CN111072526B - Preparation method of resin monomer for ion exchange membrane - Google Patents
Preparation method of resin monomer for ion exchange membrane Download PDFInfo
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- CN111072526B CN111072526B CN201911367817.1A CN201911367817A CN111072526B CN 111072526 B CN111072526 B CN 111072526B CN 201911367817 A CN201911367817 A CN 201911367817A CN 111072526 B CN111072526 B CN 111072526B
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- ion exchange
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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Abstract
The invention disclosesA method for preparing resin monomer for ion exchange membrane comprises mixing fluorosulfonyl tetrafluoroethyl oxatetrafluoroethane (ICF)2CF2OCF2CF2SO2F) Reacting with a dehalogenating agent in a solvent to give fluorosulfonyl tetrafluoroethyloxafluoroethane (ICF)2CF2OCF2CF2SO2F) The molar ratio of the fluorine-containing monomer to the dehalogenating agent is 0.1-1: 1, the reaction temperature is 20-200 ℃, the reaction time is 2-8 h, and after the reaction is finished, the temperature is reduced, the material is discharged, and the resin monomer fluorine sulfonyl tetrafluoroethyl oxatrifluoroethylene (CF) for the ion exchange membrane is obtained by distillation2=CFOCF2CF2SO2F) And (5) producing the product. The method has the advantages of simple process, easily available raw materials, low cost, environmental protection and easy industrialization.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a resin monomer for an ion exchange membrane.
Background
Perfluorinated ion exchange resins were first developed and commercialized by dupont in the 60's united states in the 20 th century because of their excellent properties, and perfluorinated ion exchange membranes were subsequently successfully used in the chlor-alkali industry. Besides, the perfluorinated ion exchange resin can also be applied to the fields of fuel cells and water treatment.
Although perfluorinated ion exchange membranes have been widely used in the chlor-alkali industry, their scale of production is still small relative to other conventional polymers. When fuel cells are used on a large scale as a new power source, perfluorinated ion exchange membranes will also have a larger scale of demand, which presents a great challenge and opportunity for polymer manufacturers to drive current stage membrane production towards lower cost and better performance. In the application process of the perfluorinated ion exchange membrane, the perfluorinated sulfonic acid ion exchange membrane prepared from the short-chain perfluorinated sulfonic acid ion exchange resin has excellent performance, and becomes a research hotspot.
The structure of the perfluorosulfonic acid ion exchange resin is as follows:
among them, short-chain perfluorosulfonic acid membranes (i.e. when m is 0 and n is 2) exhibit more excellent performance, but the synthesis of sulfonic acid monomers with short side chains often requires multiple reactions to prepare, so that the process is complex and the cost is high, thereby affecting commercialization.
For example, U.S. Pat. No. 4,4940525 reports the replacement of hexafluoropropylene oxide and FCOCF by chloropentafluoropropylene oxide2SO2F reacting to obtain chloro-perfluoroacyl-fluorine, and decarboxylating to obtain CF2=CFOCF2CF2SO2The method of the F monomer comprises the following reaction equation:
the raw material of the monochloro-pentafluoro-epoxy propane is difficult to prepare, so the cost is much higher than that of a long-chain sulfonic acid monomer, and the commercialization is influenced.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a method for preparing an ion exchange resin monomer, which has the advantages of simple process, low cost and easy industrialization.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for preparing resin monomer for ion exchange membrane comprises mixing fluorosulfonyl tetrafluoroethyl oxatetrafluoroethane (ICF)2CF2OCF2CF2SO2F) Reacting with a dehalogenating agent in a solvent, wherein the molar ratio of the fluorosulfonyl tetrafluoroethyl oxa-tetrafluoroethane to the dehalogenating agent is 1: 0.5-2.5, the reaction temperature is 20-200 ℃, the reaction time is 1-10 h, and after the reaction is finished, cooling, discharging and distilling to obtain the resin monomer fluorosulfonyl tetrafluoroethyl oxa trifluoroethylene (CF) for the ion exchange membrane2=CFOCF2CF2SO2F) And (5) producing the product.
In a preferred embodiment of the present invention, the dehalogenation agent is a metal or a metal halide salt in powder form.
In a preferred embodiment of the present invention, the metal is one of zinc, copper, iron and magnesium.
In a preferred embodiment of the present invention, the metal halide salt is one of ferric chloride, cupric iodide, barium chloride and aluminum chloride.
The solvent in the invention can be non-protonic solvents such as ketones, ethers, nitriles, amides and esters. As a preferred embodiment of the present invention, the solvent is one of tetrahydrofuran, acetonitrile, Dimethylformamide (DMF), methyltetrahydrofuran, azomethylpyrrolidone, and ethylene glycol dimethyl ether.
In a preferred embodiment of the present invention, the reaction temperature is 50 to 150 ℃.
In a preferred embodiment of the present invention, the reaction time is 2 to 8 hours.
In a preferred embodiment of the present invention, the molar ratio of the fluorosulfonyl tetrafluoroethyloxyiodoethane to the dehalogenating agent is 1: 0.7-2.
In a preferred embodiment of the present invention, the mass ratio of the solvent to the fluorosulfonyl tetrafluoroethyloxyiodoethane is 0.5 to 1.5: 1.
The invention relates to a preparation method of a resin monomer for an ion exchange membrane, which is ICF2CF2OCF2CF2SO2F is taken as a starting material, and the sulfonic acid membrane monomer (CF) can be prepared by one-step dehalogenation reaction2=CFOCF2CF2SO2F) The product has the advantages of simple process, easily obtained raw materials, atom economy, low cost, environmental protection and easy industrialization. The reaction principle is as follows:
ICF2CF2OCF2CF2SO2F→CF2=CFOCF2CF2SO2F
ICF2CF2OCF2CF2SO2preparation of CF by F dehalogenation2=CFOCF2CF2SO2F, the selection of the dehalogenating agent has great influence on the reaction result, and the dehalogenating agent enables the reaction to be smoothAnd the occurrence of side reactions is reduced.
ICF2CF2OCF2CF2SO2Preparation of CF by F dehalogenation2=CFOCF2CF2SO2F, the variety of the solvent has a great influence on the reaction, and if the protic solvent is selected, more hydrogen head byproducts are generated, so that the product yield is influenced. Therefore, in the present invention, one of aprotic solvents such as tetrahydrofuran, acetonitrile, DMF, methyltetrahydrofuran, nitrogen methyl pyrrolidone, and ethylene glycol dimethyl ether is preferable.
ICF2CF2OCF2CF2SO2Preparation of CF by F dehalogenation2=CFOCF2CF2SO2F, the reaction temperature has great influence on the reaction, the hydrogen head and coupling byproducts are more when the temperature is too high, and the reaction is slower or even impossible when the temperature is too low. Therefore, the reaction temperature is 20-200 ℃ and the preferable reaction temperature is 50-150 ℃.
ICF2CF2OCF2CF2SO2Preparation of CF by F dehalogenation2=CFOCF2CF2SO2F, the molar ratio of the fluorosulfonyl tetrafluoroethyl oxatetrafluoroethane to the dehalogenating agent has a certain influence on the reaction, if the molar ratio is too high, the conversion of the raw material is incomplete, and if the molar ratio is too low, more byproducts are generated. Therefore, the molar ratio of the fluorosulfonyl tetrafluoroethyloxyiodoethane to the dehalogenating agent in the present invention is 1:0.5 to 2.5, preferably 1:0.7 to 2.
Compared with the prior art, the invention has the following advantages:
1. the method has the advantages of simple process, easy industrialization, easily obtained raw materials, short steps and industrial value;
2. the method is environment-friendly, can prepare the product by one-step reaction, obviously reduces the three wastes, has atom economy and meets the requirement of environmental protection.
3. The yield is high, and is more than 90 percent, and the highest yield can reach 96 percent.
Detailed Description
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.
Example 1
213g of tetrahydrofuran and 130g (2mol) of zinc powder are added into a 2L stainless steel reaction kettle with a stirrer, the temperature is raised to 50 ℃, 426g of ICF is slowly and continuously added2CF2OCF2CF2SO2F (1mol) reacts for 1h, the reaction is continued for 1h after the feeding is finished, the reaction is stopped, the temperature is reduced and the material is discharged to obtain a crude product, and the crude product is distilled to obtain 257g of a product, the yield is 92 percent, and the purity is 99.5 percent.
Example 2
Adding 639g DMF and 24g (1mol) magnesium powder into a 2L stainless steel reaction kettle with stirring, heating to 150 deg.C, slowly and continuously adding 426g ICF2CF2OCF2CF2SO2F (1mol) reacts for 1h, the reaction is stopped after the reaction is continued for 2h after the feeding is finished, the temperature is reduced and the material is discharged to obtain a crude product, and the crude product is distilled to obtain CF2=CFOCF2CF2SO2252g of F product, yield 90% and purity 99.6%.
Example 3
426g acetonitrile and 95g (1.5mol) copper powder were added to a 2L stainless steel reactor with stirring, the temperature was raised to 120 ℃ and 426g ICF was slowly and continuously added2CF2OCF2CF2SO2F (1mol) reacts for 1h, the reaction is stopped after the reaction is continued for 3h after the feeding is finished, the temperature is reduced and the material is discharged to obtain a crude product, and the crude product is distilled to obtain CF2=CFOCF2CF2SO2254g of F product, 91% yield and 99.5% purity.
Example 4
315g of methyl tetrahydrofuran and 95g (1.7mol) of iron powder are added into a stainless steel reaction kettle with a 2L stirring function, the temperature is raised to 100 ℃, 426g of ICF is slowly and continuously added2CF2OCF2CF2SO2F (1mol) reacts for 1h, the reaction is stopped after the reaction is continued for 4h after the feeding is finished, the temperature is reduced and the material is discharged to obtain a crude product, and the crude product is distilled to obtain CF2=CFOCF2CF2SO2260g of F product, 93 percent of yield and 99.7 percent of purity.
Example 5
525g of N-methyl pyrrolidone and 120g (0.7) of ferric chloride are added into a stainless steel reaction kettle with a 2L stirring function, the temperature is raised to 80 ℃, 426g of ICF is slowly and continuously added2CF2OCF2CF2SO2F (1mol) reacts for 1h, the reaction is stopped after the reaction is continued for 5h after the feeding is finished, the temperature is reduced and the material is discharged to obtain a crude product, and the crude product is distilled to obtain CF2=CFOCF2CF2SO2269g of F product, 96% yield and 99.8% purity.
Example 6
250g of ethylene glycol dimethyl ether and 150g (1.1mol) of copper chloride are added into a stainless steel reaction kettle with a 2L stirrer, the temperature is raised to 60 ℃, 426g of ICF is slowly and continuously added2CF2OCF2CF2SO2F (1mol) reacts for 1h, the reaction is stopped after the reaction is continued for 6h after the feeding is finished, the temperature is reduced and the material is discharged to obtain a crude product, and the crude product is distilled to obtain CF2=CFOCF2CF2SO2263g of F product, 94% of yield and 99.6% of purity.
Example 7
470g of tetrahydrofuran and 170g (0.8mol) of barium chloride are added into a stainless steel reaction kettle with a 2L stirring function, the temperature is raised to 70 ℃, 426g of ICF is slowly and continuously added2CF2OCF2CF2SO2F (1mol) reacts for 1h, the reaction is stopped after the reaction is continued for 7h after the feeding is finished, the temperature is reduced and the material is discharged to obtain a crude product, and the crude product is distilled to obtain CF2=CFOCF2CF2SO2257g of F product, 92% yield and 99.5% purity.
Claims (6)
1. The preparation method of the resin monomer for the ion exchange membrane is characterized by comprising the steps of reacting fluorosulfonyl tetrafluoroethyl oxa-tetrafluoroethane with a dehalogenation agent in a solvent, wherein the molar ratio of the fluorosulfonyl tetrafluoroethyl oxa-tetrafluoroethane to the dehalogenation agent is 1: 0.5-2.5, the reaction temperature is 20-200 ℃, the reaction time is 1-10 hours, cooling, discharging and distilling after the reaction is finished to obtain the resin monomer fluorosulfonyl tetrafluoroethyl oxa-trifluoroethylene product for the ion exchange membrane, wherein the dehalogenation agent is one of powdered ferric chloride, copper iodide, barium chloride and aluminum chloride.
2. The method of preparing a resin monomer for an ion exchange membrane according to claim 1, wherein the solvent is one of tetrahydrofuran, acetonitrile, dimethylformamide, methyltetrahydrofuran, azomethylpyrrolidone, and ethylene glycol dimethyl ether.
3. The method for preparing the resin monomer for the ion exchange membrane according to claim 1, wherein the reaction temperature is 50 to 150 ℃.
4. The method for preparing the resin monomer for the ion exchange membrane according to claim 1, wherein the reaction time is 2-8 h.
5. The method for preparing a resin monomer for an ion exchange membrane according to claim 1, wherein the molar ratio of the fluorosulfonyl tetrafluoroethyloxyethyl iodoethane to the dehalogenating agent is 1: 0.7-2.
6. The method for preparing a resin monomer for an ion exchange membrane according to claim 1, wherein the mass ratio of the solvent to the fluorosulfonyl tetrafluoroethyloxafluoroethane is 0.5-1.5: 1.
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US4275226A (en) * | 1978-08-25 | 1981-06-23 | Asahi Glass Company, Ltd. | Process for producing fluorovinyl ether |
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