CN114989468B - Main chain polyarylether ion exchange membrane based on spiral ring twisted structure and preparation method thereof - Google Patents
Main chain polyarylether ion exchange membrane based on spiral ring twisted structure and preparation method thereof Download PDFInfo
- Publication number
- CN114989468B CN114989468B CN202210580243.1A CN202210580243A CN114989468B CN 114989468 B CN114989468 B CN 114989468B CN 202210580243 A CN202210580243 A CN 202210580243A CN 114989468 B CN114989468 B CN 114989468B
- Authority
- CN
- China
- Prior art keywords
- dihydroxy
- tetramethyl
- ion exchange
- main chain
- aminated
- 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
Links
Classifications
-
- 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
-
- 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
- C08G65/48—Polymers modified by chemical after-treatment
- C08G65/485—Polyphenylene oxides
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- 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)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Polyethers (AREA)
Abstract
The invention belongs to the technical field of anion exchange membranes, aims to improve the ion transfer performance and the dimensional stability of an anion exchange membrane, and provides a main chain polyarylether ion exchange membrane based on a spiro-twisted structure and a preparation method thereof. The prepared membrane has lower ion exchange groups and still has better ion conductivity, and can be applied to neutral batteries.
Description
Technical Field
The invention belongs to the technical field of anion exchange membranes, and relates to a main chain polyarylether ion exchange membrane based on a spiral ring twisted structure and a preparation method thereof.
Background
Along with the improvement of living standard of people, the demand of people to the energy is continuously increased, the reserves of traditional fossil energy are not enough to satisfy the demands of people, and the burning of a large amount of fossil fuel can cause environmental pollution, so the research of renewable energy is imperative, renewable energy such as wind energy, solar energy, hydroenergy and the like generates electricity, the problem of discontinuous and unstable restriction factors is existed, the impact can be caused to the electric wire netting, and the development and utilization of safe and reliable electric energy storage technology is very necessary. Redox Flow Batteries (RFBs) have attracted considerable attention in recent years as one of the most promising large energy storage systems. The main components of the device consist of an electrode, an electrolyte and a membrane. Among these, the membrane is one of the most important components, which not only affects the overall cycle performance, but also determines the economic viability of the system. The membrane separates the positive and negative half-cells and prevents cross-contamination of the active species in the bipolar electrolyte while providing the required ionic conductivity. The ideal membrane should have high ionic conductivity, low water absorption, swelling rate and permeability of the active substance; good chemical stability and low cost. Conventional ion exchange membranes such as QA-PAEK membranes reported by Dongyang Chen and Michael A.Hickner in Macromolecules and QAPS membranes reported by Jung Pan, yao Li, et al in Energy Environ, all have high electrical conductivity, but have a problem of large swelling rate due to too high water absorption rate of the ion exchange group. It is therefore of current interest to find polymers with high conductivity at lower ion exchange groups.
Disclosure of Invention
The invention aims to ensure that the ion transfer performance of an anion exchange membrane is improved under the condition of having lower ion exchange groups, and provides a preparation method of a main chain polyarylether ion exchange membrane based on a spiro twisted structure, which comprises the following steps: the polyarylether polymer with the main chain containing the spiro distorted structure and large steric hindrance is synthesized, and then the polymer is quaternized to obtain the polyarylether functionalized polymer with the main chain containing the spiro distorted structure, and a membrane is prepared. The prepared membrane has high ionic conductivity under relatively low ion exchange groups, and can be applied to neutral aqueous organic flow batteries.
The technical scheme of the invention is as follows:
a polyarylether ion exchange membrane based on a spiro-distorted main chain is provided, wherein the structure of the spiro-distorted main chain quaternary ammonium polyarylether is as follows:
wherein: n is a positive number between 0 and 0.5; r is-H/-CH 2 -N-(CH 3 ) 2
A preparation method of a spiro twisted main chain quaternary ammonium type polyarylether ion exchange membrane comprises the following steps:
(1) Synthesis of 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane: dissolving bisphenol A in methanesulfonic acid, and stirring at room temperature for 4 days; pouring the reaction solution into ice water for precipitation, filtering, washing and drying to obtain a crude product, recrystallizing by using absolute ethyl alcohol, cooling, filtering and drying to obtain a product 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral biindane;
the structural formula of the 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane is as follows:
the w/v of the methyl sulfonic acid of the bisphenol A in the reaction solvent is 45 to 65 percent;
(2) Synthesis of aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane: dissolving 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane in absolute ethyl alcohol, sequentially adding 37% formaldehyde aqueous solution and 40% dimethylamine aqueous solution, reacting for 24 hours at a certain temperature, filtering, washing and drying the reaction solution to obtain aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane;
the aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane has the following structural formula:
wherein R is-H/-CH 2 -N-(CH 3 ) 2 ；
The 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane: formaldehyde: the molar ratio of dimethylamine is: 1:1 to 10:1 to 10;
the certain temperature is 30-80 ℃;
the w/v of the 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral double indane dissolved in the absolute ethyl alcohol is 14.3 to 16.7 percent;
(3) Synthesis of aminated bisphenol fluorene: dissolving bisphenol fluorene in absolute ethyl alcohol, sequentially adding 37% aqueous solution of formaldehyde and 40% aqueous solution of dimethylamine, reacting for 24 hours at a certain temperature, filtering, washing and drying the reaction solution to obtain a crude product, recrystallizing the crude product with a mixed solution of toluene and absolute ethyl alcohol, cooling, filtering and drying to obtain an aminated bisphenol fluorene monomer;
the aminated bisphenol fluorene has the following structural formula:
wherein R is-H/-CH 2 -N-(CH 3 ) 2 ；
The bisphenol fluorene: formaldehyde: the molar ratio of dimethylamine is: 1:1 to 10:1 to 10;
the certain temperature is 30-80 ℃;
the volume ratio of the toluene to the absolute ethyl alcohol mixed solution is 3:1;
(4) Synthesizing polyarylether based on a spiro twisted functionalized main chain: under the protection of inert gas, dissolving aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane, aminated bisphenol fluorene, perfluorobiphenyl and potassium carbonate in N, N-dimethylacetamide, and reacting at 65 ℃ for a certain time with constant temperature; pouring the reaction solution into a precipitator A, filtering, washing and drying to obtain the main chain polyarylether based on the spiro and twisted structure;
the aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane: aminated bisphenol fluorene: perfluoro biphenyl: the molar ratio of potassium carbonate is x:1-x:1: 2-5, x is less than 0.5;
the w/v of the total mass of the aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bis-indane, aminated bisphenol fluorene and perfluorobiphenyl in the solvent A is 17-25 percent;
the certain time is 8 to 16 hours;
the precipitant A is one of ethanol, methanol and water;
(5) Quaternized polyarylether based on spiro twisted functionalized structural backbone: taking 1 equivalent of the polyarylether polymer based on the spiro and distorted and functionalized main chain obtained in the step (4), adding the polyarylether polymer into DMAC (dimethylacetamide), stirring to form white emulsion, adding 2-8 equivalents of methyl iodide, and reacting at the temperature of 30-50 ℃ for 24-48 hours; slowly pouring the mixed solution into the stirred solution of the solvent C to precipitate a target product, washing the target product for a plurality of times by using the solvent C, performing suction filtration, and drying the target product in a constant-temperature drying oven;
the solvent C is ethyl acetate, acetone or diethyl ether;
(6) Dissolving the quaternized polymer synthesized in the step (5) in a solvent B to prepare a membrane casting solution; dripping the casting solution on a casting glass plate, and fully drying in an oven to prepare the quaternary amination ion exchange membrane based on the spiro and twisted functionalized main chain polyarylether with the thickness of 30-70 m; and stripping the ion exchange membrane from the cast membrane glass plate lightly; soaking the ion exchange membrane in deionized water at room temperature for 12h to remove impurities; then, soaking the ion exchange membrane in 3M NaCl solution for 12h to perform sufficient ion exchange; then soaking the ion exchange membrane in deionized water to remove residual NaCl on the surface of the membrane;
the solvent B is one of N, N-dimethylacetamide and N, N-dimethylformamide;
the w/v of the casting solution is 2.6-2.7%;
the units of w/v are g/ml.
The drying temperature of the film formed in the step (5) is 50-80 ℃, and the time is 6-24 hours.
The invention has the advantages that the polyarylether ion exchange membrane with the main chain of the spiral ring twisted structure applied to the neutral flow battery is designed and prepared through condensation and quaternization reaction. The introduction of the spiro structure into the main chain of the membrane can increase steric hindrance to a certain extent, effectively improve the ion conduction capability of the membrane and enable the membrane to have higher ion conductivity and ion selectivity at the same time. The polyarylether ion exchange membrane with the spiro-twisted main chain prepared by the method can show excellent battery performance, the energy efficiency of the polyarylether ion exchange membrane is far superior to that of a commercial anion exchange membrane such as an AMVN membrane, the polyarylether ion exchange membrane has good stability, the efficiency of the battery does not obviously attenuate after the battery is circulated for 1000 circles, and no obvious quality loss exists after the battery is soaked in an electrolyte solution for 14 days.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Synthesis of 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane: 40g of bisphenol A was dissolved in 70ml of methanesulfonic acid and stirred at room temperature for 4 days; pouring the reaction solution into ice water for precipitation, filtering, washing and drying to obtain a crude product, recrystallizing with absolute ethyl alcohol, recrystallizing, cooling, filtering and drying to obtain a product 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane;
the structural formula of the 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral double indane is as follows:
synthesis of aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane: 5g (16.2 mmol) of 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane is dissolved in 30ml of absolute ethanol, 5ml of 37 percent formaldehyde solution and 6ml of 40 percent dimethylamine aqueous solution are sequentially added, the mixture reacts for 24 hours at 40 ℃, the reaction solution is filtered, washed for 3 times by hot water and then is dried in an oven at 40 ℃ for 24 hours, and white powder is obtained.
The aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane has the formula (R) 1 is-H; r is 2 is-CH 2 -N-(CH 3 ) 2 )：
Synthesis of aminated bisphenol fluorene: 12g (34.2 mmol)Dissolving bisphenol fluorene in 72ml of absolute ethyl alcohol, sequentially adding 18ml of 37 percent formaldehyde solution and 21.6ml of 40 percent dimethylamine aqueous solution, reacting for 24 hours at 40 ℃, filtering the reaction solution, washing for 3 times by hot water and hot absolute methanol, and drying for 24 hours in a 40 ℃ oven to obtain white powder; and (3) mixing the obtained white powder with toluene and absolute ethyl alcohol in a volume ratio of 3:1, recrystallizing, cooling, filtering, and drying in an oven at 40 ℃ for 24h to obtain white powder. The aminated bisphenol fluorene has the following structural formula (R) 1 is-H; r is 2 is-CH 2 -N-(CH 3 ) 2 )：
Synthesizing polyarylether based on a spiro twisted functionalized main chain: aminated 0.0845g (0.2 mmol) aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane, 0.8363g (1.8 mmol) aminated bisphenol fluorene, 0.6603g (2.0 mmol) perfluorobiphenyl and 0.6911g (5.0 mmol) potassium carbonate were dissolved in 9ml solvent N, N-dimethylacetamide under inert gas protection and reacted for 14h with constant temperature at 60 ℃; pouring the reaction solution into absolute ethyl alcohol for precipitation, filtering, washing and drying to obtain a main chain polyarylether DASBP-10 polymer main chain based on a spiro and twisted structure;
quaternization: adding 0.5g of DASBP-10 polymer main chain of the polyarylether polymer based on the spiro-twisted functionalized main chain obtained in the last step into DMAC, stirring to form a transparent solution, adding 0.5ml of methyl iodide, and reacting at 40 ℃ for 24 hours; slowly pouring the mixed solution into a stirred solvent ethyl acetate, washing for several times, performing suction filtration, and drying in a constant-temperature drying oven;
preparing a main chain polyarylether anion exchange membrane based on a spiro twisted functionalized structure: dissolving the DASBP-10 synthesized in the last step into a film casting agent DMAC to obtain a film casting solution with the concentration of 28 g/L; dropwise adding the casting solution onto a casting glass plate, fully drying in an oven, and slightly peeling the polyarylether ion exchange membrane with the main chain of the spiral twisted structure from the casting glass plate; soaking the main chain polyarylether ion exchange membrane with the spiral ring twisted structure in deionized water at room temperature for 12 hours to remove impurities; then, soaking the polyarylether ion exchange membrane with the main chain with the spiral twisted structure in 3M NaCl solution for 12 hours to perform sufficient ion exchange; and then soaking the polyarylether ion exchange membrane with the spiral ring twisted structure main chain in deionized water to remove residual NaCl on the surface of the membrane.
The anion-exchange membrane obtained in this example had the following structure (R) 1 is-H; r 2 is-CH 2 -N-(CH 3 ) 2 )：
Tests show that the prepared polyarylether ion exchange membrane without the main chain with the spiral ring twisted structure has the ionic conductivity of 16.23mS cm at 25 DEG C -1 The water absorption rate was 21.05%, and the swelling degree was 9.3%. In a neutral flow battery, 40mA cm -2 At the time of electrical density, CE was 96.9% and EE was 85.8%. The polyarylether ion exchange membrane with the spiro twisted main chain prepared in the embodiment has higher ion conductivity under the condition of similar ion exchange groups due to the aminated spiro monomer containing the ion exchange groups and large steric hindrance, and the ion conductivity at 25 ℃ is 22.19mS cm -1 The water absorption was 22.7% and the swelling degree was 8.3%. In a neutral flow battery, 40mA cm -2 At the time of electrical sealing, CE was 97.2% and EE was 86.7%. The film showed relatively good performance.
Example 2
5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane, aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane, synthesis of aminated bisphenol fluorenes: same as example 1
Synthesizing polyarylether based on a spiro twisted functionalized main chain: aminated 0.1691g (0.4 mmol) aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindan, 0.7434g (1.6 mmol) aminated bisphenol fluorene, 0.6603g (2.0 mmol) perfluorobiphenyl and 0.6911g (5.0 mmol) potassium carbonate were dissolved in 9ml solvent N, N-dimethylacetamide under inert gas protection and reacted for 14h with constant temperature at 60 ℃; pouring the reaction solution into absolute ethyl alcohol for precipitation, filtering, washing and drying to obtain a main chain polyarylether DASBP-20 polymer main chain based on a spiro-twisted structure;
quaternization: adding 0.5g of DASBP-20 polymer main chain of the polyarylether polymer based on the spiro-distorted and functionalized structure main chain obtained in the previous step into DMAC, stirring to form a transparent solution, adding 0.5ml of iodomethane, and reacting at 40 ℃ for 24 hours; slowly pouring the mixed solution into a stirred solvent ethyl acetate, washing for a plurality of times, carrying out suction filtration, and drying in a constant-temperature drying oven;
preparing a main chain polyarylether anion exchange membrane based on a spiro twisted functionalized structure: dissolving the DASBP-20 synthesized in the last step into a casting film agent DMAC to form a casting film solution with the concentration of 28 g/L; dropwise adding the casting solution onto a casting glass plate, fully drying in an oven, and slightly stripping the polyarylether ion exchange membrane with the main chain of the spiral ring and twisted structure from the casting glass plate; soaking the polyarylether ion exchange membrane with the main chain of the spiral ring and the twisted structure in deionized water at room temperature for 12 hours to remove impurities; then, soaking the polyarylether ion exchange membrane with the main chain with the spiral twisted structure in 3M NaCl solution for 12 hours to perform sufficient ion exchange; and then soaking the polyarylether ion exchange membrane with the spiral ring twisted structure main chain in deionized water to remove residual NaCl on the surface of the membrane.
The anion-exchange membrane obtained in this example had the following structure (R) 1 is-H; r 2 is-CH 2 -N-(CH 3 ) 2 )：
Tests show that the ion conductivity of the polyarylether ion exchange membrane with the spiro twisted main chain prepared in the embodiment at 25 ℃ is 25.89mS cm -1 The water absorption was 26.0% and the swelling degree was 9.1%. In a neutral flow battery, 40mA cm -2 At the time of electrical sealing, CE was 98.0% and EE was 88.4%. The film showed relatively good performance.
Example 3
5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane, aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane, synthesis of aminated bisphenol fluorenes: same as example 1
Synthesis of main chain polyarylether based on spiro distorted and functionalized structure: aminated 0.2536g (0.6 mmol) aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane, 0.6505g (1.4 mmol) aminated bisphenol fluorene, 0.6603g (2.0 mmol) perfluorobiphenyl and 0.6911g (5.0 mmol) potassium carbonate were dissolved in 9ml solvent N, N-dimethylacetamide under inert gas protection and reacted for 14h at 60 ℃ with constant temperature; pouring the reaction solution into absolute ethyl alcohol for precipitation, filtering, washing and drying to obtain a main chain polyarylether DASBP-30 polymer main chain based on a spiro-twisted structure;
quaternization: taking 0.5g of the polyarylether polymer based on the spiro and twisted functionalized main chain obtained in the last step, adding the DASBP-30 polymer main chain into DMAC, stirring to form a transparent solution, adding 0.5ml of methyl iodide, and reacting at 40 ℃ for 24 hours; slowly pouring the mixed solution into a stirred solvent ethyl acetate, washing for several times, performing suction filtration, and drying in a constant-temperature drying oven;
preparing a main chain polyarylether anion exchange membrane based on a spiro twisted functionalized structure: dissolving the DASBP-30 synthesized in the last step into a film casting agent DMAC to form a film casting solution with the concentration of 28 g/L; dropwise adding the casting solution onto a casting glass plate, fully drying in an oven, and slightly peeling the polyarylether ion exchange membrane with the main chain of the spiral twisted structure from the casting glass plate; soaking the main chain polyarylether ion exchange membrane with the spiral ring twisted structure in deionized water at room temperature for 12 hours to remove impurities; then, soaking the polyarylether ion exchange membrane with the main chain with the spiral twisted structure in 3M NaCl solution for 12 hours to perform sufficient ion exchange; and then soaking the polyarylether ion exchange membrane with the main chain of the spiral ring twisted structure in deionized water to remove residual NaCl on the surface of the membrane.
The anion-exchange membrane obtained in this example had the following structure (R) 1 is-H; r 2 is-CH 2 -N-(CH 3 ) 2 )：
Tests show that the ion conductivity of the polyarylether ion exchange membrane with the spiro twisted main chain prepared in the embodiment at 25 ℃ is 23.07mS cm -1 The water absorption rate was 23.4% and the swelling degree was 8.5%. In a neutral flow battery, 40mA cm -2 At the time of electrical sealing, CE was 98.3% and EE was 85.7%. The film showed relatively good performance.
Claims (3)
1. A main chain polyarylether ion exchange membrane based on a spiral ring twisted structure is characterized in that the main chain polyarylether based on the spiral ring twisted structure has the following structure:
wherein R is 1 is-H; r 2 is-CH 2 -N-(CH 3 ) 2 。
2. The preparation method of the polyarylether ion exchange membrane based on the spiro twisted main chain is characterized by comprising the following steps:
(1) Synthesis of 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane: dissolving bisphenol A in methanesulfonic acid, and stirring at room temperature for 4 days; pouring the reaction solution into ice water for precipitation, filtering, washing and drying to obtain a crude product, recrystallizing with absolute ethyl alcohol, cooling, filtering and drying to obtain a product 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane;
the structural formula of the 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral double indane is as follows:
the w/v of the bisphenol A in the methanesulfonic acid is 45-65 percent;
(2) Synthesis of aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane: dissolving 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane in absolute ethanol, sequentially adding 37wt.% of formaldehyde aqueous solution and 40wt.% of dimethylamine aqueous solution, reacting for 24 hours under a certain temperature condition, filtering, washing and drying the reaction solution to obtain aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bisindane;
the aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane has the following structural formula:
wherein R is 1 is-H; r is 2 is-CH 2 -N-(CH 3 ) 2 ；
The 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane: formaldehyde: the molar ratio of dimethylamine is: 1:1 to 10:1 to 10;
the certain temperature is 30-80 ℃;
the w/v of the 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral double indane dissolved in the absolute ethyl alcohol is 14.3 to 16.7 percent;
(3) Synthesis of aminated bisphenol fluorene: dissolving bisphenol fluorene in absolute ethyl alcohol, sequentially adding 37wt.% of formaldehyde aqueous solution and 40wt.% of dimethylamine aqueous solution, reacting for 24 hours at a certain temperature, filtering, washing and drying the reaction solution to obtain a crude product, recrystallizing the crude product with a mixed solution of toluene and absolute ethyl alcohol, cooling, filtering and drying to obtain an aminated bisphenol fluorene monomer;
the aminated bisphenol fluorene has the following structural formula:
wherein R is 1 is-H; r 2 is-CH 2 -N-(CH 3 ) 2 ；
The bisphenol fluorene: formaldehyde: the molar ratio of dimethylamine is: 1:1 to 10:1 to 10;
the certain temperature is 40-80 ℃;
the volume ratio of the toluene to the absolute ethyl alcohol mixed solution is 3:1;
(4) Synthesizing polyarylether based on a spiro twisted functionalized main chain: under the protection of inert gas, dissolving aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane, aminated bisphenol fluorene, perfluorobiphenyl and potassium carbonate in N, N-dimethylacetamide, and keeping the temperature constant at 65 ℃ for reaction for a certain time; pouring the reaction solution into a precipitator A, filtering, washing and drying to obtain the main chain polyarylether based on the spiro twisted structure;
the aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-helical bis-indan: aminated bisphenol fluorene: perfluoro biphenyl: the molar ratio of potassium carbonate is x:1-x:1:2 to 5, x is less than 0.5;
the w/v of the total mass of the aminated 5, 5-dihydroxy-3, 3-tetramethyl-1, 1-spiral bisindane, aminated bisphenol fluorene and perfluorobiphenyl in the solvent A is 17-25 percent;
the certain time is 8 to 16 hours;
the precipitant A is one of ethanol, methanol and water;
(5) Quaternized polyarylether based on spiro twisted functionalized structural backbone: adding 1 equivalent of the polyarylether polymer based on the spiro-twisted functionalized main chain obtained in the step (4) into DMAC (dimethylacetamide), stirring to form white emulsion, adding 2-8 equivalents of methyl iodide, and reacting at 30-50 ℃ for 24-48 h; slowly pouring the mixed solution into the stirred solution of the solvent C to precipitate a target product, washing the target product for a plurality of times by using the solvent C, performing suction filtration, and drying the target product in a constant-temperature drying oven;
the solvent C is ethyl acetate, acetone or diethyl ether;
(6) Dissolving the quaternized polymer synthesized in the step (5) in a solvent B to prepare a membrane casting solution; dripping the casting solution on a casting glass plate, and fully drying in a drying oven to prepare the quaternary amination ion exchange membrane based on the main chain polyarylether with the thickness of 30-70 m and the spirocyclic distortion functionalized structure; and stripping the ion exchange membrane from the cast glass plate lightly; soaking the ion exchange membrane in deionized water at room temperature for 12h to remove impurities; then, soaking the ion exchange membrane in 3M NaCl solution for 12h to perform sufficient ion exchange; then soaking the ion exchange membrane in deionized water to remove residual NaCl on the surface of the membrane;
the solvent B is one of N, N-dimethylacetamide and N, N-dimethylformamide;
the w/v of the casting solution is 2.6-2.7%;
the units of the above w/v are all g/ml.
3. The method according to claim 2, wherein the drying temperature of the film formed in the step (5) is 50 to 80 ℃ for 6 to 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210580243.1A CN114989468B (en) | 2022-05-26 | 2022-05-26 | Main chain polyarylether ion exchange membrane based on spiral ring twisted structure and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210580243.1A CN114989468B (en) | 2022-05-26 | 2022-05-26 | Main chain polyarylether ion exchange membrane based on spiral ring twisted structure and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114989468A CN114989468A (en) | 2022-09-02 |
| CN114989468B true CN114989468B (en) | 2023-02-14 |
Family
ID=83029051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210580243.1A Active CN114989468B (en) | 2022-05-26 | 2022-05-26 | Main chain polyarylether ion exchange membrane based on spiral ring twisted structure and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114989468B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516526A (en) * | 2011-12-01 | 2012-06-27 | 中山大学 | Polyarylether compound containing quaternary ammonium salt side group and fluorenyl and preparation method and application thereof |
| CN109762190A (en) * | 2018-12-28 | 2019-05-17 | 吉林大学 | The polyarylether series anion-exchange membrane material and preparation method thereof of the side chain salt groups of spiro quaternary ammonium containing N- |
| CN110372857A (en) * | 2019-07-29 | 2019-10-25 | 福州大学 | A kind of fluorinated poly arylene ether anion-exchange membrane and preparation method thereof containing three quaternary ammonium salt side chains |
| CN114181053A (en) * | 2021-12-29 | 2022-03-15 | 大连理工大学盘锦产业技术研究院 | Preparation method of diphenol monomer with lateral group containing trifluoromethyl and polyarylether polymer thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6653434B2 (en) * | 2015-09-22 | 2020-02-26 | 国立大学法人山梨大学 | Method for producing anion exchange resin, method for producing electrolyte membrane for fuel cell, method for producing binder for forming electrode catalyst layer, method for producing battery electrode catalyst layer, and method for producing fuel cell |
-
2022
- 2022-05-26 CN CN202210580243.1A patent/CN114989468B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516526A (en) * | 2011-12-01 | 2012-06-27 | 中山大学 | Polyarylether compound containing quaternary ammonium salt side group and fluorenyl and preparation method and application thereof |
| CN109762190A (en) * | 2018-12-28 | 2019-05-17 | 吉林大学 | The polyarylether series anion-exchange membrane material and preparation method thereof of the side chain salt groups of spiro quaternary ammonium containing N- |
| CN110372857A (en) * | 2019-07-29 | 2019-10-25 | 福州大学 | A kind of fluorinated poly arylene ether anion-exchange membrane and preparation method thereof containing three quaternary ammonium salt side chains |
| CN114181053A (en) * | 2021-12-29 | 2022-03-15 | 大连理工大学盘锦产业技术研究院 | Preparation method of diphenol monomer with lateral group containing trifluoromethyl and polyarylether polymer thereof |
Non-Patent Citations (1)
| Title |
|---|
| Design of low dielectric constant and high transparent polyarylate containing spiral ring;Lu, Haoran etal;《Polymer》;20210716;123948 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114989468A (en) | 2022-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11949137B2 (en) | Comb-shaped structure polybenzimidazole anion exchange membrane with high conductivity and preparation method thereof | |
| CN113659180B (en) | Anion exchange membrane containing twisted aryl and ketone monomer, adhesive, preparation and application | |
| CN104877136B (en) | A kind of long-chain branch polysulfones anionic membrane and preparation method thereof | |
| CN109638326B (en) | Preparation method of polybenzimidazole anion exchange membrane | |
| CN108987773B (en) | Trimethylamine functionalized polyaryl indole anion exchange membrane and preparation method thereof | |
| CN109096473B (en) | Aromatic piperidine amphoteric ion exchange membrane without aryl ether bond and preparation method thereof | |
| CN114702635B (en) | Preparation method of Schiff base crown ether polymer and application of Schiff base crown ether polymer in anion exchange membrane | |
| CN115109391B (en) | Preparation method and application of polyarylpiperidine anion-exchange membrane with quaternary ammonium side chain | |
| CN110372902A (en) | A kind of fluorine-containing polyfluorene ether anion-exchange membrane of side chain bi-quaternary ammonium salt ionic | |
| CN110041519B (en) | Long-chain branch poly (arylene ether nitrile) anion exchange membrane and preparation method thereof | |
| CN105622442A (en) | Tert-butyl spirobifluorene compound and preparation method and application thereof | |
| CN114133555A (en) | Preparation method of cross-linked fluorine-containing polyfluorene ether anion exchange membrane | |
| CN110372857B (en) | Fluorine-containing polyarylether anion exchange membrane containing tri-quaternary ammonium salt side chain and preparation method thereof | |
| CN113437341B (en) | Amphoteric ion conduction membrane for flow battery and preparation method thereof | |
| CN113471498B (en) | Multi-quaternary ammonium side long-chain type polysulfone anion-exchange membrane and preparation method thereof | |
| CN110317356B (en) | Multifunctional crosslinking type polyarylene butanedione anion exchange membrane and preparation method thereof | |
| CN114989468B (en) | Main chain polyarylether ion exchange membrane based on spiral ring twisted structure and preparation method thereof | |
| CN107968214B (en) | Hydrophilic long-side-chain alkaline anion exchange membrane and preparation method thereof | |
| US9379406B2 (en) | Method for making anion electrolyte membrane | |
| CN113480741B (en) | Chelating Cu 2+ Preparation method of metal organic framework material and application of metal organic framework material in chitosan composite anion membrane | |
| CN112675927B (en) | Multi-piperazinium functionalized anion exchange membrane and preparation method thereof | |
| CN113501959B (en) | Polyether sulphone polymer for vanadium flow battery and preparation method thereof | |
| CN112708155B (en) | Cyano structure side chain-based sulfonated polyarylether ion exchange membrane and preparation method thereof | |
| CN109232936B (en) | Anion exchange membrane for all-vanadium redox flow battery and preparation method thereof | |
| CN113871671A (en) | Preparation method of multi-cation cross-linked anion exchange membrane |
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 |