CN109232881A - A kind of fluorinated poly arylene ether compound and preparation method thereof containing pendent sulfonic acid - Google Patents
A kind of fluorinated poly arylene ether compound and preparation method thereof containing pendent sulfonic acid Download PDFInfo
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- CN109232881A CN109232881A CN201811073757.8A CN201811073757A CN109232881A CN 109232881 A CN109232881 A CN 109232881A CN 201811073757 A CN201811073757 A CN 201811073757A CN 109232881 A CN109232881 A CN 109232881A
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- sulfonic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4006—(I) or (II) containing elements other than carbon, oxygen, hydrogen or halogen as leaving group (X)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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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 kind of fluorinated poly arylene ether compound and preparation method thereof containing pendent sulfonic acid.The present invention synthesizes a kind of tetraallyl compound TABPA first, then polycondensation reaction is carried out at room temperature with the bisphenol-A of different proportion and decafluorobiphenyl, prepare a series of polyether compounds containing tetraallyl segment and fluorine atom, again by being reacted with excessive 3-sulfydryl-1-propane sulfonic acid sodium, to introduce the pendent sulfonic acid of dense distribution, the fluorinated poly arylene ether compound containing pendent sulfonic acid of final obtained different ions content at allyl.The series compound can be dissolved in N, N- dimethyl acetamide, N, dinethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide isopolarity aprotic solvent, it can be formed a film by solution-cast, gained proton exchange membrane has many advantages, such as that proton conductivity is high, oxidation stability is good, thermal stability is good, high mechanical strength.
Description
Technical field
The present invention relates to a kind of fluorinated poly arylene ether compound and preparation method thereof containing pendent sulfonic acid, belongs to proton exchange
Field of membrane material.
Background technique
With social progress, energy crisis and environmental problem have become an important factor for restricting human kind sustainable development.
Proton Exchange Membrane Fuel Cells with many merits such as high energy conversion rate, low pollution emissions receives more and more attention.
Core component one of of the proton exchange membrane as the battery not only has the function of separating anode and cathode, also acts as conduction matter
The effect of son.Although commercialized Nafion film has excellent proton conductivity, there are some disadvantages, such as production cost for it
It is high, preparation process is relative complex, mechanical strength under the condition of high temperature and high humidity is lower, fuel permeability is big etc..Therefore, it finds low
Cost, high performance proton exchange membrane material are extremely urgent.
Sulfonated polyether is high due to having many advantages, such as good mechanical property, thermal stability and chemical stability, is closed extensively
Note.For example, Pang Jinhui et al. (Chinese invention patent, grant number: 102746508B) discloses a kind of sulfonated polyether sulphone proton
Exchange membrane and preparation method thereof, the proton conductivity of this kind of film at room temperature are 0.063 S cm-1, reachable at 100 DEG C
0.131 S cm-1.However, monomer preparation process involved in this method is complicated, and the proton conductivity of products therefrom is lower.
In order to improve the proton conductivity of sulfonated polyether, researchers propose a kind of gathering with ion clustering architecture by design synthesis
Close the strategy of object.Such as Guibin Li et al. people (Polymer Chemistry, 2015,6 (32): 5911-5920) is reported
Sulfonated polyether sulphone form ion clustering architecture because having soft pendent sulfonic acid, proton conductivity can reach close
The level of Nafion membrane.However, the limited length for the pendent sulfonic acid that the document is reported, limits its self assembly and proton conducting
Ability.As it can be seen that preparing the excellent sulfonated polyether compound of proton conductivity by reasonable MOLECULE DESIGN, proton is handed over
The development for changing membrane cell has great importance.
Summary of the invention
The object of the present invention is to provide a kind of fluorinated poly arylene ether compound containing pendent sulfonic acid, the compound have
The advantages that excellent proton conductivity, oxidation stability, mechanical performance and thermal stability, have in proton exchange membrane field huge
Application prospect.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of fluorinated poly arylene ether compound containing pendent sulfonic acid, structural formula are as follows:
In formula I, x=20 ~ 100, y=5 ~ 100.
The preparation method of it is a further object to provide a kind of fluorinated poly arylene ether compound containing pendent sulfonic acid,
Itself the following steps are included:
(1) by tetraallyl compound TABPA, bisphenol-A and decafluorobiphenyl are dissolved in polar non-solute, are with cesium fluoride
Catalyst carries out polymerization 10 ~ 60 hours in 0-80 DEG C under protection of argon gas, reaction solution is then poured into volume ratio under stiring
It is precipitated in the methanol aqueous solution of 1:1, filters and collect precipitating, it is 10 ~ 40 hours dry in 60 ~ 100 °C of vacuum drying oven, it is made
Fluorinated poly arylene ether compound,
The tetraallyl compound TABPA has the following structure:
The polymerization reaction formula of the fluorinated poly arylene ether compound are as follows:
In this step, the mole of decafluorobiphenyl is equal to the sum of TABPA and the mole of bisphenol-A, while being equal to rubbing for cesium fluoride
0.2 ~ 1 times of that amount.
(2) by fluorinated poly arylene ether compound obtained by step (1) and 3-sulfydryl-1-propane sulfonic acid sodium be dissolved in volume ratio be 1 ~
The N-Methyl pyrrolidone of 5:1 and the in the mixed solvent of dimethyl sulfoxide, using crown ether as catalyst, azodiisobutyronitrile is to cause
Agent reacts 10 ~ 100 hours at 60 ~ 150 DEG C, then cools to room temperature, pour into dialysis 3 days in dialysis bag；Finally, by dialysis bag
In substance drying to get arrive the fluorinated poly arylene ether compound containing pendent sulfonic acid.Its chemical equation are as follows:
3-sulfydryl-1-propane sulfonic acid sodium and the mole of crown ether are allyl mole in fluorinated poly arylene ether compound in this step
2 ~ 6 times of amount；The mole of azodiisobutyronitrile is 0.2 ~ 1 times of allyl mole in fluorinated poly arylene ether compound；Crown ether
For any one in 18- crown ether -6,12- crown ether -4,15- crown ether -5.
Above-mentioned tetraallyl compound TABPA's the preparation method is as follows:
1) in polar non-solute, 4,4 '-diallyl bisphenols, bromopropene and Anhydrous potassium carbonate are pressed into 1:2 ~ 10:2 ~ 5
Molar ratio mixed dissolution, be warming up to 50 ~ 120 DEG C under inert gas protection, react 1 ~ 100 hour, then reactant is fallen
Entering volume is that precipitating is precipitated in 2 ~ 10 times of polar non-solute of deionized water used, precipitating is collected by filtration, then through recrystallizing
Purification obtains compound II.The compound II has the following structure:
2) compound II is heated to 200 ~ 260 DEG C under protection of argon gas, constant temperature 1 ~ 5 hour, is then cooled to room temperature, by column
Purification obtains tetraallyl compound TABPA.
Above-mentioned polar non-solute be DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, N-Methyl pyrrolidone,
Any one in dimethyl sulfoxide；The quality of all reactants in the volume of the polar non-solute and each reaction system
The ratio of sum is 2 ~ 20:1 ml/g.
A kind of fluorinated poly arylene ether compound containing pendent sulfonic acid of gained of the invention can be used for preparing proton exchange membrane.
The present invention first synthesizes tetraallyl compound TABPA, then polymerize to obtain containing fluorine atom with bisphenol-A and decafluorobiphenyl
Polyether compound, then it is reacted with excessive 3-sulfydryl-1-propane sulfonic acid sodium, at allyl introduce sulfonic group,
The fluorinated poly arylene ether compound containing pendent sulfonic acid of final obtained different ions content.The series compound can be dissolved in N, N-
Dimethyl acetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone, dimethyl sulfoxide isopolarity aprotic solvent, can be with
It is formed a film by solution-cast, gained proton exchange membrane is high with proton conductivity, oxidation stability is good, thermal stability is good, mechanical
The advantages that intensity is high.
Compared with prior art, the invention has the following beneficial effects:
(1) raw material that the present invention uses is cheap for common industrial chemicals, is easy to get；Wherein, bisphenol-a reaction activity
Height, product good film-forming property.
(2) present invention carries out polymerization reaction at low temperature, and easy to operate, side reaction is few, and molecular weight of product is high.
(3) present invention is remarkably improved the oxidation stability of product using decafluorobiphenyl as polymerized monomer.
(4) present invention is introduced into sulfonic group the long side chain terminal of polymer, while guaranteeing that dense distribution is (every in polymer
A TABPA segment can introduce four pendent sulfonic acids), ion cluster is advantageously formed, to improve proton conductivity.
(5) the sulfonic group content of products therefrom of the present invention can be controlled by the molar ratio of compound TABPA.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of compound II in the embodiment of the present invention；
Fig. 2 is the nuclear magnetic resonance spectroscopy of tetraallyl compound TABPA in the embodiment of the present invention；
Fig. 3 is the nuclear magnetic resonance spectroscopy of fluorinated poly arylene ether compound FPAE-25 in the embodiment of the present invention；
Fig. 4 is the infrared spectrogram of fluorinated poly arylene ether compound FPAE-25 in the embodiment of the present invention；
Fig. 5 is the nuclear magnetic resonance spectroscopy of the fluorinated poly arylene ether compound SFPAE-25 in the embodiment of the present invention containing pendent sulfonic acid；
Fig. 6 is the infrared spectrogram of the fluorinated poly arylene ether compound SFPAE-25 in the embodiment of the present invention containing pendent sulfonic acid.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
The preparation of 1 tetraallyl compound TABPA of embodiment
By 2 g(6.5 mmol) 4,4'- diallyl bisphenol, 1.7 mL(19.4 mmol) allyl bromide, bromoallylene, 1.8 g(13.0
Mmol) Anhydrous potassium carbonate and 30 mL n,N-dimethylacetamide are added in three-necked flask, under the protection of argon gas, are warming up to
80 DEG C, magnetic agitation is reacted 48 hours, is poured into be precipitated in 200 mL deionized waters by reaction solution after reaction and be precipitated, filtering is received
Collection precipitates simultaneously dry, then with ethyl alcohol recrystallization, obtains compound II, yield 93%.Then, compound II is protected in argon gas
Property under, in 1 hour of 240 DEG C of constant temperature, then cool to room temperature, purify by column up to compound TABPA, yield 66%.
The preparation of 2 fluorinated poly arylene ether compound FPAE-25 of embodiment
1.3500 g(4.04 mmol) decafluorobiphenyl and 0.6849 g(3 mmol) bisphenol-A, 0.3886 g(1 mmol) TABPA,
3.03 g(15 mmol) cesium fluoride, 0.05 g calcium hydride (be used for drying) and 16 mL N-Methyl pyrrolidones are added to three mouthfuls
In flask, reaction solution is poured into 200 mL by room temperature magnetic agitation 24 hours under the protection of argon gas under stiring after reaction
It is precipitated in the mixed solution (1:1, v/v) of first alcohol and water, it is small to be collected by filtration in the vacuum drying oven for be deposited in 80 DEG C dry 24
When to get fluorinated poly arylene ether compound FPAE-25, intrinsic viscosity is 1.1 dL/g, yield 95%.
The preparation of 3 fluorinated poly arylene ether compound FPAE-30 of embodiment
The inventory of bisphenol-A in embodiment 2 is changed to 0.6392 g(2.8 mmol), the inventory of TABPA is changed to 0.4663 g
Embodiment 2 is pressed in (1.2 mmol), remaining operation, and the intrinsic viscosity of gained fluorinated poly arylene ether compound FPAE-30 is 0.86 dL/
G, yield 93%.
The preparation of 4 fluorinated poly arylene ether compound FPAE-35 of embodiment
The inventory of bisphenol-A in embodiment 2 is changed to 0.5936 g(2.6 mmol), the inventory of TABPA is changed to 0.5440 g
Embodiment 2 is pressed in (1.4 mmol), remaining operation, and the intrinsic viscosity of gained fluorinated poly arylene ether compound FPAE-35 is 0.92 dL/
G, yield 94%.
The preparation of 5 fluorinated poly arylene ether compound FPAE-40 of embodiment
The inventory of bisphenol-A in embodiment 2 is changed to 0.5479 g(2.4 mmol), the inventory of TABPA is changed to 0.6217 g
Embodiment 2 is pressed in (1.6 mmol), remaining operation, and the intrinsic viscosity of gained fluorinated poly arylene ether compound FPAE-40 is 1.01 dL/
G, yield 93%.
The preparation of fluorinated poly arylene ether compound SFPAE-25 of the embodiment 6 containing pendent sulfonic acid
In Example 2 gained fluorinated poly arylene ether compound (FPAE-25) 0.5 g(0.89 mmol), 3- sulfydryl -1- propane sulphur
Sour 0.63 g(3.56 mmol of sodium), -6 0.94 g(3.56 mmol of 18- crown ether), 0.074 g(0.45 of azodiisobutyronitrile
Mmol), 12 mL of mixed solvent (2:1, v/v) of N-Methyl pyrrolidone and dimethyl sulfoxide is added to the three-necked flask of 25mL
In, it reacting 3 days for 80 DEG C, is then cooled to room temperature under protection of argon gas, Yu Shuizhong changed 3 water with half membrane dialyzing 3 days daily,
Finally, the substance in dialysis bag is dried to get the fluorinated poly arylene ether compound SFPAE-25 containing pendent sulfonic acid, characteristic is arrived
Viscosity is 1.7 dL/g, yield 87%.
The preparation of fluorinated poly arylene ether compound SFPAE-30 of the embodiment 7 containing pendent sulfonic acid
In Example 3 gained fluorinated poly arylene ether compound (FPAE-30) 0.5 g(0.88 mmol), 3- sulfydryl -1- propane sulphur
Sour 0.75 g(4.22 mmol of sodium), -6 1.12 g(4.22mmol of 18- crown ether), 0.087 g(0.53 of azodiisobutyronitrile
Mmol), 14 mL of mixed solvent (2:1, v/v) of N-Methyl pyrrolidone and dimethyl sulfoxide is added to the three-necked flask of 25mL
In, it is prepared by operation described in embodiment 6, the characteristic of fluorinated poly arylene ether compound SFPAE-30 of the gained containing pendent sulfonic acid
Viscosity is 1.3 dL/g, yield 85%.
The preparation of fluorinated poly arylene ether compound SFPAE-35 of the embodiment 8 containing pendent sulfonic acid
In Example 4 gained fluorinated poly arylene ether compound (FPAE-35) 0.5 g(0.86 mmol), 3- sulfydryl -1- propane sulphur
Sour 0.86 g(4.82 mmol of sodium), -6 1.27 g(4.82 mmol of 18- crown ether), 0.099 g(0.60 of azodiisobutyronitrile
Mmol), 16 mL of mixed solvent (2:1, v/v) of N-Methyl pyrrolidone and dimethyl sulfoxide is added to the three-necked flask of 25mL
In, it is prepared by operation described in embodiment 6, the characteristic of fluorinated poly arylene ether compound SFPAE-35 of the gained containing pendent sulfonic acid
Viscosity is 2.0 dL/g, yield 82%.
The preparation of fluorinated poly arylene ether compound SFPAE-40 of the embodiment 9 containing pendent sulfonic acid
Gained fluorinated poly arylene ether compound (FPAE-40) 0.5g(0.85 mmol in Example 5), 3- sulfydryl -1- propane sulfonic acid
0.97 g(5.44 mmol of sodium), -6 1.44 g(5.44 mmol of 18- crown ether), 0.112 g(0.68 of azodiisobutyronitrile
Mmol), 18 mL of mixed solvent (2:1, v/v) of N-Methyl pyrrolidone and dimethyl sulfoxide is added to the three-necked flask of 25mL
In, it is prepared by operation described in embodiment 6, the characteristic of fluorinated poly arylene ether compound SFPAE-40 of the gained containing pendent sulfonic acid
Viscosity is 1.9 dL/g, yield 82%.
The proton exchange membrane that embodiment 10 is prepared based on the fluorinated poly arylene ether compound containing pendent sulfonic acid
Fluorine-containing 0.5 g of sulfonated polyether compound of long side chain type based on tetraallyl bisphenol-A made from Example 6-9, point
It is not dissolved in 10mL n,N-dimethylacetamide, pours and cast from horizontal positioned plate glass after ultrasonic deaeration, then true
80 DEG C drying 12 hours, i.e., form membranaceous product in glass plate in empty baking oven.Film is peeled from glass plate, with 1mol/L's
It is acidified in sulfuric acid solution, then sulfuric acid extra in film is cleaned with deionized water, fluorine-containing sulfonated polyether is finally made
Proton exchange membrane.Through characterizing, obtained film properties are as shown in table 1:
The performance comparison data of the different films of table 1
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with repair
Decorations, are all covered by the present invention.
Claims (8)
1. a kind of fluorinated poly arylene ether compound containing pendent sulfonic acid, which is characterized in that its structural formula are as follows:
In formula I, x=20 ~ 100, y=5 ~ 100.
2. a kind of preparation method of fluorinated poly arylene ether compound containing pendent sulfonic acid according to claim 1, feature
It is, comprising the following steps:
(1) by tetraallyl compound TABPA, bisphenol-A and decafluorobiphenyl are dissolved in polar non-solute, are with cesium fluoride
Catalyst carries out polymerization 10 ~ 60 hours in 0-80 DEG C under protection of argon gas, reaction solution is then poured into volume ratio under stiring
It is precipitated in the methanol aqueous solution of 1:1, filters and collect precipitating, it is 10 ~ 40 hours dry in 60 ~ 100 °C of vacuum drying oven, it is made
Fluorinated poly arylene ether compound,
The structure of the tetraallyl compound TABPA is as follows:
；
(2) fluorinated poly arylene ether compound obtained by step (1) and 3-sulfydryl-1-propane sulfonic acid sodium are dissolved in volume ratio is 1 ~ 5:1
N-Methyl pyrrolidone and dimethyl sulfoxide in the mixed solvent, using crown ether as catalyst, azodiisobutyronitrile is initiator,
It is reacted 10 ~ 100 hours at 60 ~ 150 DEG C, then cools to room temperature, pour into dialysis 3 days in dialysis bag；Finally, by dialysis bag
Substance drying to get arrive the fluorinated poly arylene ether compound containing pendent sulfonic acid.
3. a kind of preparation method of the fluorinated poly arylene ether compound containing pendent sulfonic acid as claimed in claim 2, feature exist
In, tetraallyl compound as described in step (1) TABPA's the preparation method is as follows:
1) in polar non-solute, 4,4 '-diallyl bisphenols, bromopropene and Anhydrous potassium carbonate are pressed into 1:2 ~ 10:2 ~ 5
Molar ratio mixed dissolution, be warming up to 50 ~ 120 DEG C under inert gas protection, react 1 ~ 100 hour, then reactant is fallen
Entering volume is that precipitating is precipitated in 2 ~ 10 times of polar non-solute of deionized water used, precipitating is collected by filtration, then through recrystallizing
Purification obtains compound II, and the structure of the compound II is as follows:
；
2) compound II is heated to 200 ~ 260 DEG C under protection of argon gas, constant temperature 1 ~ 5 hour, is then cooled to room temperature, by column
Purification obtains tetraallyl compound TABPA.
4. a kind of preparation method of the fluorinated poly arylene ether compound containing pendent sulfonic acid as claimed in claim 2 or claim 3, feature
It is, the polar non-solute is n,N-dimethylacetamide, n,N-Dimethylformamide, N-Methyl pyrrolidone, two
Any one in methyl sulfoxide；In the volume of the polar non-solute and each reaction system the quality of all reactants and
Ratio be 2 ~ 20:1 ml/g.
5. a kind of preparation method of the fluorinated poly arylene ether compound containing pendent sulfonic acid as claimed in claim 2, feature exist
In in step (1), the mole of decafluorobiphenyl is equal to the sum of TABPA and the mole of bisphenol-A, while being equal to rubbing for cesium fluoride
0.2 ~ 1 times of that amount.
6. a kind of preparation method of the fluorinated poly arylene ether compound containing pendent sulfonic acid as claimed in claim 2, feature exist
In 3-sulfydryl-1-propane sulfonic acid sodium and the mole of crown ether are allyl mole in fluorinated poly arylene ether compound in step (2)
2 ~ 6 times of amount；The mole of azodiisobutyronitrile is 0.2 ~ 1 times of allyl mole in fluorinated poly arylene ether compound.
7. a kind of preparation method of the fluorinated poly arylene ether compound containing pendent sulfonic acid as claimed in claim 2, feature exist
In, crown ether described in step (2) be 18- crown ether -6,12- crown ether -4, any one in 15- crown ether -5.
8. a kind of fluorinated poly arylene ether compound containing pendent sulfonic acid as described in claim 1 is in preparation proton exchange membrane
Using.
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| CN110591081A (en) * | 2019-09-16 | 2019-12-20 | 中国电建集团铁路建设有限公司 | Carboxyl-functionalized fluorine-containing polyarylether resin and preparation method thereof |
| CN112521597A (en) * | 2020-11-25 | 2021-03-19 | 吉林大学 | Sulfhydryl-containing polyarylether compound, preparation method and application thereof, antibacterial ultrafiltration membrane and preparation method thereof |
| WO2023089982A1 (en) * | 2021-11-17 | 2023-05-25 | 本州化学工業株式会社 | Curable resin composition, varnish, prepreg, and cured product |
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| XIALIN CHEN ET AL: "Partially fluorinated poly(arylene ether)s bearing long alkyl sulfonate side chains for stable and highly conductive proton exchange membranes", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110591081A (en) * | 2019-09-16 | 2019-12-20 | 中国电建集团铁路建设有限公司 | Carboxyl-functionalized fluorine-containing polyarylether resin and preparation method thereof |
| CN110591081B (en) * | 2019-09-16 | 2021-12-03 | 中国电建集团铁路建设有限公司 | Carboxyl-functionalized fluorine-containing polyarylether resin and preparation method thereof |
| CN112521597A (en) * | 2020-11-25 | 2021-03-19 | 吉林大学 | Sulfhydryl-containing polyarylether compound, preparation method and application thereof, antibacterial ultrafiltration membrane and preparation method thereof |
| CN112521597B (en) * | 2020-11-25 | 2021-08-20 | 吉林大学 | Sulfhydryl-containing polyarylether compound, preparation method and application thereof, antibacterial ultrafiltration membrane and preparation method thereof |
| WO2023089982A1 (en) * | 2021-11-17 | 2023-05-25 | 本州化学工業株式会社 | Curable resin composition, varnish, prepreg, and cured product |
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| CN109232881B (en) | 2021-07-13 |
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