CN106750301B - Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application - Google Patents

Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application Download PDF

Info

Publication number
CN106750301B
CN106750301B CN201611065449.1A CN201611065449A CN106750301B CN 106750301 B CN106750301 B CN 106750301B CN 201611065449 A CN201611065449 A CN 201611065449A CN 106750301 B CN106750301 B CN 106750301B
Authority
CN
China
Prior art keywords
sulfonated polyether
pyridine groups
copolymer containing
water
containing pyridine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611065449.1A
Other languages
Chinese (zh)
Other versions
CN106750301A (en
Inventor
李野
芦艾
耿呈祯
余凤湄
张倩
孙素明
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Chemical Material of CAEP
Original Assignee
Institute of Chemical Material of CAEP
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Material of CAEP filed Critical Institute of Chemical Material of CAEP
Priority to CN201611065449.1A priority Critical patent/CN106750301B/en
Publication of CN106750301A publication Critical patent/CN106750301A/en
Application granted granted Critical
Publication of CN106750301B publication Critical patent/CN106750301B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/20—Polysulfones
    • C08G75/23—Polyethersulfones
    • 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
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyethers (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Fuel Cell (AREA)

Abstract

The invention belongs to polymeric material fields, and in particular to a kind of sulfonated polyether sulphone and preparation method thereof containing pyridine groups.The present invention is that monomer prepares the different polyether sulphone of sulfonation degree using nucleophilic condensation polymerization by adjusting sulfonated monomer and the ingredient proportion of non-sulfonated monomer with dichloropyridines such as 3,5- dichloropyridines.Meanwhile the ingredient proportion of pyridine monomer is adjusted, prepare the different sulfonated polyether sulphone of pyridine content.Sulfonated polyether sulphone polymer film containing pyridine groups of the invention has good dimensional stability, chemical stability, alcohol-rejecting ability, has potential application prospect in fuel cell polyelectrolyte film field.

Description

Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of sulfonated polyether sulfone copolymer containing pyridine groups and Preparation method, the application of the invention further relates to the described sulfonated polyether sulfone copolymer containing pyridine groups.
Background technique
Polyelectrolyte membrane cell has many advantages, such as that starting speed is fast, specific energy is high, safe and portable, it is considered to be electronic Automobile, portable power supplies, the reliable energy device in stationary electric power plant.The working principle of fuel cell, polyelectrolyte film need With isolation fuel and oxygen, isolation electronics and proton conducting ability, while require its with preferable dimensional stability, Mechanical performance, thermal stability and antioxidative stabilizer.It is widely used at present and the proton exchange membrane being commercialized is mainly the U.S. The Nafion series membranes of DuPont production, proton-conducting and chemical stability are very excellent.However, in use Can generate toxic fluoride when waste processing and cause environmental pollution, and preparation process is complicated, expensive, fuel Permeability height causes fuel battery performance to decline, these all limit the extensive use of Nafion membrane.
Sulfonated polyether sulphone quasi polymer membrane material has good mechanical performance, chemical stability and thermal stability, especially It is compared with Nafion membrane, and methanol permeability is low, cheap, and discarded sulfonated polyether sulphone film is easy degradation, will not Pollution is generated to environment, thus is expected to become the novel polyelectrolyte membrane material of substitution Nafion membrane.However, virtue poly- for sulfonation For ether sulfone class membrane material, when sulfonation degree is higher, film can largely absorb water and excessively be swollen and even dissolve, and cause methanol crossover tight Weight, mechanical performance decline, reduces the service life.And sulfonation degree it is low when, the water content in proton conductivity and film is not able to satisfy again Requirement.By being introduced into ionomer structure into film, a kind of effective modified method is had proven to be.By utilizing alkali Property group and acidic-group form ionic bond, form fine and close membrane structure, membrane material effectively inhibited excessively to be swollen, high membrane material Mechanical performance and chemical stability, while the transmission of fuel can be hindered.In the present invention, pyridine groups are introduced directly into poly- In the main chain for closing object, the sulfonated poly aryl ether ketone containing pyridine groups is prepared.Pyridine groups are a kind of alkali molecules structures, it can be with With sulfonic acid group effective interaction on main polymer chain, ionic bond is formed, to improve the comprehensive performance of membrane material.
Summary of the invention
The present invention is from the angle of molecular structure, by Design and optimization chemical structure, is prepared for the sulphur containing pyridine groups Change polyarylether sulfone copolymer, and provides application of the type material in terms of polymer dielectric film material.
The obtained sulfonated polyether sulfone copolymer containing pyridine groups of the present invention is by following four structures alone with list Key connection is constituted, as follows:
Wherein AR1For any one in following structural formula:
Wherein AR2For any one in following structural formula:
Its reaction equation is as follows:
The preparation method of the above-mentioned sulfonated polyether sulfone copolymer containing pyridine groups, its step are as follows:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added a mol it is bis- Phenol monomer, b mol dichloropyridine monomer, 4,4 '-dichloro diphenyl sulfone of c mol, 3,3 '-sodium disulfonate -4 d mol, 4 '-dichloros Diphenyl sulphone (DPS), using 1.05a~1.5a mol potassium carbonate or sodium carbonate as salt forming agent, with dimethylformamide, dimethyl acetamide, N- Methyl pyrrolidone, dimethyl sulfoxide or sulfolane are solvent, and using toluene or dimethylbenzene as water entrainer, reaction system solid content is 15%~30%；At 120 DEG C~140 DEG C with water 3~6 hours, water entrainer is then steamed, then be warming up to 140 DEG C~200 DEG C continuation Reaction 6~30 hours；It is poured the mixture into after fully reacting in distilled water or acetone, obtains yellowish color strip-shaped solid, be ground into It uses acetone washing 3~5 times, then is washed with distilled water 3~5 times after fine powder；It is finally dried at 60 DEG C~80 DEG C to get to containing pyrrole The sulfonated polyether sulfone copolymer of piperidinyl group.
In above-mentioned steps, a=b+c+d；By controlling the ratio of b and c+d, pyridine groups in adjustable polymer Content, and a > b > 0；By controlling the ratio of d and b+c, the sulfonation degree of adjustable polymer, and a > d > 0, a > c > 0, 2 > 2d/a > 0, sulfonation degree 2d/a.
Wherein, selected dichloropyridine monomer be 2,3- dichloropyridine, 2,4- dichloropyridines, 2,5- dichloropyridines, 2, 6- dichloropyridine, 3,4- dichloropyridines, one of 3,5- dichloropyridines, structure is as follows:
Wherein, selected biphenol monomer be tetramethyl biphenyl diphenol, it is hydroquinone, '-biphenyl diphenol, hexafluoro bisphenol-a, double Phenol A, phenyl hydroquinone, trifluoromethyl hydroquinone, 4,4 '-dihydroxydiphenylsulisomers, in 4,4 '-dihydroxy benaophenonels One kind, structure is as follows:
The application of the invention further relates to the described sulfonated polyether sulfone copolymer containing pyridine groups, particular as polymer Membrane materials for electrolyte is applied in fuel cell.
Sulfonated polyether sulphone co-polymer membrane material prepared by the present invention containing pyridine groups have preferable dimensional stability, Lower methanol permeability and higher antioxidative stabilizer and good proton conductivity, thus it is electric with traditional fragrant adoption Solution plasma membrane is compared, and is a kind of novel polymer dielectric film material haveing excellent performance, being capable of dielectric film in a fuel cell Field has a good application prospect.
Specific embodiment
Embodiment 1:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.1mol it is bis- Phenol A, 0.02mol 2,3- dichloropyridine, 4,4 '-dichloro diphenyl sulfone of 0.03mol, 3,3 '-sodium disulfonate -4 0.05mol, 4 ' - Dichloro diphenyl sulfone, using 1.05mol potassium carbonate as salt forming agent, using dimethylformamide as solvent, using toluene as water entrainer；120 DEG C band water 3 hours, water entrainer is then steamed, then be warming up to 140 DEG C the reaction was continued 20 hours；It is poured the mixture into after fully reacting In distilled water, yellowish color strip-shaped solid is obtained, is ground into after fine powder with acetone washing 3 times, then be washed with distilled water 3 times；Finally It dries at 60 DEG C to get the sulfonated polyether sulfone copolymer containing pyridine groups for being 1.0 to sulfonation degree.
Embodiment 2:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.1mol six Fluorine bisphenol-A, 0.03mol 2,4- dichloropyridine, 4,4 '-dichloro diphenyl sulfone of 0.03mol, 3,3 '-sodium disulfonate -4 0.04mol, 4 '-dichloro diphenyl sulfones, using 1.1mol sodium carbonate as salt forming agent, using dimethyl acetamide as solvent, using dimethylbenzene as water entrainer；? 120 DEG C band water 4 hours, then steam water entrainer, then be warming up to 150 DEG C the reaction was continued 16 hours；By mixture after fully reacting It pours into acetone, obtains yellowish color strip-shaped solid, be ground into after fine powder with acetone washing 5 times, then be washed with distilled water 5 times；Most It dries afterwards at 80 DEG C to get the sulfonated polyether sulfone copolymer containing pyridine groups for being 0.8 to sulfonation degree.
Embodiment 3:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.1mol pairs Benzenediol, 0.01mol 2,5- dichloropyridine, 4,4 '-dichloro diphenyl sulfone of 0.02mol, 3,3 '-sodium disulfonate -4 0.06mol, 4 '-dichloro diphenyl sulfones, using 1.2mol potassium carbonate as salt forming agent, using N-Methyl pyrrolidone as solvent, using toluene as water entrainer；? 130 DEG C band water 5 hours, then steam water entrainer, then be warming up to 170 DEG C the reaction was continued 14 hours；By mixture after fully reacting It pours into distilled water, obtains yellowish color strip-shaped solid, be ground into after fine powder with acetone washing 4 times, then be washed with distilled water 4 times； Finally dry at 70 DEG C to get the sulfonated polyether sulfone copolymer containing pyridine groups for being 1.2 to sulfonation degree.
Embodiment 4:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.1mol tri- Trifluoromethylphenyl hydroquinone, 0.04mol 2,6- dichloropyridine, 4,4 '-dichloro diphenyl sulfone of 0.01mol, 0.05mol 3,3 '- 4,4 '-dichloro diphenyl sulfone of sodium disulfonate-, using dimethyl sulfoxide as solvent, is with dimethylbenzene using 1.3mol sodium carbonate as salt forming agent Water entrainer；120 DEG C band water 3 hours, then steam water entrainer, then be warming up to 170 DEG C the reaction was continued 18 hours；After fully reacting It pours the mixture into acetone, obtains yellowish color strip-shaped solid, be ground into after fine powder with acetone washing 3 times, then washed with distillation It washs 3 times；Finally dry at 60 DEG C to get the sulfonated polyether sulfone copolymer containing pyridine groups for being 1.0 to sulfonation degree.
Embodiment 5:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.1mol connection Benzenediol, 0.05mol 3,4- dichloropyridine, 4,4 '-dichloro diphenyl sulfone of 0.02mol, 3,3 '-sodium disulfonate -4 0.03mol, 4 '-dichloro diphenyl sulfones, using 1.4mol potassium carbonate as salt forming agent, using sulfolane as solvent, using toluene as water entrainer；In 140 DEG C of bands Water 4 hours, water entrainer is then steamed, then is warming up to 200 DEG C the reaction was continued 6 hours；Distillation is poured the mixture into after fully reacting In water, yellowish color strip-shaped solid is obtained, is ground into after fine powder with acetone washing 5 times, then be washed with distilled water 5 times；Finally 80 It dries at DEG C to get the sulfonated polyether sulfone copolymer containing pyridine groups for being 0.6 to sulfonation degree.
Embodiment 6:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added 0.1mol benzene Base hydroquinone, 0.06mol 3,5- dichloropyridine, 4,4 '-dichloro diphenyl sulfone of 0.02mol, 3,3 '-disulfonic acid of 0.02mol 4,4 '-dichloro diphenyl sulfone of sodium-, using dimethylformamide as solvent, is band water with dimethylbenzene using 1.5mol sodium carbonate as salt forming agent Agent；120 DEG C band water 6 hours, then steam water entrainer, then be warming up to 150 DEG C the reaction was continued 30 hours；It will be mixed after fully reacting It closes object to pour into acetone, obtains yellowish color strip-shaped solid, be ground into after fine powder with acetone washing 4 times, then be washed with distilled water 4 It is secondary；Finally dry at 70 DEG C to get the sulfonated polyether sulfone copolymer containing pyridine groups for being 0.4 to sulfonation degree.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that those skilled in the art Member can be designed that a lot of other modification and implementations, these modifications and implementations will fall in principle disclosed in the present application Within scope and spirit.

Claims (3)

1. the preparation method of the sulfonated polyether sulfone copolymer containing pyridine groups,
The sulfonated polyether sulfone copolymer containing pyridine groups is to be connected and composed by following four structures alone with singly-bound,
Wherein AR1For any one in following structural formula:
Wherein AR2For any one in following structural formula:
It is characterized by comprising following steps:
Equipped with mechanical agitator, water-taker, thermometer, condenser pipe, nitrogen protection there-necked flask in, be added a mol bis-phenol list Body, b mol dichloropyridine monomer, 4,4 '-dichloro diphenyl sulfone of c mol, 3,3 '-sodium disulfonate -4 d mol, 4 '-dichloros Sulfone, using 1.05a~1.5a mol potassium carbonate or sodium carbonate as salt forming agent, with dimethylformamide, dimethyl acetamide, N- methyl Pyrrolidones, dimethyl sulfoxide or sulfolane are solvent, and using toluene or dimethylbenzene as water entrainer, reaction system solid content is 15% ~30%；120 DEG C~140 DEG C band water 3~6 hours, then steam water entrainer, then be warming up to 140 DEG C~200 DEG C the reaction was continued 6~30 hours；It is poured the mixture into after fully reacting in distilled water or acetone, obtains yellowish color strip-shaped solid, be ground into fine powder It uses acetone washing 3~5 times, then is washed with distilled water 3~5 times afterwards；It is finally dried at 60 DEG C~80 DEG C to get to containing pyridyl group The sulfonated polyether sulphone of group；
Wherein, a=b+c+d；By controlling the ratio of b and c+d, the content of pyridine groups in adjustable polymer, and a > b > 0；By controlling the ratio of d and b+c, the sulfonation degree of adjustable polymer, and 0,2 > 2d/a > 0 of a > d > 0, a > c >, Sulfonation degree is 2d/a.
2. the preparation method of the sulfonated polyether sulfone copolymer containing pyridine groups as described in claim 1, it is characterised in that: institute The dichloropyridine monomer of selection be 2,3- dichloropyridine, 2,4- dichloropyridines, 2,5- dichloropyridines, 2,6- dichloropyridines, 3,4- Dichloropyridine, one of 3,5- dichloropyridines, structure is as follows:
3. the preparation method of the sulfonated polyether sulfone copolymer containing pyridine groups as described in claim 1, it is characterised in that: institute The biphenol monomer of selection is tetramethyl biphenyl diphenol, hydroquinone, '-biphenyl diphenol, hexafluoro bisphenol-a, bisphenol-A, phenyl to benzene two Phenol, trifluoromethyl hydroquinone, 4, one of 4 '-dihydroxydiphenylsulisomers, 4,4'-Dihydroxybenzophenone, structure is such as Under:
CN201611065449.1A 2016-11-28 2016-11-28 Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application Active CN106750301B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611065449.1A CN106750301B (en) 2016-11-28 2016-11-28 Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611065449.1A CN106750301B (en) 2016-11-28 2016-11-28 Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application

Publications (2)

Publication Number Publication Date
CN106750301A CN106750301A (en) 2017-05-31
CN106750301B true CN106750301B (en) 2019-03-22

Family

ID=58902065

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611065449.1A Active CN106750301B (en) 2016-11-28 2016-11-28 Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application

Country Status (1)

Country Link
CN (1) CN106750301B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109929112A (en) * 2019-03-11 2019-06-25 长春工业大学 New pyridine graft sulfonation poly(aryl ether ketone) sulfone proton exchange membrane and preparation method thereof
CN113004512B (en) * 2019-12-20 2021-11-02 中国科学院大连化学物理研究所 Polymer and preparation method and application thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103087337B (en) * 2011-11-01 2015-08-05 清华大学 A kind of poly-pyrrole throat/sulfonated polymer composite proton exchange membrane material and preparation method thereof and application
CN103788374A (en) * 2012-10-29 2014-05-14 中国石油化工股份有限公司 Sulfonated polyarylether sulfone and preparation method thereof, and reverse osmosis membrane and making method thereof
KR101995527B1 (en) * 2012-12-28 2019-07-02 코오롱인더스트리 주식회사 Reinforced composite membrane for fuel cell and membrane-electrode assembly for fuel cell comprising the same
CN105524268B (en) * 2016-02-18 2017-09-15 中国工程物理研究院化工材料研究所 Sulfonated polyether ketone copolymers of the group containing benzothiazole and preparation method thereof
CN105789667B (en) * 2016-03-17 2018-02-02 常州大学 A kind of side chain is containing more Sulfonic acid structures poly (aryl ether sulfone ketone) proton exchange membrane materials and preparation method thereof

Also Published As

Publication number Publication date
CN106750301A (en) 2017-05-31

Similar Documents

Publication Publication Date Title
Li et al. Polymer electrolyte membranes derived from new sulfone monomers with pendent sulfonic acid groups
Shang et al. Synthesis and characterization of sulfonated fluorene-containing poly (arylene ether ketone) for proton exchange membrane
Nakabayashi et al. Polymer electrolyte membranes based on cross-linked highly sulfonated multiblock copoly (ether sulfone) s
JP5740030B2 (en) Copolymer of sulfonated polyethersulfone containing hydroxy group and method for producing the same, polymer electrolyte membrane for fuel cell, and membrane electrode assembly including the same
CN102585204B (en) Side-chain sulfonic acid type polyarylether, preparation method thereof and application of polyarylether in preparation of proton exchange membrane
CN103113589B (en) Side-chain sulfonated polyaryletherketone sulphone as well as preparation method and application
TWI403537B (en) Polymer electrolyte membrane
CN101161639A (en) Solid acid, polymer electrolyte membrane including the same, and fuel cell using the polymer electrolyte membrane
CN105418921A (en) Cross-linkable polyimide with high sulfonation degree as well as preparation method and application thereof in proton exchange membranes
CN106750301B (en) Sulfonated polyether sulfone copolymer containing pyridine groups, preparation method and application
CN103642032B (en) Containing the branched sulphonated polyaryletherketone of benzoxazole ring side base, preparation method and application thereof
CN105601906B (en) Sulfonated poly aryl ether ketone cross linking membrane of sulfur-bearing ehter bond and preparation method thereof
CN102120874A (en) Sulfonated polyarylether polymer ion exchange membrane containing crosslinking groups and application thereof
CN107805302B (en) A kind of fluorine-containing sulfonated polyether compound of long side chain type and preparation method thereof based on bisphenol S
Zhang et al. Novel sulfonated poly (ether ether ketone ketone) s for direct methanol fuel cells usage: Synthesis, water uptake, methanol diffusion coefficient and proton conductivity
CN1233626C (en) Sulfonated monomer, polymer and its synthesis method
KR101223708B1 (en) Tri-block Copolymer and Electrolyte Membrane Made from the Same
CN106750191B (en) Sulfonated polyether ketone copolymers of the main chain containing pyridine groups, preparation method and application
CN1291973C (en) 1,3-di(3-sodium sulfonate group-4-fluoro-benzoyl) benzene and polymers and their synthesis method
KR101286265B1 (en) Sulfonated poly(sulfone-ketone) copolymer, polymer electrolyte comprising the same, and mehtod for preparing the same
CN100358935C (en) Sulfonated polyether ketone copolymer and its synthesis
CN100528935C (en) Sulfonated copolymer synthetized by 1,3-2(3-diisobutyl sodium-4-fluroben-formoyl) and its method
JP2014071971A (en) Solid polymer electrolyte membrane and fuel cell using the same
CN105542150B (en) Sulfonated polyether ketone copolymers of the side base containing benzothiazole and preparation method thereof
CN109988278A (en) A method of improving polyether-ether-ketone sulfonation degree

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant