 ℃ and estimates to be poured over can not flow out sheet glass on the sheet glass time, be poured over casting film-forming on the clean sheet glass then, put into vacuum drying oven, vacuum volatilization solvent under 40 ℃ of temperature gets dry finished product blend film.
Claims (8)
- One class formation be shown below sulfonated fluorene-containing polyarylether (ketone):
N=50 in the following formula～150, X 1=0.1～1, works as X 1Less than 1 o'clock, X 2=0; Work as X 1Equal at 1 o'clock, X 2=0～0.5;
Or
- 2. the preparation method of the described sulfonated fluorene-containing polyarylether of claim 1 (ketone), select polyarylether containing fluorene (ketone) for use (II), make dissolution with solvents with methylene dichloride or trichloromethane, strength of solution is 0.5～5%wt, dripping concentration is the methylene dichloride or the chloroform soln of the chlorsulfonic acid of 0.1～10%wt, the fluorenyl structural unit of polyarylether containing fluorene in the reactant (ketone) and the mol ratio of chlorsulfonic acid are 1: (2-10), at room temperature carrying out sulfonation handles, methylene dichloride or the trichloromethane as solvent removed in reaction end hypsokinesis, obtain the brown precipitate product, be required sulfonated fluorene-containing polyarylether (ketone) (I); Reaction process is shown below:N=50 in the following formula～150, X 1=0.1～1, works as X 1Less than 1 o'clock, X 2=0; Work as X 1Equal at 1 o'clock, X 2=0～0.5;Or
- 3. in accordance with the method for claim 2, it is characterized in that prepared sulfonated fluorene-containing polyarylether (ketone) product remake and be further purified processing, concrete grammar is: give a baby a bath on the third day after its birth time with normal hexane, dissolve with polar aprotic solvent, with among the 3%wt NaOH and 4～10 hours, the NaOH consumption equals 1～3 times of amount of substance of reactant chlorsulfonic acid, and then with 5%v/v HCl solution acidifying 4～10 hours, and the consumption of HCl is 1～4 times of amount of substance of NaOH consumption; Product after the acidifying changes dialysis in the semi-permeable membranes dialysis bag over to, removes small molecular weight impurity, changes water every day one time, and the water until the dialysis bag outside is neutral; The product of dialysis changes in the distilling flask, uses the Rotary Evaporators evaporate to dryness, obtains the sulfonated fluorene-containing polyarylether (ketone) of purifying.
- 4. the application of the described sulfonated fluorene-containing polyarylether of claim 1 (ketone) in the preparation proton exchange membrane.
- 5. according to the described application of claim 4, it is characterized in that sulfonated fluorene-containing polyarylether (ketone) is used to prepare single component film.
- 6. according to the described application of claim 4, it is characterized in that sulfonated fluorene-containing polyarylether (ketone) is used for preparing composite membrane with other superpolymer blend.
- 7. according to the described application of claim 4, it is characterized in that sulfonated fluorene-containing polyarylether (ketone) is used for that blend prepares hybrid film with inorganics.
- 8. according to the described application of one of claim 4-7, it is characterized in that the proton exchange membrane material of described proton exchange membrane as fuel cell.
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| CN107634248A (en) * | 2016-05-11 | 2018-01-26 | 常州大学 | A kind of application of the PEM based on polyfluorene |
| CN107634248B (en) * | 2016-05-11 | 2020-03-20 | 常州大学 | Application of proton exchange membrane based on polyfluorene |
| CN106910923A (en) * | 2017-02-13 | 2017-06-30 | 常州大学 | One class hexafluoro isopropyl containing hexichol structure side chain type sulfonated polyaryletherketone proton exchange membrane material and preparation method thereof |
| CN106910923B (en) * | 2017-02-13 | 2019-12-06 | 常州大学 | Side chain type sulfonated polyaryletherketone proton exchange membrane material containing diphenylhexafluoroisopropyl structure and preparation method thereof |
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