CN101704915B - Ionomer and ion exchange membrane material containing same - Google Patents
Ionomer and ion exchange membrane material containing same Download PDFInfo
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- CN101704915B CN101704915B CN200910230064XA CN200910230064A CN101704915B CN 101704915 B CN101704915 B CN 101704915B CN 200910230064X A CN200910230064X A CN 200910230064XA CN 200910230064 A CN200910230064 A CN 200910230064A CN 101704915 B CN101704915 B CN 101704915B
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- anhydrous
- polymkeric substance
- sulfonic acid
- acid group
- fluorine resin
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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 invention discloses an ionomer and an ion exchange membrane material containing the same. The ionomer contains a perfluocarbon polymer main chain and a branched chain connected with the polymer main chain, wherein a structural formula of the branched chain is shown in a figure; and the main chain thereof has a perfluocarbon structure. In the formula, R is -CF3, -C2F5, -C3F7, -OCF3, -OC2F5 or -OC3F7; x, y and z are an integer between 1 and 10,000 respectively; x/(x+y+z) is between 45 and 85 percent, y/(x+y+z) is between 10 and 45 percent, and z/(x+y+z) is between 0.1 and 10 percent (molar ratio); and m is 1 or 2, and n is an integer between 1 and 6. The fluoropolymer can be prepared into an ion exchange membrane by adopting a resin solution casting method.
Description
Technical field
The invention belongs to polymeric material field, relate to a kind of ionic polymer particularly and as the application of proton exchange membrane.
Background technology
Recently, along with increase to environment and energy consumption concern, and the commercialization of fuel cell car, press for and develop reliable, high performance fuel cell, this battery can be operated at ambient temperature, has energy-efficient and needs exploitation can increase the polymeric film of fuel efficiency.Fuel cell is new energy production system, and the energy that this system will produce by the electrochemical reaction of fuel and oxidizing gas directly changes into electric energy.
Ionic conductive polymer membrane is widely used in the proton exchange membrane between anode of fuel cell and negative electrode.Less swelling capacity when being used for the demanding ionic conductivity of polymkeric substance, electrochemical stability, acceptable mechanical property, the thermostability under working temperature of ionic conductive polymer membrane, the possibility that is processed to low resistance thin film and absorption liquid or the like.In their main chains, contain and fluoridize alkylidene group and contain the fluorinated polymer films of sulfonic acid group,, be used for ion-conducting membrane at present as the Nafion of Dupont in the fluorinated vinyl ether side chain terminal.Yet, because when be used for DMFCs, fancy price with cause that methyl alcohol passes the problem with lower-performance, makes such fluorinated polymer films not be suitable for the automobile fuel battery.
For addressing these problems, broad research can give each base polymer of dielectric film appropriate electrical chemical property and thermostability.The representative example of polymkeric substance comprises heat-resisting aromatic(based)polymer like this, as polyphenyl and miaow sound of crying or vomiting, polyethersulfone, polyetherketone etc.Yet, to such an extent as to these aromatic(based)polymers too rigidity can not dissolve and process film forming.
In addition, a large amount of practices is verified, and the material of employing main chain perfluoro can prolong the work-ing life of polymeric film greatly, improves dimensional stability and proton conductive.How in conjunction with the special machine performance and the thermostability of perfluorinated material, absorbing the electroconductibility of heat-resisting aromatic(based)polymer simultaneously, is the emphasis direction and the field of research at present.
GB1096879 proposes with the poly-α of sulfonation, β, and β-trifluorostyrene prepares improved ion exchange resin.The polymkeric substance that Japanese Patent (spy opens 2000-138068) proposes figure (A) structure is used to prepare ion-exchange membrane.
On this basis, the polymkeric substance of United States Patent (USP) (US5684192) proposition figure (B) structure is used for the ion-exchange membrane prepare.
For similar imagination, the polymkeric substance that patent (WO 96/40798) proposes figure (C) structure is used for the ion-exchange membrane prepare.
In addition, patent US6774150 and US7037950 adopt the polymkeric substance of figure (D) structure to be used for the ion-exchange membrane prepare.
The common ground of these inventions is to have adopted α, β, and β-trifluorostyrene is as polymerization or comonomer, and its main chain is perfluor or the fluorine-containing structure of part.But, because foregoing invention all adopted a large amount of aromatic monomers as polymer raw, cause the polymer molecule rigidity that makes too strong, cause ion-exchange membrane snappiness prepared therefrom not enough, even be difficult to dissolving and processing film forming.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of fluorine resin and its production and application with sulfonic acid group.
A kind of fluorine resin with sulfonic acid group, the side chain that this polymkeric substance contains a kind of main polymer chain and is connected with main polymer chain, described main polymer chain is a perfluoroalkyl chain, it is characterized in that: this polymkeric substance has the general formula shown in the formula (I):
R is-CF in the formula
3,-C
2F
5,-C
3F
7,-OCF
3,-OC
2F
5Or-OC
3F
7X, y, z are respectively 1～10000 integer; And x/ (x+y+z)=45%～85%, y/ (x+y+z)=10%～45%, z/ (x+y+z)=0.1%～10% is mol ratio; Wherein, m is 1 or 2, and n is the integer of 1-6;
In the branched structure formula of described fluorine resin with sulfonic acid group, group-(CF
2)
n-SO
3H is connected to contraposition, ortho position or a position of the chemical bond that is connected with main chain in the phenyl ring.
Preferably, described number-average molecular weight with fluorine resin of sulfonic acid group is 80000-1000000.
Preferably, described loading capacity with fluorine resin of sulfonic acid group is 0.85-1.50mmol/g.
The present invention also provides described preparation method with fluorine resin of sulfonic acid group, comprises the following steps:
1) with tetrafluoroethylene, tetrafluoroethylene derivative and α, β, β-trifluorostyrene causes copolymerization through free radical in the presence of dispersion agent, water and initiator; Obtain containing the polymkeric substance of phenyl ring; Tetrafluoroethylene, α, β, the feed ratio of β-trifluorostyrene and tetrafluoroethylene derivative is 45～85: 10～45: 0.1～10, mol ratio;
2) in the presence of catalyzer and in the nitrogen atmosphere, in anhydrous solvent, contain the polymkeric substance and the sulfoalkyl reagent contact reacts of phenyl ring, isolate the polymkeric substance of the sulfoalkylization that obtains; Acidifying then obtains having the fluorine resin of sulfonic acid group.
The described tetrafluoroethylene derivative of step 1) is: R 1216, perfluor 1-butylene, perfluor 1-amylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether or perfluoro propyl vinyl ether; Described dispersion agent is the perfluoroalkyl ethers that contains the trimeric cyanamide structure; Described initiator is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
The perfluoroalkyl ethers dispersion agent that contains the trimeric cyanamide structure is the melamine derivative that a class has the perfluoroalkyl ethers chain link, and its general molecular formula is:
A+b=2 wherein, b is 0 or 1, and c is 1～10 integer.Can buy also and can make by oneself according to known technology.
Preferably, step 2) be 0-200 ℃ with the catalytic temperature of reaction of sulfoalkyl reagent in, the reaction times is 1-200 hour;
Preferably, the catalyzer step 2) is selected from aluminum trichloride (anhydrous), Anhydrous Ferric Chloride, solid phosphoric acid, hydrogen fluoride and/or BF
3-H
3PO
4In one or more;
Preferably, the described sulfoalkyl reagent step 2) is selected from 1,2-R 116 sultone, 1,3-perfluoropropane sultone, 1,4-perfluorinated butane sultone, 1,5-perflenapent sultone and/or 1, one or more in the 6-perflexane sultone;
The mol ratio of described sulfoalkyl reagent, catalyzer, the polymkeric substance that contains phenyl ring and the anhydrous solvent preferably, step 2) is 1: 0.1-3: 0.01-2: 2-30;
Preferably, step 2) the described anhydrous solvent described in is selected from anhydrous chloroform, anhydrous ethylene dichloride, anhydrous cyclohexane, anhydrous dimethyl Asia sough (DMSO), anhydrous N, in dinethylformamide (DMF), anhydrous N,N-dimethylacetamide (DMAc), anhydrous N-Methyl pyrrolidone (NMP), anhydrous propanone, anhydrous methylethylketone, anhydrous pimelinketone and/or the anhydrous oil of mirbane one or more.
Step 2) described acidifying, can adopt any known method to carry out, can use any known acid or acidic solution, example hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid etc., concentration to acidic solution does not have special requirement, and the dilute solution or the strong solution of acid all can meet the requirements of acidizing effect.
Preferably, the application with fluorine resin of sulfonic acid group of the present invention, this resin can be dissolved in high boiling organic solvent or the solvent combination.High boiling organic solvent or group of solvents are combined into: (DMSO), anhydrous N sough in the anhydrous dimethyl Asia, in dinethylformamide (DMF), anhydrous N,N-dimethylacetamide (DMAc), anhydrous N-Methyl pyrrolidone (NMP) and/or the anhydrous pimelinketone one or more;
Application with fluorine resin of sulfonic acid group of the present invention, the equipment of required employing dissolves at high temperature during its dissolving, and the part that contacts with resin and solution adopts the Langaloy material, prevents to introduce in resin and solution the foreign ion foul solution;
Application with fluorine resin of sulfonic acid group of the present invention, this fluorine resin with sulfonic acid group can adopt solution casting method to be prepared into ion-exchange membrane.
Preferably, the application with fluorine resin of sulfonic acid group of the present invention, this resin solution can obtain homogeneous membrane or composite membrane by solvent evaporates by casting method on smooth flat.
Advantage of the present invention is: the fluorine resin with sulfonic acid group of the present invention has the perfluor main chain, and is very stable under hot and humid high current condition, is suitable for the application of long playing ion-exchange membrane.
Embodiment:
The measuring method of the loading capacity of polymkeric substance provided by the invention (IEC) adopts alkali formula titration measuring, and determination step is: 1. with polymkeric substance provided by the invention 120 ℃ of following vacuum-dryings 6 hours; 2. the M (gram) that dried polymkeric substance provided by the invention weighed, and immerse in the certain density sodium hydroxide solution of 50mL, under 50 ℃, stirred or leave standstill 24 hours, to carry out ion-exchange fully; 3. be indicator with phenolphthalein, get 20mL soak solution (must not sucking-off resin particle), with the finite concentration hydrochloric acid soln to its titration, the consumption of record hydrochloric acid soln; 4. calculate loading capacity or proton exchange capacity by following formula:
c
1: the volumetric molar concentration of standard caustic soda solution, the mol/L of unit;
c
2: the volumetric molar concentration of hydrochloric acid standard solution, the mol/L of unit;
V: the volume of the hydrochloric acid standard solution that the titration sodium hydroxide solution spends, Unit;
M: the quality of perfluorinated sulfonic resin in the tool plug Erlenmeyer flask, the g of unit.
Following embodiment will the present invention is described in further detail, but the invention is not restricted to these specific exampless.Example 1-8 has described the preparation and the sulfonation of various polymkeric substance; Example 9-12 has described the preparation that sulfonated polymer is applied to ion exchange membrane material.
Embodiment 1:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 18.5g and 0.2g dibenzoyl peroxide, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, R 1216 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 14.52%, and the R 1216 weight percentage is 4.32%, and the tetrafluoroethylene weight percentage is 81.16%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous oil of mirbane and 20.2 grams 1 again, 3-perfluoropropane sultone.After polystyrene resin fully dissolves, slowly add the anhydrous BF of 15.7 grams again
3-H
3PO
4Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 0.90mmol/g.
Embodiment 2:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 21.5g and 0.2g dibenzoyl peroxide, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluoro methyl vinyl ether 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 15.97%, and the perfluoro methyl vinyl ether weight percentage is 3.37%, and the tetrafluoroethylene weight percentage is 80.66%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous oil of mirbane and 21.5 grams 1 again, 2-R 116 sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram anhydrous hydrogen fluorides again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.00mmol/g.
Embodiment 3:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 22.9g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, R 1216 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 17.76%, and the R 1216 weight percentage is 3.05%, and the tetrafluoroethylene weight percentage is 79.19%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous oil of mirbane and 22.5 grams 1 again, 2-R 116 sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram Anhydrous Ferric Chlorides again.Under the condensing reflux state, keeping temperature of reaction is 50 ℃ then, and reaction was carried out 100 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.04mmol/g.
Embodiment 4:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 24.5g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluoroethylvinyl ether 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 19.37%, and the perfluoroethylvinyl ether weight percentage is 3.01%, and the tetrafluoroethylene weight percentage is 77.52%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 50 milliliters of anhydrous pimelinketone and 23.5 grams 1 again, 2-R 116 sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram aluminum trichloride (anhydrous)s again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.11mmol/g.
Embodiment 5:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 26.5g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, R 1216 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 20.45%, and the R 1216 weight percentage is 2.90%, and the tetrafluoroethylene weight percentage is 76.65%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 70 milliliters of anhydrous oil of mirbane and 25.5 grams 1 again, 2-R 116 sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram aluminum trichloride (anhydrous)s again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 200 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.20mmol/g.
Embodiment 6:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 27.5g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluor 1-butylene 6g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 20.75%, and perfluor 1-butylene weight percentage is 2.90%, and the tetrafluoroethylene weight percentage is 76.35%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 80 milliliters of anhydrous methylethylketones and 25.5 grams 1 again, 2-R 116 sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram aluminum trichloride (anhydrous)s again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 240 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.23mmol/g.
Embodiment 7:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 30.5g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, R 1216 8g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 25.73%, and the R 1216 weight percentage is 4.30%, and the tetrafluoroethylene weight percentage is 69.97%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 90 milliliters of anhydrous cyclohexanes and 35.5 grams 1 again, 3-perfluoropropane sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram aluminum trichloride (anhydrous)s again.Under the condensing reflux state, keeping temperature of reaction is 80 ℃ then, and reaction was carried out 30 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 300 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.31mmol/g.
Embodiment 8:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 50.5g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, R 1216 8g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 44.73%, and the R 1216 weight percentage is 3.23%, and the tetrafluoroethylene weight percentage is 52.04%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 100 milliliters of anhydrous N-Methyl pyrrolidone (NMP) and 55.5 grams 1 again, 5-perflenapent sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram aluminum trichloride (anhydrous)s again.Under the condensing reflux state, keeping temperature of reaction is 180 ℃ then, and reaction was carried out 5 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 300 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.48mmol/g.
Embodiment 9:
(1) polyreaction
Is being furnished with stirring, heating, add 23.2g in the 1L high pressure stainless steel cauldron of nitrogen access equipment and contain the perfluoroalkyl ethers of trimeric cyanamide structure and 185g distilled water as dispersion agent, solvent, α, β, β-trifluorostyrene 45.5g and 0.2g Diisopropyl azodicarboxylate, with air in the high pure nitrogen replacement reaction kettle, feed tetrafluoroethylene 95g, perfluor 1-amylene 8g is warming up to 80 ℃ of stirring reaction 6h, and reaction finishes postcooling, venting, make the still internal pressure become normal pressure, emit product, precipitating in the big water gaging from discharge pipe, filter, get powdery product, repeatedly distillation washing, 100 ℃ of vacuum-dryings.Dispersion agent and moisture are mutually, separatory recycles.
Prepared polymer materials shows α by the test of fluorine nuclear-magnetism, β, and β-trifluorostyrene weight percentage is 37.51%, and the R 1216 weight percentage is 3.56%, and the tetrafluoroethylene weight percentage is 58.93%.
(2) sulfonation is handled
In the four-hole boiling flask that is connected with nitrogen protection, add the polymer powder that obtains in the 13 gram steps (1), add 100 milliliters of anhydrous N again, dinethylformamide (DMF) and 55.5 grams 1,4-perfluorinated butane sultone.After polystyrene resin fully dissolves, slowly add 16.0 gram solid phosphoric acids again.Under the condensing reflux state, keeping temperature of reaction is 10 ℃ then, and reaction was carried out 160 hours.
Reactant solution is poured into termination reaction in 500 milliliters of frozen water mixing solutionss that contain 50 milliliters of concentrated hydrochloric acids.Filter out granulated polymer, polymkeric substance is joined in the sodium hydroxide solution of 300 milliliter of 0.5 mol soaked overnight, in and resin in residual hydrochloric acid, and then with a large amount of deionized water wash polymer beads, be neutral to water, filter out the hydrolysate of aluminum chloride.With twice of the dilute sulphuric acid of 0.5 mol exchange resin is reduced to acidity (consumption of the dilute sulphuric acid of 0.5 mol is 100 times of sulfonate radical molar weight of polymkeric substance) again, with deionized water wash to neutral.110 ℃ of following vacuum-dryings, obtain polymkeric substance provided by the invention then.The IEC value of this polymkeric substance is 1.22mmol/g.
Embodiment 9:
Casting film-forming:
The polymkeric substance that obtains among the 10 gram embodiment 1 is dissolved among the 90 gram DMF, obtains the solution that polymer content is a mass concentration 10%.Getting 12 milliliters of solution, to be coated onto area be on 200 square centimeters the glass planar, to be warmed up to 200 ℃ of solvent flashings by 60 ℃ in horizontal heated oven, obtains thickness and be 30 microns proton exchange membrane provided by the invention.
Embodiment 10:
Casting film-forming:
The polymkeric substance that obtains among the 20 gram embodiment 1 is dissolved among the 80 gram NMP, obtains the solution that polymer content is a mass concentration 20%.Getting 20 milliliters of solution, to add area be on 200 square centimeters the glass planar, to be warmed up to 190 ℃ of solvent flashings by 50 ℃ in horizontal heated oven, obtains thickness and be 100 microns proton exchange membrane provided by the invention.
Embodiment 11:
Casting film-forming:
The polymkeric substance that obtains among the 25 gram embodiment 1 is dissolved among the 75 gram DMAc, obtains the solution that polymer content is a mass concentration 25%.Getting 30 milliliters of solution, to add area be on 200 square centimeters the glass planar, to be warmed up to 190 ℃ of solvent flashings by 50 ℃ in horizontal heated oven, obtains thickness and be 190 microns proton exchange membrane provided by the invention.
Embodiment 12:
Among the above embodiment 1 to 8, synthesize and have the loading capacity fluoropolymer and all can adopt the film of embodiment 9,10,11 to be prepared to obtain ion-exchange membrane.
Claims (6)
1. fluorine resin with sulfonic acid group, the side chain that this polymkeric substance contains a kind of main polymer chain and is connected with main polymer chain, described main polymer chain is a perfluoroalkyl chain, it is characterized in that: this polymkeric substance has the general formula shown in the formula (I):
R is-CF in the formula
3,-C
2F
5,-C
3F
7,-OCF
3,-OC
2F
5Or-OC
3F
7X, y, z are respectively 1～10000 integer; And x/ (x+y+z)=45%～85%, y/ (x+y+z)=10%～45%, z/ (x+y+z)=0.1%～10% is mol ratio; Wherein, m is 1 or 2, and n is the integer of 1-6;
Described fluorine resin with sulfonic acid group, its preparation method comprises the following steps:
1) with tetrafluoroethylene, tetrafluoroethylene derivative and α, β, β-trifluorostyrene causes copolymerization through free radical in the presence of dispersion agent, water and initiator; Obtain containing the polymkeric substance of phenyl ring; Tetrafluoroethylene, α, β, the feed ratio of β-trifluorostyrene and tetrafluoroethylene derivative is 45～85: 10～45: 0.1～10, mol ratio;
2) in the presence of catalyzer and in the nitrogen atmosphere, in anhydrous solvent, contain the polymkeric substance and the sulfoalkyl reagent contact reacts of phenyl ring, isolate the polymkeric substance of the sulfoalkylization that obtains; Acidifying then obtains having the fluorine resin of sulfonic acid group;
The described tetrafluoroethylene derivative of step 1) is: R 1216, perfluor 1-butylene, perfluor 1-amylene, perfluoro methyl vinyl ether, perfluoroethylvinyl ether or perfluoro propyl vinyl ether; Described dispersion agent is the perfluoroalkyl ethers that contains the trimeric cyanamide structure; Described initiator is Diisopropyl azodicarboxylate or dibenzoyl peroxide.
2. the fluorine resin with sulfonic acid group as claimed in claim 1 is characterized in that, described number-average molecular weight with fluorine resin of sulfonic acid group is 80000-1000000.
3. the fluorine resin with sulfonic acid group as claimed in claim 1 is characterized in that, described loading capacity with fluorine resin of sulfonic acid group is 0.85-1.50mmol/g.
4. the fluorine resin with sulfonic acid group as claimed in claim 1 is characterized in that step 2) in the catalytic temperature of reaction of sulfoalkyl reagent be 0-200 ℃, the reaction times is 1-200 hour; Step 2) catalyzer described in is selected from aluminum trichloride (anhydrous), Anhydrous Ferric Chloride, solid phosphoric acid, hydrogen fluoride and/or BF
3-H
3PO
4In one or more; Step 2) the sulfoalkyl reagent described in is selected from 1,2-R 116 sultone, 1,3-perfluoropropane sultone, 1,4-perfluorinated butane sultone, 1,5-perflenapent sultone and/or 1, one or more in the 6-perflexane sultone; Step 2) anhydrous solvent described in is selected from that anhydrous chloroform, anhydrous ethylene dichloride, anhydrous cyclohexane, anhydrous dimethyl Asia are soughed, anhydrous N, in dinethylformamide, anhydrous N,N-dimethylacetamide, anhydrous N-Methyl pyrrolidone, anhydrous propanone, anhydrous methylethylketone, anhydrous pimelinketone and/or the anhydrous oil of mirbane one or more.
5. the fluorine resin with sulfonic acid group as claimed in claim 1 is characterized in that step 2) described in the mol ratio of sulfoalkyl reagent, catalyzer, the polymkeric substance that contains phenyl ring and anhydrous solvent be 1: 0.1～3: 0.01～2: 2～30.
6. the application with fluorine resin of sulfonic acid group as claimed in claim 1, this resin solution obtains homogeneous or cluster ion exchange membrane by solvent evaporates by casting method on smooth flat.
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| EP1139472A1 (en) * | 2000-03-31 | 2001-10-04 | Asahi Glass Company Ltd. | Electrolyte membrane for solid polymer type fuel cell and producing method thereof |
| EP1553444A1 (en) * | 2002-07-18 | 2005-07-13 | Konica Minolta Photo Imaging, Inc. | Silver halide color photographic sensitive material and it image forming method |
| CN101237054A (en) * | 2008-02-03 | 2008-08-06 | 山东东岳神舟新材料有限公司 | An intercrossed enhanced full fluorin proton adulterated exchange film and its making method |
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| EP1139472A1 (en) * | 2000-03-31 | 2001-10-04 | Asahi Glass Company Ltd. | Electrolyte membrane for solid polymer type fuel cell and producing method thereof |
| EP1553444A1 (en) * | 2002-07-18 | 2005-07-13 | Konica Minolta Photo Imaging, Inc. | Silver halide color photographic sensitive material and it image forming method |
| CN101237054A (en) * | 2008-02-03 | 2008-08-06 | 山东东岳神舟新材料有限公司 | An intercrossed enhanced full fluorin proton adulterated exchange film and its making method |
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