Sulfonic acid and phosphonic acid copolymerized ionic polymer as well as preparation method and application thereof
By introducing sulfonic acid groups into perfluorosulfonic acid ionic polymer and synthesizing sulfonic acid phosphonic acid copolymer by using a three-step reaction method, the problem of decreasing ion conductivity of perfluorosulfonic acid ionic polymer in high temperature environment is solved, and efficient fuel cell performance and cost reduction is achieved.
Patent Information
- Application Number
- CN202311663993.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-12-06
- Publication Date
- 2025-06-06
AI Technical Summary
The existing perfluorosulfonic acid ionic polymers cannot guarantee high humidity in high temperature environments, resulting in a significant decrease in their ion conductivity and cannot meet the application requirements of fuel cells.
The sulfonic acid copolymer ionic polymer was synthesized by combining the sulfonic acid group with a perfluorosulfonic acid chlorine polymer or a perfluorosulfonic acid fluoropolymer.
It achieves the maintenance of high ion conductivity under high temperature environments, improves the performance of fuel cells, and reduces the complexity and cost of phosphonic acid monomer synthesis.
Smart Images
Figure CN120098162A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of ionic polymers, and in particular to a sulfonic acid phosphonic acid copolymer ionic polymer and a preparation method and application thereof. Background Art
[0002] Fuel cells are a clean and efficient power generation technology that converts fuel (such as hydrogen) and oxidants (such as oxygen or air) into electrical energy. The key material of fuel cells is the ion exchange membrane. Perfluorosulfonic acid ion polymers are used as exchange membranes. They have good ion conductivity at 80°C and high humidity, but when working in a high temperature environment (such as 120°C), they cannot maintain high humidity, resulting in a significant decrease in their ion conductivity (less than 0.01S / cm), which cannot meet the application requirements. The research on high temperature resistant ion exchange membranes has become a focus at home and abroad. At present, the research is mainly focused on phosphoric acid-doped aromatic heterocyclic polymer ion membranes and their fuel cell systems. Such membranes show strong ion conductivity in high temperature environments, but poor stability (with the loss of phosphoric acid, the ion conductivity decreases significantly). Therefore, phosphoric acid-doped polymer ion membranes also cannot meet the application requirements. In order to solve the problems faced by the above ion membranes, it is an effective method to introduce phosphoric acid groups into perfluorosulfonic acid ion polymers to construct sulfonic acid phosphonic acid copolymer ion exchange membranes, but the complexity of the synthesis of phosphonic acid monomers leads to a significant increase in the cost of the corresponding sulfonic acid phosphonic acid copolymers. Summary of the invention
[0003] The purpose of the present invention is to provide a sulfonic acid phosphonic acid copolymer ion polymer and a preparation method and application thereof.
[0004] The object of the present invention can be achieved by the following technical scheme: a method for preparing a sulfonic acid phosphonic acid copolymer ion polymer, using a perfluorosulfonic acid chloropolymer or a perfluorosulfonic acid fluoropolymer as a raw material, and synthesizing the sulfonic acid phosphonic acid copolymer ion polymer through three steps of reaction;
[0005]
[0006] In the formula, x is an integer of 1 to 20; y is an integer of 1 to 10; x:y=1 to 10; R 1 is selected from fluorine or chlorine; z is an integer from 1 to 10; R 2 is selected from a C1-C20 straight carbon chain or a branched carbon chain; R is selected from the following structural units:
[0007]
[0008] In the formula, m is an integer of 1-5.
[0009] Preferably, the number average molecular weight of the perfluorosulfonic acid chloropolymer or perfluorosulfonic acid fluoropolymer is 200,000 to 800,000.
[0010] More preferably, the number average molecular weight of the perfluorosulfonic acid chloropolymer or perfluorosulfonic acid fluoropolymer is 200,000 to 600,000.
[0011] More preferably, the number average molecular weight of the perfluorosulfonic acid chloropolymer or perfluorosulfonic acid fluoropolymer is 200,000 to 400,000.
[0012] Preferably, the reaction 1 comprises: reacting the polymer of formula I with an iodide salt to obtain the polymer of formula II.
[0013] Further preferably, in the reaction 1, the reaction solution is selected from dimethyl sulfoxide, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide; the iodide salt is selected from sodium iodide, potassium iodide, lithium iodide; the reaction temperature is 0°C-150°C, and the reaction time is 1-24 hours.
[0014] Preferably, the reaction 2 comprises: reacting the polymer of formula II with lithium diisopropylamide and a phosphite diester to obtain the polymer of formula III.
[0015] Further preferably, in the reaction 2, the reaction solution is selected from diethyl ether, tetrahydrofuran, and toluene; the phosphite diester is selected from diethyl phosphite and dimethyl phosphite; the reaction temperature is -80°C to 0°C, and the reaction time is 0.1 to 24 hours.
[0016] Preferably, the reaction 3 comprises: hydrolyzing the polymer of formula III in an inorganic alkali solution, and then acidifying with an inorganic acid to obtain the polymer of formula IV.
[0017] Further preferably, in reaction 3, the reaction solvent is selected from water, dimethyl sulfoxide; the inorganic base is selected from sodium hydroxide, potassium hydroxide, lithium hydroxide; the hydrolysis reaction temperature is 25°C-100°C, and the reaction time is 1-12 hours; the inorganic acid is selected from dilute sulfuric acid, dilute hydrochloric acid; the acidification reaction temperature is 25°C-100°C, and the reaction time is 1-24 hours.
[0018] Preferably, the reaction 1, reaction 2 and reaction 3 are carried out under a protective atmosphere.
[0019] Further preferably, the protective atmosphere includes nitrogen or argon.
[0020] A sulfonic acid phosphonic acid copolymer ion polymer is prepared by adopting the preparation method.
[0021] Preferably, the sulfonic acid phosphonic acid copolymer is selected from the following polymers:
[0022]
[0023] The invention discloses an application of a sulfonic acid phosphonic acid copolymer ion polymer, wherein the sulfonic acid phosphonic acid copolymer ion polymer is used for an ion exchange membrane of a fuel cell.
[0024] Compared with the prior art, the present invention has the following beneficial effects:
[0025] 1. The present invention provides a simple method for synthesizing sulfonic acid phosphonic acid copolymer ion polymer, which can significantly reduce the cost;
[0026] 2. The polymer of the present invention has higher stability than the perfluoroolefin monomer and can significantly increase the yield of the reaction;
[0027] 3. The polymerization reactivity of the perfluorophosphonate monomer and the perfluorosulfonyl fluoride monomer of the present invention is different. Direct modification of the polymer can avoid the complexity and uncontrollability of the polymerization caused by the activity of the monomer. DETAILED DESCRIPTION
[0028] The embodiments of the present invention are described in detail below. The following embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operation processes are given, but the protection scope of the present invention is not limited to the following embodiments.
[0029] The experimental methods shown in the following examples are conventional methods unless otherwise specified; the materials and reagents are purchased from commercial sources unless otherwise specified.
[0030] Example 1
[0031] Preparation of sulfonic acid phosphonic acid copolymer ion polymer P1:
[0032]
[0033] Under nitrogen protection, 1.096 g of polymer 1 (x:y=8, purchased from Dongyue Group) was added to 40 ml of dimethyl sulfoxide, 50 mg of sodium iodide was added, and the mixture was heated to 110°C and kept at the temperature for 6 hours. The reaction solution was poured into ice water, 5 ml of saturated sodium bisulfite aqueous solution was added, and after vigorous stirring for 30 minutes, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 2.
[0034] Under nitrogen protection, the polymer 2 obtained above was added to 50 ml of anhydrous ether, cooled to -30°C, 0.17 ml of lithium diisopropylamide was added dropwise, and after reacting for 30 minutes, 46 mg of diethyl phosphite was added. After reacting for 10 minutes, the reaction was quenched with ammonium chloride, the ether was removed by rotation, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 3.
[0035] Under nitrogen protection, the polymer 3 obtained above was added to a 20% sodium hydroxide aqueous solution, heated to 90°C for reaction for 5 hours to obtain a perfluoro sodium polymer, which was then treated in a 5% sulfuric acid solution at 95°C for 10 hours, during which the sulfuric acid solution was replaced every 1 hour. The obtained hydrogen polymer was washed with deionized water until neutral, and dried in a vacuum drying oven at 80°C for 24 hours to obtain a sulfonic acid phosphonic acid copolymer ion polymer P1. The total yield of the three steps was 87%.
[0036] Example 2
[0037] Preparation of sulfonic acid phosphonic acid copolymer P2:
[0038]
[0039] Under nitrogen protection, 1.096 g of polymer 1 (x:y=8, purchased from Dongyue Group) was added to 40 ml of dimethyl sulfoxide, and 75 mg of sodium iodide was added, and the mixture was heated to 110°C and kept at the temperature for 6 hours. The reaction solution was poured into ice water, and 10 ml of saturated sodium bisulfite aqueous solution was added. After vigorous stirring for 30 minutes, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 4.
[0040] Under nitrogen protection, the polymer 4 obtained above was added to 50 ml of anhydrous ether, cooled to -30°C, 0.26 ml of lithium diisopropylamide was added dropwise, and after reacting for 30 minutes, 69 mg of diethyl phosphite was added. After reacting for 10 minutes, the reaction was quenched with ammonium chloride, the ether was removed by rotation, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 5.
[0041] Under nitrogen protection, the polymer 5 obtained above was added to a 20% sodium hydroxide aqueous solution, heated to 90°C for reaction for 5 hours to obtain a perfluoro sodium polymer, which was then treated in a 5% sulfuric acid solution at 95°C for 10 hours, during which the sulfuric acid solution was replaced every 1 hour. The obtained hydrogen polymer was washed with deionized water until neutral, and dried in a vacuum drying oven at 80°C for 24 hours to obtain a sulfonic acid phosphonic acid copolymer ion polymer P2. The total yield of the three steps was 84%.
[0042] Example 3
[0043] Preparation of sulfonic acid phosphonic acid copolymer P3:
[0044]
[0045] Under nitrogen protection, 1.096 g of polymer 1 (x:y=8, purchased from Dongyue Group) was added to 40 ml of dimethyl sulfoxide, 100 mg of sodium iodide was added, and the mixture was heated to 110°C and kept at the temperature for 6 hours. The reaction solution was poured into ice water, 15 ml of saturated sodium bisulfite aqueous solution was added, and after vigorous stirring for 30 minutes, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 6.
[0046] Under nitrogen protection, the polymer 4 obtained above was added to 50 ml of anhydrous ether, cooled to -30°C, 0.34 ml of lithium diisopropylamide was added dropwise, and after reacting for 30 minutes, 92 mg of diethyl phosphite was added. After reacting for 10 minutes, the reaction was quenched with ammonium chloride, the ether was removed by rotation, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 7.
[0047] Under nitrogen protection, the polymer 7 obtained above was added to a 20% sodium hydroxide aqueous solution, heated to 90°C for reaction for 5 hours to obtain a perfluoro sodium polymer, which was then treated in a 5% sulfuric acid solution at 95°C for 10 hours, during which the sulfuric acid solution was replaced every 1 hour. The obtained hydrogen polymer was washed with deionized water until neutral, and dried in a vacuum drying oven at 80°C for 24 hours to obtain a sulfonic acid phosphonic acid copolymer ion polymer P3. The total yield of the three steps was 88%.
[0048] Example 4
[0049] Preparation of sulfonic acid phosphonic acid copolymer P4:
[0050]
[0051] Under nitrogen protection, 1.279 g of polymer 8 (x:y=8, purchased from Dongyue Group) was added to 30 ml of dimethyl sulfoxide, 50 mg of sodium iodide was added, and the mixture was heated to 80°C and kept at the temperature for 2 hours. The reaction solution was poured into ice water, 5 ml of saturated sodium bisulfite aqueous solution was added, and after vigorous stirring for 30 minutes, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 9.
[0052] Under nitrogen protection, the polymer 9 obtained above was added to 30 ml of anhydrous ether, cooled to -30°C, 0.17 ml of lithium diisopropylamide was added dropwise, and reacted for 30 minutes. Then, 46 mg of diethyl phosphite was added and reacted for 10 minutes. The reaction was quenched with ammonium chloride, the ether was removed by rotation, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 10.
[0053] Under nitrogen protection, the polymer 10 obtained above was added to a 20% sodium hydroxide aqueous solution, heated to 90°C for reaction for 5 hours to obtain a perfluoro sodium polymer, which was then treated in a 5% sulfuric acid solution at 95°C for 10 hours, during which the sulfuric acid solution was replaced every 1 hour. The obtained hydrogen polymer was washed with deionized water until neutral, and dried in a vacuum drying oven at 80°C for 24 hours to obtain a sulfonic acid phosphonic acid copolymer ion polymer P4. The total yield of the three steps was 90%.
[0054] Example 5
[0055] Preparation of sulfonic acid phosphonic acid copolymer P5:
[0056]
[0057] Under nitrogen protection, 1.279 g of polymer 8 (x:y=8, purchased from Dongyue Group) was added to 35 ml of dimethyl sulfoxide, and 75 mg of sodium iodide was added, and the mixture was heated to 80°C and kept at the temperature for 2 hours. The reaction solution was poured into ice water, and 10 ml of saturated sodium bisulfite aqueous solution was added. After vigorous stirring for 30 minutes, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 11.
[0058] Under nitrogen protection, the polymer 11 obtained above was added to 30 ml of anhydrous ether, cooled to -30°C, 0.26 ml of lithium diisopropylamide was added dropwise, and after reacting for 30 minutes, 69 mg of diethyl phosphite was added. After reacting for 10 minutes, the reaction was quenched with ammonium chloride, the ether was removed by rotation, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 12.
[0059] Under nitrogen protection, the polymer 12 obtained above was added to a 20% sodium hydroxide aqueous solution, heated to 90°C for reaction for 5 hours to obtain a perfluoro sodium polymer, which was then treated in a 5% sulfuric acid solution at 95°C for 10 hours, during which the sulfuric acid solution was replaced every 1 hour. The obtained hydrogen polymer was washed with deionized water until neutral, and dried in a vacuum drying oven at 80°C for 24 hours to obtain a sulfonic acid phosphonic acid copolymer ion polymer P5. The total yield of the three steps was 91%.
[0060] Example 6
[0061] Preparation of sulfonic acid phosphonic acid copolymer P6:
[0062]
[0063] Under nitrogen protection, 1.279 g of polymer 8 (x:y=8, purchased from Dongyue Group) was added to 40 ml of dimethyl sulfoxide, 100 mg of sodium iodide was added, and the mixture was heated to 80°C and kept at the temperature for 2 hours. The reaction solution was poured into ice water, 15 ml of saturated sodium bisulfite aqueous solution was added, and after vigorous stirring for 30 minutes, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 13.
[0064] Under nitrogen protection, the polymer 13 obtained above was added to 30 ml of anhydrous ether, cooled to -30°C, 0.34 ml of lithium diisopropylamide was added dropwise, and after reacting for 30 minutes, 92 mg of diethyl phosphite was added. After reacting for 10 minutes, the reaction was quenched with ammonium chloride, the ether was removed by rotation, the solid was filtered, washed three times with 50 ml of distilled water, and dried to obtain polymer 14.
[0065] Under nitrogen protection, the polymer 14 obtained above was added to a 20% sodium hydroxide aqueous solution, heated to 90°C for reaction for 5 hours to obtain a perfluoro sodium polymer, which was then treated in a 5% sulfuric acid solution at 95°C for 10 hours, during which the sulfuric acid solution was replaced every 1 hour. The obtained hydrogen polymer was washed with deionized water until neutral, and dried in a vacuum drying oven at 80°C for 24 hours to obtain a sulfonic acid phosphonic acid copolymer ion polymer P6. The total yield of the three steps was 90%.
[0066] The above description of the embodiments is to facilitate the understanding and use of the invention by those skilled in the art. It is obvious that those skilled in the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the present invention should be within the scope of protection of the present invention.
Claims
1. A method for preparing a sulfonic acid phosphonic acid copolymer ion polymer, It is characterized in that The sulfonic acid phosphonic acid copolymer ion polymer is synthesized by using perfluorosulfonic acid chloropolymer or perfluorosulfonic acid fluoropolymer as raw material through three steps of reaction; In the formula, x is an integer of 1 to 20; y is an integer of 1 to 10; x:y=1 to 10; R 1 is selected from fluorine or chlorine; z is an integer from 1 to 10; R 2 is selected from a C1-C20 straight carbon chain or a branched carbon chain; R is selected from the following structural units: In the formula, m is an integer of 1-5.
2. The method for preparing the sulfonic acid phosphonic acid copolymer according to claim 1, It is characterized in that The reaction 1 comprises: reacting the polymer of formula I with an iodide salt to obtain the polymer of formula II.
3. The method for preparing the sulfonic acid phosphonic acid copolymer according to claim 2, It is characterized in that In the reaction 1, the reaction solution is selected from dimethyl sulfoxide, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide; the iodide salt is selected from sodium iodide, potassium iodide, lithium iodide; the reaction temperature is 0°C-150°C, and the reaction time is 1-24 hours.
4. The method for preparing the sulfonic acid phosphonic acid copolymer according to claim 1, It is characterized in that The reaction 2 comprises: reacting the polymer of formula II with lithium diisopropylamide and a phosphite diester to obtain the polymer of formula III.
5. The method for preparing the sulfonic acid phosphonic acid copolymer according to claim 4, It is characterized in that In the reaction 2, the reaction solution is selected from diethyl ether, tetrahydrofuran, and toluene; the phosphite diester is selected from diethyl phosphite and dimethyl phosphite; the reaction temperature is -80°C to 0°C, and the reaction time is 0.1 to 24 hours.
6. The method for preparing the sulfonic acid phosphonic acid copolymer according to claim 1, It is characterized in that The reaction 3 comprises: hydrolyzing the polymer of formula III in an inorganic alkali solution, and then acidifying with an inorganic acid to obtain the polymer of formula IV.
7. The method for preparing the sulfonic acid phosphonic acid copolymer according to claim 6, It is characterized in that In the reaction 3, the reaction solvent is selected from water and dimethyl sulfoxide; the inorganic base is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide; the hydrolysis reaction temperature is 25°C-100°C and the reaction time is 1-12 hours; the inorganic acid is selected from dilute sulfuric acid and dilute hydrochloric acid; the acidification reaction temperature is 25°C-100°C and the reaction time is 1-24 hours.
8. The method for preparing the sulfonic acid phosphonic acid copolymer according to claim 1, It is characterized in that The reaction 1, reaction 2 and reaction 3 are carried out under a protective atmosphere; The protective atmosphere includes nitrogen or argon.
9. A sulfonic acid phosphonic acid copolymer ion polymer, It is characterized in that The method is prepared according to any one of claims 1 to 8.
10. Use of the sulfonic acid phosphonic acid copolymer ion polymer according to claim 9, wherein the sulfonic acid phosphonic acid copolymer ion polymer is used in an ion exchange membrane for a fuel cell.