CN118146472A - Ether-free copolymer, sulfonated aromatic polymer, ion exchange membrane and preparation method thereof - Google Patents
Ether-free copolymer, sulfonated aromatic polymer, ion exchange membrane and preparation method thereof Download PDFInfo
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- CN118146472A CN118146472A CN202410585212.4A CN202410585212A CN118146472A CN 118146472 A CN118146472 A CN 118146472A CN 202410585212 A CN202410585212 A CN 202410585212A CN 118146472 A CN118146472 A CN 118146472A
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 70
- 229920000642 polymer Polymers 0.000 title claims abstract description 70
- 229920001577 copolymer Polymers 0.000 title claims abstract description 50
- 239000003014 ion exchange membrane Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 150000002576 ketones Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 230000001376 precipitating effect Effects 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- JHNLZOVBAQWGQU-UHFFFAOYSA-N 380814_sial Chemical compound CS(O)(=O)=O.O=P(=O)OP(=O)=O JHNLZOVBAQWGQU-UHFFFAOYSA-N 0.000 claims 1
- 229910001456 vanadium ion Inorganic materials 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 17
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 14
- 229920005597 polymer membrane Polymers 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- KZJRKRQSDZGHEC-UHFFFAOYSA-N 2,2,2-trifluoro-1-phenylethanone Chemical compound FC(F)(F)C(=O)C1=CC=CC=C1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000010220 ion permeability Effects 0.000 description 5
- 238000005580 one pot reaction Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 3
- HUUPVABNAQUEJW-UHFFFAOYSA-N 1-methylpiperidin-4-one Chemical compound CN1CCC(=O)CC1 HUUPVABNAQUEJW-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000012864 cross contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
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
- C08G10/00—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or halogenated aromatic hydrocarbons only
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/18—Condensation polymers of aldehydes or ketones with aromatic hydrocarbons or their halogen derivatives only
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Ether-free copolymers, sulfonated aromatic polymers, ion exchange membranes and methods of making the same. Relates to the technical field of ion exchange membrane materials, and solves the problem that the polymer skeleton of the existing ion exchange membrane is easy to crack and age due to attack of vanadium ions. The ether-free copolymer is polymerized by aromatic monomer Ar and ketone monomer. Completely dissolving an aromatic monomer Ar in dichloromethane, cooling to 0 ℃, adding a ketone monomer, then dropwise adding an acid catalyst for catalytic polymerization, controlling the solid content to be 20% -30%, and mechanically stirring for 1-2 days at room temperature to obtain a viscous polymer solution; and (3) precipitating the polymer by immersing the product in ethanol, and washing and drying to obtain the ether-free copolymer. The ion exchange membrane prepared by the synthesis process can be prepared at kilogram level, and has remarkable commercialization potential.
Description
Technical Field
The invention relates to the technical field of ion exchange membrane materials, in particular to an ether-free copolymer, sulfonated aromatic polymer, an ion exchange membrane and a preparation method thereof.
Background
Large-scale energy storage facilities are key to solving the problems of renewable energy source intermittence, instability and the like. Various energy storage technologies have been developed in recent years, including compressed air, pumped storage, supercapacitors, solid state batteries, etc., but the problems of poor flexibility, low safety, short life, etc. have limited the widespread use of these energy storage technologies.
The flow battery (RFB) technology has the advantages of high energy conversion efficiency, flexible structural design, long service life, adjustable capacity and the like, and becomes one of the most promising technologies suitable for large-scale electrochemical energy storage application. Among them, vanadium Redox Flow Battery (VRFB) bipolar electrolytes use vanadium ions, which can prevent cross contamination of the electrolytes and can be easily recovered, which is hardly achievable in other RFB technologies. Thus, VRFB is the most developed large-scale flow battery technology. However, many challenges, including high material costs, have hampered market development of VRFB.
Ion Exchange Membranes (IEMs) are one of the key components of VRFB, with costs of 30% -40% of the hardware cost of the battery, and most commercial IEMs are not specifically developed for this application and therefore have specific functional drawbacks. For example, perfluorosulfonic acid membranes (PFSA) are often used for VRFB due to their high conductivity and excellent chemical stability, but they have both high vanadium ion permeability and high cost, which are disadvantageous for large-scale use.
The main function of the IEMs is to isolate the electrolyte of the anode and cathode, prevent the passage of redox active vanadium ions, and conduct ions between the anode and cathode to form a circuit. Its selectivity and conductivity have a great influence on cell performance (such as coulombic efficiency CE, voltage efficiency VE, and energy efficiency EE). IEMs include dense and porous membranes, most RFBs use dense IEMs as polymer electrolytes, but side chain functional IEMs have limited functional sites, and most dense IEMs have severe Trade-off effects between selectivity and conductivity; in addition, when ether linkages are present in the IEMs polymer backbone (e.g., sulfonated polyetheretherketone, sulfonated polyethersulfone, etc.), they are susceptible to attack by high vanadium ions, resulting in membrane rupture and failure.
Therefore, there is a need to design IEMs that meet the following requirements: (i) Reducing ionic resistance to enable operation at higher current densities; (ii) improved barrier properties; (iii) balancing net electrolyte transport to minimize capacity imbalance; (iv) Ensures the chemical stability of the material while being cost competitive with existing membranes.
Disclosure of Invention
In order to solve the problems of the existing ion exchange membranes, the invention provides an ether-free copolymer, a sulfonated aromatic polymer, an ion exchange membrane and a preparation method thereof.
The technical scheme of the invention is as follows:
an ether-free copolymer polymerized from aromatic monomers Ar and ketone monomers;
the aromatic monomer Ar is selected from Wherein x is more than or equal to 0 and less than or equal to 3, and x is an integer;
the ketone monomer is 、/>、/>A mixture of any two or three of (a) wherein A, B, C, D is independently selected from-CH 3、-CF3,/>One of them.
More preferably, the ketone monomer is selected fromAny two or more of them.
The invention also provides a preparation method of the ether-free copolymer, which comprises the following steps:
S1, completely dissolving an aromatic monomer Ar in dichloromethane, cooling to 0 ℃, adding a ketone monomer, then dropwise adding an acid catalyst for catalytic polymerization, controlling the solid content to be 20% -30%, and mechanically stirring for 1-2 days at room temperature to obtain a viscous polymer solution;
S2, precipitating the product into ethanol to precipitate a polymer, and washing and drying to obtain the ether-free copolymer.
When the ketone monomer isAnd/>The reaction scheme is as follows:
；
Wherein a represents the degree of polymerization, m and n represent the percentage content, and m+n=1.
Preferably, the molar ratio of the aromatic monomer Ar to the ketone monomer is 1:1.1 to 1.2.
Preferably, the acid catalyst is one or a mixture of at least two of trifluoromethanesulfonic acid, methanesulfonic acid and Eton reagent;
the volume ratio of the acid catalyst to the dichloromethane is 1:2.
The invention also provides a sulfonated aromatic polymer, which is prepared by taking the ether-free copolymer as a raw material.
The invention also provides a preparation method of the sulfonated aromatic polymer, which comprises the following steps:
And completely dissolving the ether-free copolymer in dichloromethane, dropwise adding fuming sulfuric acid at the temperature of 0 ℃, reacting for 24 hours, then immersing the reaction solution into deionized water to separate out a product, washing the product, and drying to obtain the sulfonated aromatic polymer.
Preferably, concentrated sulfuric acid is added and stirred until apparent uniformity is achieved before the oleum is added dropwise.
Preferably, the volume ratio of the dichloromethane to the concentrated sulfuric acid is 1: 1-2;
the volume ratio of fuming sulfuric acid to concentrated sulfuric acid is 1: 1-4;
The fuming sulfuric acid concentration is 10% -65%.
The invention also provides an ion exchange membrane comprising the sulfonated aromatic polymer.
The invention also provides application of the ion exchange membrane, and particularly application of the ion exchange membrane as a diaphragm in all-vanadium redox flow batteries and organic redox flow batteries.
Compared with the prior art, the invention has the following specific beneficial effects:
1. According to the invention, a series of ultra-high molecular weight polymers with main chains without ether bonds are prepared by copolymerizing low-cost and easily-obtained aromatic hydrocarbon and ketone monomers, and the main chains are successfully functionalized by post-sulfonation reaction, so that the main chain type IEMs without ether bonds with high IEC value and ultra-high molecular weight are obtained, and the ion conduction resistance of the membrane is reduced by using the high IEC value, so that the battery efficiency is improved; the swelling of the ionic membrane in the electrolyte is inhibited by utilizing the ultra-high molecular weight of the ionic membrane, and the permeation of vanadium ions is inhibited; the oxidation resistance stability of the ionic membrane is improved by using the ether-free framework. Compared with a commercial perfluorinated sulfonic acid membrane (such as a Nafion membrane), the sulfonated aromatic ion exchange membrane material has the advantages of high conductivity, low vanadium ion permeability, high size, high chemical stability and the like. The vanadium redox flow battery assembled by the ion exchange membrane has high CE, VE and EE values, the energy efficiency is still higher than 80% under the current density of 200mAcm -2, and the energy efficiency is far higher than that of a commercial perfluorinated sulfonic acid membrane, and in addition, the prepared membrane material can stably run in 1000 rounds of vanadium redox flow battery tests.
2. The ion exchange membrane prepared by the synthesis process can be prepared at kilogram level.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the ether-free copolymer B of example 2;
FIG. 2 is a nuclear magnetic resonance spectrum of the ether-free copolymer C of example 3;
FIG. 3 is a nuclear magnetic resonance spectrum of sulfonated aromatic polymer B-1S in example 2;
FIG. 4 is a nuclear magnetic resonance spectrum of a sulfonated aromatic polymer C-1S in example 3;
FIG. 5 is a gel permeation chromatogram of the ether-free copolymer B of example 2;
FIG. 6 is a gel permeation chromatogram of the ether-free copolymer C of example 3;
FIG. 7 is a nuclear magnetic resonance spectrum of the sulfonated aromatic polymer film C-1S of example 3 before and after 50 days of immersion in 1.7M VO 2 + and 3M H 2SO4 solutions;
FIG. 8 is a graph of vanadium ion permeability measurements for sulfonated aromatic polymer membranes A-1S and commercial perfluorosulfonic acid membranes of example 1;
FIG. 9 is a graphical representation of the results of vanadium ion permeability tests for sulfonated aromatic polymer membranes A-1S and commercial perfluorosulfonic acid membranes of example 1;
FIG. 10 is the sheet resistance and conductivity data for sulfonated aromatic polymer membranes A-1S and commercial perfluorosulfonic acid membranes of example 1;
FIG. 11 is a schematic diagram showing the performance test results of an all-vanadium redox flow battery assembled with sulfonated aromatic polymer membranes A-1S of example 1;
FIG. 12 is a graph showing the performance test results of the all-vanadium redox flow battery assembled by the sulfonated aromatic polymer membrane C-1S of example 3;
FIG. 13 is a schematic diagram showing the results of long-term stability performance test of all-vanadium redox flow battery of sulfonated aromatic polymer A-1S in example 1.
Detailed Description
In order to make the technical solution of the present invention clearer, the technical solution of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention, and it should be noted that the following embodiments are only used for better understanding of the technical solution of the present invention, and should not be construed as limiting the present invention.
Example 1.
Terphenyl (11.5 g,0.05 mol) was weighed into a three-necked flask, 36ml of methylene chloride was added to dissolve the terphenyl completely, trifluoroacetone (5 g,0.045 mol) and trifluoroacetophenone (0.87 g,0.005 mol) were added after the reaction was placed at 0 ℃, 18ml of trifluoromethanesulfonic acid was added dropwise to react for 24 hours to obtain a viscous copolymer solution; precipitating the copolymer solution into ethanol to separate out a polymer, repeatedly washing with ethanol, and drying at 80 ℃ to obtain an ultra-high molecular weight ether-free copolymer A;
Then, the copolymer A (10 g) was dissolved in 50ml of methylene chloride, concentrated sulfuric acid (30 ml) was added, the solution was homogenized by mechanical stirring, 20% by weight fuming sulfuric acid (20 ml) was added dropwise at 0℃for reaction for 24 hours, and the obtained viscous polymer solution was poured into water, washed with ethanol and dried to obtain a sulfonated aromatic polymer A-1S.
The structural formulas of the ether-free copolymer and the sulfonated aromatic polymer are as follows:
。
And (3) film making process: the sulfonated aromatic polymer is dissolved in an N, N-dimethylacetamide or dimethylsulfoxide solvent, and then the polymer solution is cast on a glass plate to be cast into a film.
Example 2.
The procedure of example 1 was followed to convert trifluoroacetophenone to N-methyl-4-piperidone with the feed ratio kept unchanged to give an ether-free copolymer B and a sulfonated aromatic polymer B-1S.
The structural formula is as follows:
。
Example 3.
The procedure of example 1 was followed to change the terphenyl to biphenyl with a constant feed ratio to give an ether-free copolymer C and a sulfonated aromatic polymer C-1S.
The structural formula is as follows:
。
example 4.
The procedure of example 1 was followed to convert terphenyl to 2, 3-dimethyl-2, 3-diphenylbutane with a constant feed ratio to give an ether-free copolymer D and a sulfonated aromatic polymer D-1S.
The structural formula is as follows:
。
Example 5.
Weighing terphenyl (11.5 g,0.05 mol) in a three-neck flask, adding 36ml of methylene chloride to dissolve the terphenyl completely, placing the reaction at 0 ℃, adding trifluoroacetone (5 g,0.045 mol) and trifluoroacetophenone (0.87 g,0.005 mol), dropwise adding 18ml of trifluoromethanesulfonic acid, reacting for 24 hours to obtain a viscous copolymer solution, immersing the copolymer solution in ethanol to precipitate a polymer, repeatedly washing the polymer with ethanol, and drying at 80 ℃ to obtain an ultra-high molecular weight ether-free copolymer A;
Then, the copolymer A (10 g) is dissolved in 50ml of dichloromethane, 20%wt fuming sulfuric acid (50 ml) is dripped at the temperature of 0 ℃ for 24 hours, the obtained viscous polymer solution is poured into water, ethanol is used for washing and drying, and the sulfonated aromatic polymer A-2S with the structural formula being the same as that of A-1S is obtained.
And (3) film making process: the sulfonated aromatic polymer is dissolved in an N, N-dimethylacetamide or dimethylsulfoxide solvent, and then the polymer solution is cast on a glass plate to be cast into a film.
Example 6.
The procedure of example 5 was followed, except that trifluoroacetophenone was changed to N-methyl-4-piperidone, and the feed ratio was kept constant, to obtain an ether-free copolymer B and a sulfonated aromatic polymer B-2S, which had the same structural formula as B-1S. Dissolving the B-2S film was found to be insoluble in the polymer, indicating that this method is not suitable for post sulfonation of the ether-free copolymer B.
Example 7.
The procedure of example 5 was followed to convert terphenyl to biphenyl with a constant feed ratio to give an ether-free copolymer C and a sulfonated aromatic polymer C-2S having the same structural formula as C-1S.
Example 8.
The procedure of example 5 was followed to convert terphenyl to 2, 3-dimethyl-2, 3-diphenylbutane with a constant feed ratio to give an ether-free copolymer D and a sulfonated aromatic polymer D-2S having the same structural formula as D-1S.
Example 9.
Weighing terphenyl (1000 g,4.348 mol) in a three-neck flask, adding 3L of dichloromethane to dissolve the terphenyl completely, placing the reaction at 0 ℃, adding trifluoroacetone (435 g, 3.015 mol) and trifluoroacetophenone (75.69 g,0.435 mol), dropwise adding 1.5L of trifluoromethanesulfonic acid, reacting for 24 hours to obtain a viscous copolymer solution, immersing the copolymer solution in ethanol to precipitate a polymer, repeatedly washing the polymer with ethanol, and drying the polymer solution at 80 ℃ to obtain an ultra-high molecular weight ether-free copolymer A';
then, copolymer A (1000 g) was dissolved in 5L of methylene chloride, concentrated sulfuric acid (2.6L) was added, the solution was homogenized under mechanical stirring, 20% by weight fuming sulfuric acid (1.7L) was added dropwise at 0℃for 24 hours, and the obtained viscous polymer solution was poured into water, washed with ethanol and dried to obtain sulfonated aromatic polymer A '-1S', which had the same structural formula as in example 1.
This example is an example of kilogram-scale production of a sulfonated aromatic polymer, which is inexpensive and readily available in materials, has been able to achieve kilogram-scale production, and is excellent in performance.
Comparative example 1.
The polymerization and functionalization two-step reactions were completed by a one-pot process:
Terphenyl (11.5 g,0.05 mol) was weighed into a three-necked flask, 36ml of methylene chloride was added to dissolve the terphenyl completely, trifluoroacetone (5 g,0.045 mol) and trifluoroacetophenone (0.87 g,0.005 mol) were added after the reaction was placed at 0 ℃, 18ml of trifluoromethanesulfonic acid was added dropwise to react for 24 hours to obtain a viscous copolymer solution;
Then directly adding concentrated sulfuric acid (30 ml), mechanically stirring to make the solution uniform, dropwise adding 20%wt fuming sulfuric acid (20 ml) at 0 ℃ for reaction for 24 hours, pouring the obtained viscous polymer solution into water, washing with ethanol and drying to obtain the sulfonated aromatic polymer A-3S, wherein the structural formula of the sulfonated aromatic polymer A-3S is the same as that of A-1S.
Comparative example 2.
The trifluoroacetophenone was changed to N-methyl-4-piperidone according to the procedure of comparative example 1, and the feed ratio was kept unchanged, to obtain a sulfonated aromatic polymer B-3S, which had the same structural formula as B-1S. The B-3S film was dissolved, and the polymer was found to be insoluble, indicating that the sulfonated aromatic polymer B-3S, which can be used as an ion exchange film, could not be prepared by a one-pot method.
Comparative example 3.
According to the procedure of comparative example 1, the terphenyl was changed to biphenyl with the feed ratio kept unchanged to obtain a sulfonated aromatic polymer C-3S having the same structural formula as C-1S. Dissolving the C-3S film, finding that the polymer is insoluble, indicates that the sulfonated aromatic polymer C-3S which can be used as an ion exchange film cannot be prepared by a one-pot method.
Comparative example 4.
The procedure of comparative example 1 was followed to convert terphenyl to 2, 3-dimethyl-2, 3-diphenylbutane with the feed ratio maintained constant and to sulfonate aromatic polymer D-3S. The D-3S film is dissolved, the polymer is not dissolved, and the method shows that the sulfonated aromatic polymer D-3S cannot be prepared by a one-pot method, and the structural formula of the sulfonated aromatic polymer D-3S is the same as that of the sulfonated aromatic polymer D-1S.
The preparation process of the comparative example is to complete the polymerization and functionalization two-step reaction by a one-pot method, but sometimes the prepared polymer cannot be processed into a film due to the crosslinked state, and the preparation and application of the ion exchange membrane are difficult to realize.
Characterization example.
The ether-free copolymer B obtained in example 2 was subjected to nuclear magnetic resonance hydrogen spectrum test, and the result is shown in FIG. 1; the ether-free copolymer C obtained in example 3 was subjected to nuclear magnetic resonance hydrogen spectrum test, and the results are shown in FIG. 2.
The results of nuclear magnetic resonance hydrogen spectrum test on the sulfonated aromatic polymer B-1S obtained in example 2 are shown in FIG. 3; the results of nuclear magnetic resonance hydrogen spectrum test on the sulfonated aromatic polymer C-1S obtained in example 3 are shown in FIG. 4.
Gel permeation chromatography was performed on the ether-free copolymer B obtained in example 2, and the results are shown in fig. 5; gel permeation chromatography was performed on the sulfonated ether-free copolymer C obtained in example 3, and the results are shown in FIG. 6. As can be seen from gel permeation chromatograms, the ether-free copolymer provided by the application has ultrahigh molecular weight, the number average molecular weight can be up to 17 ten thousand, and the weight average molecular weight can be up to 32 ten thousand.
Effect example.
The nuclear magnetic resonance spectrum of the sulfonated aromatic polymer film C-1S obtained in example 3 before and after soaking in 1.7M VO 2 + and 3M H 2SO4 solution for 50 days is shown in FIG. 7. The nuclear magnetic hydrogen spectrum is not changed before and after soaking, which shows that the sulfonated aromatic polymer without ether bond has excellent chemical stability.
The sulfonated aromatic polymer films A-1S obtained in example 1 and the commercial perfluorosulfonic acid film (Nation 212) were each subjected to a vanadium ion permeability test, and the test chart is shown in FIG. 8. The detection result of the concentration change of vanadium ions is shown in fig. 9, and it can be seen that compared with the commercial perfluorinated sulfonic acid membrane, the sulfonated aromatic polymer A-1S provided by the application has greatly improved vanadium resistance, and can effectively prevent capacity attenuation of the battery.
The sheet resistance and conductivity data for the sulfonated aromatic polymer films A-1S and commercial perfluorosulfonic acid films obtained in example 1 are shown in FIG. 10. As shown in the picture, compared with a commercial perfluorinated sulfonic acid membrane, the sulfonated aromatic polymer membrane A-1S has lower surface resistance and higher conductivity, so that the working efficiency of the battery can be greatly improved, and the energy loss is reduced.
The performance of the all-vanadium redox flow battery assembled by the sulfonated aromatic polymer membrane A-1S obtained in example 1 was tested, and the results of the coulombic efficiency CE, the voltage efficiency VE and the energy efficiency EE tests are shown in FIG. 11. The performance of the all-vanadium redox flow battery assembled by the sulfonated aromatic polymer membrane C-1S obtained in example 3 was tested, and the results of the coulombic efficiency CE, the voltage efficiency VE and the energy efficiency EE tests are shown in FIG. 12. From the above graph, it can be seen that the sulfonated aromatic polymer membrane provided by the application has high energy efficiency, voltage efficiency and coulombic efficiency, and the voltage efficiency and energy efficiency are still higher than 80% at a current density of 200mA cm -2, which benefits from the high IEC value and ultra-high molecular weight.
The long-term stability performance test was conducted on the all-vanadium redox flow battery of the sulfonated aromatic polymer a-1S obtained in example 1, and the results are shown in fig. 13. From the figure, the sulfonated aromatic polymer membrane can stably run in 1000 rounds of all-vanadium flow battery test, which shows that the sulfonated aromatic polymer membrane has excellent chemical stability, and benefits from the main chain polymer skeleton without ether bonds.
Claims (10)
1. An ether-free copolymer is characterized in that the ether-free copolymer is polymerized by aromatic monomers Ar and ketone monomers;
the aromatic monomer Ar is selected from Wherein x is more than or equal to 0 and less than or equal to 3, and x is an integer;
the ketone monomer is Any two or more of them.
2. A process for the preparation of the ether-free copolymer as claimed in claim 1, comprising the steps of:
S1, completely dissolving an aromatic monomer Ar in dichloromethane, cooling to 0 ℃, adding a ketone monomer, then dropwise adding an acid catalyst for catalytic polymerization, controlling the solid content to be 20% -30%, and mechanically stirring for 1-2 days at room temperature to obtain a viscous polymer solution;
S2, precipitating the product into ethanol to precipitate a polymer, and washing and drying to obtain the ether-free copolymer.
3. The method for producing an ether-free copolymer according to claim 2, wherein the molar ratio of the aromatic monomer Ar to the ketone monomer is 1:1.1 to 1.2.
4. The method for producing an ether-free copolymer according to claim 2, wherein the acid catalyst is one or a mixture of at least two of trifluoromethanesulfonic acid, methanesulfonic acid, and eaton's reagent;
the volume ratio of the acid catalyst to the dichloromethane is 1:2.
5. A sulfonated aromatic polymer prepared from the ether-free copolymer of claim 1.
6. A method of preparing a sulfonated aromatic polymer as defined in claim 5, comprising the steps of:
And completely dissolving the ether-free copolymer in dichloromethane, dropwise adding fuming sulfuric acid at the temperature of 0 ℃, reacting for 24 hours, then immersing the reaction solution into deionized water to separate out a product, washing the product, and drying to obtain the sulfonated aromatic polymer.
7. The method of claim 6, wherein concentrated sulfuric acid is added and stirred until the appearance of the product is uniform before the oleum is added dropwise.
8. The method for preparing a sulfonated aromatic polymer according to claim 7, wherein said volume ratio of methylene chloride and concentrated sulfuric acid is 1: 1-2;
the volume ratio of fuming sulfuric acid to concentrated sulfuric acid is 1: 1-4;
The fuming sulfuric acid concentration is 10% -65%.
9. An ion exchange membrane comprising the sulfonated aromatic polymer of claim 5.
10. The use of the ion exchange membrane of claim 9 as a separator in all vanadium flow batteries and organic flow batteries.
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| Title |
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| HUITING LIN: "Highly-conductive proton exchange membrane of sulfonated poly(biphenyl alkylene) copolymers for H2/O2 fuel cell with 2.62 W cm-2 power density", JOURNAL OF MEMBRANE SCIENCE, 24 January 2024 (2024-01-24), pages 122479 * |
| WOO-HYUNG LEE: "Robust Hydroxide Ion Conducting Poly(biphenyl alkylene)s for Alkaline Fuel Cell Membranes", ACS MACRO LETTERS, 16 July 2015 (2015-07-16), pages 814 - 818 * |
| 李婷婷: "主链全碳型芳基聚合物质子交换膜", 化学进展, 7 August 2023 (2023-08-07), pages 1559 - 1578 * |
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