CN100336843C - Sulfonated high polymer containing bisphenol fluorine, synthesis and application thereof - Google Patents
Sulfonated high polymer containing bisphenol fluorine, synthesis and application thereof Download PDFInfo
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- CN100336843C CN100336843C CNB2005100336600A CN200510033660A CN100336843C CN 100336843 C CN100336843 C CN 100336843C CN B2005100336600 A CNB2005100336600 A CN B2005100336600A CN 200510033660 A CN200510033660 A CN 200510033660A CN 100336843 C CN100336843 C CN 100336843C
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- monomer
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- bisphenol fluorene
- sulfonated
- high polymer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a sulfonated superpolymer containing bisphenol fluorene, synthesis thereof and application thereof. The structure of the compound is shown in type (I), and the compound has the synthetic processes that a bisphenol fluorene monomer, a sulfonated dihalo monomer and a dihalo monomer carry out copolymerization under the function of potassium carbonate in a polar aprotic solvent, and the sulfonated superpolymer having different degrees of sulphonation and containing the bisphenol fluorene is prepared by adjusting the molar ratio of the sulfonated dihalo monomer to the dihalo monomer. A proton exchange membrane prepared by the superpolymer has the advantages of low cost, high stability, high mechanical strength, good water absorbability, large proton exchange capacity, etc., and has latent application value in the field of fuel cells.
Description
Technical field
The present invention relates to sulfonated high polymer and synthetic and application thereof that a class contains bisphenol fluorene.
Technical background
At present, the energy and environment problem is one of the focus of world attention.Since middle period, along with scientific-technical progress, process of industrialization is accelerated from twentieth century, and the consumption of conventional energy resources is constantly quickened.Because conventional energy resourcess such as burning petroleum, Sweet natural gas, coal are emitted a large amount of obnoxious flavoures, for example carbon monoxide, carbonic acid gas, sulfide, oxynitride etc., cause the deterioration of global environment, Greenhouse effect, the every aspect that ozonosphere is impaired, adverse weather has had influence on people's life, partial area also are subjected to the attack of acid rain, photo-chemical smog.
The energy and ecocrisis are the problems that Sustainable development must overcome.The various countries scientist is devoted to seek the new way of efficiently utilizing the energy that the raising energy utilization rate reduces environmental pollution simultaneously, and fuel cell is the prefered method that can solve this difficult problem simultaneously of generally acknowledging at present.Because fuel cell directly is converted into electric energy with chemical energy, without the overheated machine process, is not subjected to the restriction of carnot's working cycle, so efficiency far is higher than common internal combustion engine and steamer.Fuel cell still is a kind of method of utilizing the energy of cleaning, and by hydrogen fuel cell, its product is water, and is environmentally friendly.
Proton Exchange Membrane Fuel Cells (PEMFC) be 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.The research PEMFC that spends huge sums one after another of country such as the U.S., Japan, Germany, Canada and each major company thereof is with its car power source as 21st century.Someone estimates that fuel cell car will be popularized at the year two thousand twenty.
(Proton Exchange Membrane is one of the critical material of PEMFC PEM) to proton exchange membrane, and the performance of PEM directly influences the fuel cell overall performance.At present, the PEM of widespread use is the Nafion film of E.I.Du Pont Company in the world, and it is a kind of perfluorinated sulfonic acid type proton exchange membrane, and structural formula is as follows:
X=6-10 wherein; Y, z=1
It is stable that the Nafion film has chemical property, thermally-stabilised, the physical strength height, and advantage such as proton conductivity is big, proton conductivity reaches 10 under the saturated condition of suction
-2-10
-1Scm
-1, be assembled in that the Nafion film can be in 80 ℃ of following non-stop runs up to ten thousand hours the PEMFC.But there is complex synthetic route in the Nafion film, and the preparation cost height hinders when pure coefficient is low to be higher than 100 ℃ with temperature and sharply descends the degradation deficiency owing to dehydration causes proton conductivity.Now, the research staff of various countries is devoted to seek the better Nafion film substitute of performance.New PEM must meet following requirement: the production cost that (1) is lower; (2) all can keep good proton conductivity at high temperature (greater than 100 ℃) and low temperature (less than 0 ℃); (3) good mechanical properties
Summary of the invention
What the object of the present invention is to provide that a class low cost can prepare fuel cell PEM contains sulfonated high polymer of bisphenol fluorene and preparation method thereof, and the application of such superpolymer in preparation PEM (particularly fuel cell PEM).
The present invention also provides a series products yield height, the preparation method of the PEM that process is simple and economic.
The structure of the sulfonated high polymer that contains two bisphenol fluorenes of the present invention is as the formula (1):
In the formula (I): m+n=10-100; R=H or CH
3 
The synthetic route of the sulfonated high polymer that contains bisphenol fluorene of the present invention is as follows:
The structure of the bisphenol fluorene monomer 2 that is adopted is suc as formula shown in (II):
R=H or CH
3
2a 2b
(II)
The sulfonation dihalo-monomer 3 that is adopted and the structure of dihalo-monomer 4 are suc as formula shown in (III):
3B：X＝-SO
2-，Y＝F； 4B：X＝-SO
2-，Y＝F；
3C：X＝-SO
2-，Y＝Cl) 4C：X＝-SO
2-，Y＝Cl)
(III)
The reaction formula that synthesizes the sulfonated high polymer that contains bisphenol fluorene is suc as formula shown in (IV):
The different sulfonated high polymer that contains bisphenol fluorene shown in formula (IV) lining is with symbol " 1R3
x" difference; distinguishing used bisphenol fluorene monomer with R is 2a or 2b; different sulfonation dihalo-monomer 3A, 3B or the 3C of 3 expressions, subscript x represent the ratio of the amount sum of the amount of sulfonation dihalo-monomeric substance and sulfonation dihalo-monomer and dihalo-monomeric substance, represent with percentage ratio.For example: polymkeric substance 1aA
80Expression uses monomer 2a and monomer 3A and 4A copolymerization synthetic, and wherein the amount of substance of 3A accounts for 80% of 3A and 4A amount of substance sum; Polymkeric substance 1aB
40Expression is synthetic synthetic with monomer 4B copolymerization with monomer 2a and monomer 3B, and wherein the amount of substance of 3B accounts for 40% of 3B and 4B amount of substance sum.Polymkeric substance 1bC
60Expression is synthetic synthetic with monomer 4C copolymerization with monomer 2b and monomer 3C, and wherein the amount of substance of 3C accounts for 60% of 3C and 4C amount of substance sum.
The sulfonated high polymer 1R3 that contains bisphenol fluorene of the present invention
xSynthetic can adopt the conventional method for preparing polyarylether.Concrete steps are:
Shown in (IV), reactant 2,3,4 and dewatering agent salt of wormwood, toluene and reaction solvent are added in the reaction vessel, the amount of substance of reactant 2 equals the amount of substance sum of reactant 3 and 4, the amount of substance of salt of wormwood is 1.1-1.5 a times of reactant 2, and the toluene consumption is 5-6 times of reactant 2 mmole numbers in milliliter; Reaction solvent is polar aprotic solvent such as N, N-N,N-DIMETHYLACETAMIDE (DMAc), methyl-sulphoxide (DMSO), N, dinethylformamide (DMF) or N-Methyl pyrrolidone (NMP) etc., solvent volume (is unit with the milliliter) is 3-4 times of reactant 2 (is unit with the mmole); Entire reaction is carried out under nitrogen protection, and induction stirring 140-155 ℃ of reaction 2-3 hour, is taken the water that reaction process generates out of by toluene earlier, continues to be warmed up to 165-180 ℃ then and keeps 18-21 hour.Reaction solution precipitates in methanol aqueous solution, filters, and collects product in 80-110 ℃ of vacuum drying oven dry 24-48 hour, promptly obtains the required sulfonated high polymer that contains bisphenol fluorene.
The sulfonated high polymer that contains bisphenol fluorene of the present invention 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 the sulfonated high polymer that contains bisphenol fluorene of the present invention is: the described sulfonated high polymer that contains bisphenol fluorene is dissolved in polar aprotic solvent DMAc, DMF, among DMSO or the NMP, make proton exchange membrane material at 55-80 ℃ of dustfree environment solvent flashing with the solution coating method.Concrete steps are: the sulfonated high polymer that will contain bisphenol fluorene is dissolved among polar aprotic solvent such as DMAc, DMSO, DMF or the NMP etc., in the aqueous hydrochloric acid of 8-10wt%, precipitate, kept 6-8 hour at 60-80 ℃, the polymkeric substance after the acidifying is removed inorganic salt with dialysis process; Filter, wash three times, 80 ℃ vacuum-drying 24-48 hour; Again with the DMAc dissolving, be mixed with mass concentration is 10-20% solution to resulting polymers, and 55-80 ℃ of (the best is 60 ℃) solvent flashing obtains proton exchange membrane (PEM) under dustless condition.
The present invention has synthesized the sulfonated high polymer that sulfonic acid type that a class can be used for preparing proton exchange membrane cheaply contains bisphenol fluorene.Utilize bisphenol fluorene monomer 2 and the dihalo-monomer 3 and the dihalo-monomer 4 that contain disulfonic acid sodium base to carry out copolyreaction in polar aprotic solvent, a synthetic class contains the sulfonated high polymer of bisphenol fluorene.Such superpolymer promptly obtains the floride-free PEM of the novel excellent combination property of a class through precipitation, purification, acidifying, dissolving system film.Such PEM material has following characteristics:
1. utilize industrial chemicals cheap and easy to get, adopt conventional preparation polyarylether route, simple, solved the cost problem of material.
2. polyarylether is as functional high molecule material, has excellent chemical physics performance and mechanical propertys such as high temperature resistant, creep resistance, high strength, obdurability, in aspect widespread uses such as electronic industry, space flight apparatus and military engineerings.The sulfonated high polymer that synthetic of the present invention contains bisphenol fluorene has the skeleton of polyarylether, can satisfy PEMFC to the physical chemistry of PEM and the requirement of mechanical property.
3. the general method for preparing the sulfonated polyether material is to make the polyarylether high molecule compound earlier, then with its sulfonation.The sulfonic acid group attack be the higher aromatic ring of electron density, therefore be easier to take place the reaction of reversible desulfonation.The present invention directly uses through the sulfonated monomer, and sulfonic acid group is connected on more inactive aromatic ring, and polymer chemistry character is more stable.
4. the sulfonic acid group of the sulfonated high polymer that contains bisphenol fluorene that the present invention is prepared is connected on the phenyl ring of band electron-withdrawing group, helps improving the acidity of sulfonic acid group, and the proton conductivity of superpolymer is strengthened.
5. the sulfonated high polymer that institute of the present invention synthetic contains bisphenol fluorene can change the sulfonation degree of polymkeric substance by adjusting sulfonation dihalo-monomer and the monomeric mol ratio of dihalo-, can obtain the sulfonated high polymer of the satisfied different working conditionss of different water-intake rates, proton conductivity.
Embodiment:
One, the synthetic embodiment that contains the sulfonated high polymer of bisphenol fluorene
Embodiment 1-1, polymkeric substance 1RA
100Synthetic:
With 0.7008g (2mmol) bisphenol fluorene monomer 2a; 0.8466g (2mmol) sulfonation dihalo-monomer 3A; 0.3455g (2.5mmol) Anhydrous potassium carbonate; 8mL DMSO and 10mL toluene; add in the there-necked flask, under the nitrogen protection, be warmed up to 150 ℃; kept 2 hours under the magnetic agitation; utilize toluene to take the water of generation out of, be warmed up to 175 ℃ then, reacted 20 hours; cooling; with in 8: 2 the methanol-water mixing solutions of reactant impouring 100mL volume ratio, filter under constantly stirring, use distilled water wash three times; 80 ℃ of vacuum-dryings 24 hours, get 1.3037g sodium type sulfonated polymer 1RA
100, productive rate 89%.
Embodiment 1-2, polymkeric substance 1RA
80Synthetic:
With 0.7008g (2mmol) bisphenol fluorene monomer 2a; 0.6757g (1.6mmol) sulfonation dihalo-monomer 3A; 0.0873g (0.4mmol) dihalo-monomer 4A; 0.3455g (2.5mmol) Anhydrous potassium carbonate, 8mL DMSO and 10mL toluene add in the there-necked flask; under the nitrogen protection; be warmed up to 150 ℃, kept 2 hours under the magnetic agitation, utilize toluene to take the water of generation out of; be warmed up to 175 ℃ then; reacted 20 hours, cooling is constantly stirred down in 8: 2 the methanol-water mixing solutions of reactant impouring 100mL volume ratio; filter; with distilled water wash three times, 80 ℃ of vacuum-dryings 24 hours, 1.3045g sodium type sulfonated polymer 1RA
80, productive rate 94%.
Embodiment 1-3, polymkeric substance 1RA
60Synthetic:
With 0.7008g (2mmol) bisphenol fluorene monomer 2a; 0.5068g (1.2mmol) sulfonation dihalo-monomer 3A; 0.1746g (0.8mmol) dihalo-monomer 4A; 0.3455g (2.5mmol) Anhydrous potassium carbonate, 7mL DMSO and 10mL toluene add in the there-necked flask; under the nitrogen protection; be warmed up to 150 ℃, kept 3 hours under the magnetic agitation, utilize toluene to take the water of generation out of; be warmed up to 175 ℃ then; reacted 20 hours, cooling is constantly stirred down in 1: 1 the methanol-water mixing solutions of reactant impouring 100mL volume ratio; filter; with distilled water wash three times, 80 ℃ of vacuum-dryings 24 hours, 1.2185g sodium type sulfonated polymer 1RA
60, productive rate 94%.
Embodiment 1-4, polymkeric substance 1RA
50Synthetic:
With 0.7008g (2mmol) bisphenol fluorene monomer 2a; 0.4223g (1mmol) sulfonation dihalo-monomer 3A; 0.2182g (1mmol) dihalo-monomer 4A; 0.3455g (2.5mmol) Anhydrous potassium carbonate, 7mL DMSO and 10mL toluene add in the there-necked flask; under the nitrogen protection; be warmed up to 150 ℃, kept 3 hours under the magnetic agitation, utilize toluene to take the water of generation out of; be warmed up to 175 ℃ then; reacted 20 hours, cooling is constantly stirred down in 1: 1 the methanol-water mixing solutions of reactant impouring 100mL volume ratio; filter; with distilled water wash three times, 80 ℃ of vacuum-dryings 24 hours, 1.2310g sodium type sulfonated polymer 1RA
50, productive rate 98%.
Embodiment 1-5, polymkeric substance 1RA
40Synthetic:
With 0.7008g (2mmol) bisphenol fluorene monomer 2a; 0.3378g (0.8mmol) sulfonation dihalo-monomer 3A; 0.2618g (1.2mmol) dihalo-monomer 4A; 0.3455g (2.5mmol) Anhydrous potassium carbonate, 6mL DMSO and 10mL toluene add in the there-necked flask; under the nitrogen protection; be warmed up to 150 ℃, kept 2 hours under the magnetic agitation, utilize toluene to take the water of generation out of; be warmed up to 175 ℃ then; reacted 20 hours, cooling is constantly stirred down in 1: 1 the methanol-water mixing solutions of reactant impouring 100mL volume ratio; filter; with distilled water wash three times, 80 ℃ of vacuum-dryings 24 hours, 1.2154g sodium type sulfonated polymer 1RA
40, productive rate 100%.
Embodiment 1-6, polymkeric substance 1RA
20Synthetic:
With 0.7008g (2mmol) bisphenol fluorene monomer 2a; 0.1689g (0.4mmol) sulfonation dihalo-monomer 3A; 0.3491g (1.6mmol) dihalo-monomer 4A; 0.3455g (2.5mmol) Anhydrous potassium carbonate, 6mL DMSO and 10mL toluene add in the there-necked flask; under the nitrogen protection; be warmed up to 150 ℃, kept 3 hours under the magnetic agitation, utilize toluene to take the water of generation out of; be warmed up to 175 ℃ then; reacted 20 hours, cooling is constantly stirred down in 1: 1 the methanol-water mixing solutions of reactant impouring 100mL volume ratio; filter; with distilled water wash three times, 80 ℃ of vacuum-dryings 24 hours, 1.1036g sodium type sulfonated polymer 1RA
20, productive rate 97%.
Two, the embodiment of preparation PEM
Embodiment 2-1, by polymkeric substance 1RA
100The preparation proton exchange membrane
Will be as the synthetic sodium type sulfonated polymer 1RA of embodiment 1-1 institute
100Being dissolved in and being made into concentration among the DMAc is 10% solution, precipitates in the aqueous hydrochloric acid of 80mL concentration 10%, keeps 6 hours at 60 ℃, and the polymkeric substance after the acidifying is removed inorganic salt with dialysis process and just obtained sulfonic acid-based polymer.Filter, wash three times, 80 ℃ of vacuum-drying 48 hours.Again with the DMAc dissolving, be mixed with concentration is 10% solution to the gained sulfonic acid-based polymer, pours glass dish 60 ℃ of solvent flashing system films under dustless condition of smooth cleaning into, desolvates for thoroughly removing, and resulting film was 110 ℃ of vacuum-dryings 24 hours.
Embodiment 2-2, by polymkeric substance 1RA
80The preparation proton exchange membrane
With the polymkeric substance 1RA among the embodiment 2-1
100Change polymkeric substance 1RA into
80, the preparation method is with embodiment 2-1.
Embodiment 2-3, by polymkeric substance 1RA
60The preparation proton exchange membrane
With the polymkeric substance 1RA among the embodiment 2-1
100Change polymkeric substance 1RA into
60, the preparation method is with embodiment 2-1.
Embodiment 2-4, by polymkeric substance 1RA
50The preparation proton exchange membrane
With the polymkeric substance 1RA among the embodiment 2-1
100Change polymkeric substance 1RA into
50, the preparation method is with embodiment 2-1.
Embodiment 2-5, by polymkeric substance 1RA
40The preparation proton exchange membrane
With the polymkeric substance 1RA among the embodiment 2-1
100Change polymkeric substance 1RA into
40, the preparation method is with embodiment 2-1.
Embodiment 2-6, by polymkeric substance 1RA
20The preparation proton exchange membrane
With the polymkeric substance 1RA among the embodiment 2-1
100Change polymkeric substance 1RA into
20, the preparation method is with embodiment 2-1.
Claims (4)
1. a class formation is suc as formula the preparation method of the sulfonated high polymer that contains bisphenol fluorene shown in (I),
In the formula (1): m+n=10-100; R=H or CH
3
Its concrete steps are: reactant 2,3,4 and dewatering agent salt of wormwood, toluene and reaction solvent are added in the reaction vessel, the amount of substance of reactant 2 equals the amount of substance sum of reactant 3 and 4, the amount of substance of salt of wormwood is 1.1-1.5 a times of reactant 2, and the toluene consumption is 5-6 times of reactant 2 mmole numbers in milliliter; Reaction solvent is a polar aprotic solvent, and solvent volume is that unit is 3-4 a times of reactant 2 mmole numbers with the milliliter; Entire reaction is carried out under nitrogen protection, and induction stirring 140-155 ℃ of reaction 2-3 hour, is taken the water that reaction process generates out of by toluene earlier, continues to be warmed up to 165-180 ℃ then and keeps 18-21 hour; Reaction solution precipitates in methanol aqueous solution, filters, and collects product in 80-110 ℃ of vacuum-drying 24-48 hour, promptly obtains the required sulfonated high polymer that contains bisphenol fluorene:
Described reactant 2 is the bisphenol fluorene monomer, and its structure is suc as formula shown in (II):
R=H or CH
3
2a 2b
(II) ：
Described reactant 3 and 4 is respectively sulfonation dihalo-monomer and dihalo-monomer, and its structure is suc as formula shown in (III):
2. method according to claim 1 is characterized in that described polar aprotic solvent is a N,N-dimethylacetamide, N, dinethylformamide, methyl-sulphoxide or N-Methyl pyrrolidone.
3. the application of the sulfonated high polymer that contains bisphenol fluorene that claim 1 makes in the preparation proton exchange membrane, it is characterized in that the described sulfonated high polymer that contains bisphenol fluorene is dissolved in polar aprotic solvent N, the N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, in methyl-sulphoxide or the N-Methyl pyrrolidone, use the solution coating method, solvent flashing makes proton exchange membrane material under 55-80 ℃ of dustfree environment.
4. application according to claim 3 is characterized in that the proton exchange membrane material of described proton exchange membrane as fuel cell.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100336600A CN100336843C (en) | 2005-03-23 | 2005-03-23 | Sulfonated high polymer containing bisphenol fluorine, synthesis and application thereof |
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|---|---|---|---|
| CNB2005100336600A CN100336843C (en) | 2005-03-23 | 2005-03-23 | Sulfonated high polymer containing bisphenol fluorine, synthesis and application thereof |
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| CN100336843C true CN100336843C (en) | 2007-09-12 |
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| KR100634551B1 (en) * | 2005-10-12 | 2006-10-16 | 삼성에스디아이 주식회사 | Crosslinked proton conductive copolymer and fuel cell comprising the same |
| CN101691423B (en) * | 2009-09-18 | 2011-06-08 | 中山大学 | Fluorinated modified sulfonated polyarylether and preparation method and application thereof |
| CN113336936B (en) * | 2021-06-07 | 2023-08-29 | 上海应用技术大学 | Sulfonated aromatic phosphine oxide polymer containing bisphenol fluorene, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252696A (en) * | 1991-11-07 | 1993-10-12 | Bayer Aktiengesellschaft | Water-dispersible polyisocyanate mixtures, a process for their preparation and their use in two-component aqueous compositions |
| CN1324880A (en) * | 2001-07-05 | 2001-12-05 | 上海交通大学 | Polyether ketone with pendant sulfonate radical and pendant carboxylate radical and its prepn. |
| JP2002367629A (en) * | 2001-06-12 | 2002-12-20 | Honda Motor Co Ltd | Electrode structure for solid polymer furl cell |
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2005
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252696A (en) * | 1991-11-07 | 1993-10-12 | Bayer Aktiengesellschaft | Water-dispersible polyisocyanate mixtures, a process for their preparation and their use in two-component aqueous compositions |
| JP2002367629A (en) * | 2001-06-12 | 2002-12-20 | Honda Motor Co Ltd | Electrode structure for solid polymer furl cell |
| CN1324880A (en) * | 2001-07-05 | 2001-12-05 | 上海交通大学 | Polyether ketone with pendant sulfonate radical and pendant carboxylate radical and its prepn. |
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