Method for preparing perfluorinated organic carboxylic acid compound from perfluorinated organic carboxylic ester

Abstract

The invention relates to the technical field of perfluoro fine chemical engineering, in particular to a method for preparing a perfluoro organic carboxylic acid compound from perfluoro organic carboxylic ester, and particularly relates to a method for preparing a reactive perfluoro organic carboxylic acid compound from perfluoro organic carboxylic ester. The method comprises the following steps: carrying out hydrolysis reaction on perfluorinated organic carboxylate and an alkaline aqueous solution to generate a perfluorinated organic carboxylate solution, drying the generated perfluorinated organic carboxylate solution, preparing a perfluorinated organic carboxylate aqueous solution again, and carrying out ion exchange with hydrogen-type cation exchange resin to convert the perfluorinated organic carboxylate aqueous solution into a perfluorinated organic carboxylic acid aqueous solution. And performing post-treatment on the perfluorinated organic carboxylic acid aqueous solution to obtain the perfluorinated organic carboxylic acid compound. The preparation process of the method does not involve organic solvents such as sulfuric acid, hydrochloric acid and other acidic solutions, and the method has the advantages of simple operation, stable process, high product purity, safety, short reaction time, high yield and the like.

Description

Technical Field

[0001] This invention relates to the field of perfluorinated fine chemical technology, specifically to a method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters, and particularly to a method for preparing reactive perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters. Background Technology

[0002] Reactive perfluorinated organic carboxylic acids are an important class of perfluorinated fine chemicals. The carboxyl groups (-COOH) in their molecular structure not only endow them with water solubility and surface activity, but more importantly, the double bonds they contain can serve as reaction sites. Through polymerization, amidation, and other reactions, they can covalently bond to other materials (such as polymers, nanoparticles, and biomolecules), thereby achieving permanent material modification. For example, introducing carboxylic acid groups into the polymer backbone through polymerization can permanently endow the polymer with excellent surface properties, improving its interfacial hydrophilicity and affinity with other materials. They can also be applied in emulsion polymerization to prepare coatings and adhesives, serving as reactive emulsifiers that can participate in copolymerization, replacing traditional physical emulsifiers. This fundamentally solves the problem of emulsifier migration and precipitation, significantly improving the film stability and long-term storage stability of the emulsion.

[0003] The common industrial route for preparing perfluorinated organic carboxylic acids, especially reactive ones, involves first obtaining perfluorinated carboxylic acid esters or salts through methods such as telomerization or electrolytic fluorination, followed by hydrolysis and acidification to obtain the target product, perfluorinated carboxylic acid. Traditional methods for preparing perfluorinated carboxylic acids from perfluorinated carboxylic acid salts typically employ acidification with strong inorganic acids (such as sulfuric acid or hydrochloric acid), as illustrated in CN 117567265 A and CN 118791375 A. A typical chemical reaction formula is as follows: R f -COOM + H2SO4→ R f -COOH + MHSO4 Where R f It is a perfluoroalkyl, alkoxy, or alkenyl ether, and M is a metal ion such as Na. + K + NH4 + wait.

[0004] However, this traditional strong acid acidification process has many inherent defects and environmental problems: (1) Generates a large amount of by-product salts and wastewater: The reaction will generate equimolar amounts of hydrogen sulfate (such as NaHSO4) or other inorganic salts. These by-products are difficult to separate from the products, and are difficult and costly to treat as industrial waste, which puts a serious burden on the environment.

[0005] (2) Severe equipment corrosion: The strong acid (such as sulfuric acid) used in the reaction process is highly corrosive and has extremely high requirements for production equipment, pipelines, storage tanks, etc. Special alloys or plastic-lined materials are required, which greatly increases the investment and maintenance costs of equipment.

[0006] (3) Difficult product purification: The use of excessive inorganic acid may introduce inorganic anionic impurities such as sulfate into the product. It is necessary to go through multiple water washing, distillation and other complex purification steps to obtain high-purity products. The process is long and the yield loss is large.

[0007] (4) High cost of treating waste: The treatment of perfluorinated, acidic wastewater and waste salt requires expensive environmental protection facilities, which greatly increases production costs and contradicts the current concept of green chemical industry and sustainable development.

[0008] To overcome the aforementioned drawbacks, although some studies have attempted to use other acidifying agents or processes, none have fundamentally solved the pollution and cost problems. Therefore, this invention proposes a novel process for preparing perfluorinated organic carboxylic acids from perfluorinated organic carboxylic acid esters without the use of strong acids. Summary of the Invention

[0009] The purpose of this invention is to overcome the shortcomings of the existing technology in preparing perfluorocarboxylic acids by acidifying perfluorocarboxylic acid salts (esters) with strong acids such as sulfuric acid, such as generating a large amount of waste salt, corroding equipment, polluting the environment, and making it difficult to purify the product, and to provide a simple, environmentally friendly method for preparing perfluoroorganic carboxylic acids with high product purity.

[0010] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters includes the following steps: Perfluorinated organic carboxylic acid esters undergo hydrolysis with alkaline aqueous solutions to generate perfluorinated organic carboxylic acid salt solutions. The generated perfluorinated organic carboxylic acid salt solutions are dried and then reconstituted into perfluorinated organic carboxylic acid salt aqueous solutions. These solutions are then converted into perfluorinated organic carboxylic acid aqueous solutions through ion exchange with a hydrogen-form cation exchange resin. The perfluorinated organic carboxylic acid aqueous solutions are then post-treated to obtain perfluorinated organic carboxylic acid compounds.

[0011] The principle of ion exchange reaction is as follows: R f -COOM + H + -Resin → Rf-COOH + M + -Resin Where M represents a metal ion, such as sodium ion, potassium ion, ammonium ion, etc., and H + -Resin represents hydrogen-form cation exchange resin, R f It is a perfluoroalkyl, alkoxy, or alkenyl ether.

[0012] Preferably, the structural formula of the perfluorinated organic carboxylic acid ester is shown in formula (I): , Formula (I) Where x is an integer from 0 to 5, y is an integer from 1 to 5, R represents an alkyl group, and the structural formula is C0. n H 2n+1 n is an integer from 1 to 5.

[0013] Preferably, the alkaline aqueous solution includes one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, lithium hydroxide aqueous solution, and ammonia aqueous solution, with a mass concentration of 1-50%.

[0014] Preferably, the molar ratio of the perfluorinated organic carboxylic ester to the alkaline substance in the alkaline aqueous solution is 1:1 to 1:5, and more preferably 1:1 to 1:2.

[0015] Preferably, the hydrolysis reaction is carried out under the following conditions: stirring at a temperature of 25~150℃ for 0~10h.

[0016] A perfluorinated organic carboxylic acid ester is hydrolyzed with an alkaline aqueous solution to prepare a perfluorinated organic carboxylic acid salt solution containing low-boiling-point alcohol volatiles. The low-boiling-point volatiles are removed from the perfluorinated organic carboxylic acid salt solution by drying to obtain a pure perfluorinated carboxylic acid salt solid.

[0017] Preferably, the drying process includes spray drying, vacuum oven drying, and rotary evaporation drying.

[0018] Preferably, the process of reconstituted into a perfluorinated organic carboxylate aqueous solution specifically involves: drying the perfluorinated organic carboxylate solution and mixing it with pure water to prepare a perfluorinated organic carboxylate aqueous solution with a mass concentration of 1-80%, and then stirring and dispersing it at room temperature for 10-60 minutes.

[0019] Further preferably, the perfluorinated organic carboxylic acid salt aqueous solution is dried and then mixed with pure water to prepare a perfluorinated organic carboxylic acid salt aqueous solution with a mass concentration of 10-70%.

[0020] More preferably, the aqueous solution of perfluorinated organic carboxylate is dried and then mixed with pure water to prepare an aqueous solution of perfluorinated organic carboxylate with a mass concentration of 10-50%.

[0021] Preferably, the hydrogen-form cation exchange resin includes a hydrogen-form gel-type strong acid cation exchange resin and a hydrogen-form macroporous strong acid cation exchange resin, and more preferably a hydrogen-form macroporous strong acid cation exchange resin.

[0022] Preferably, the ion exchange includes column chromatography and batch stirred exchange, and more preferably batch stirred exchange.

[0023] More preferably, the chromatography column exchange method adopts a top-in, bottom-out exchange mode, with an aspect ratio of 0.5 to 10, a flow rate of 0.5 BV / h to 4 BV / h, and a temperature of 20 to 100°C. More preferably, the aspect ratio is 0.5 to 5, the flow rate is 0.5 BV / h to 2 BV / h, and the temperature is 40 to 80°C.

[0024] More preferably, the batch stirring exchange method refers to adding a hydrogen-form cation exchange resin to an aqueous solution of a perfluorinated organic carboxylate, wherein the molar equivalent ratio of the perfluorinated organic carboxylate to the hydrogen-form cation exchange resin is 1:1 to 1:5, and then separating the ion exchange resin after stirring at 25-100℃ for 1-10 hours.

[0025] Preferably, the post-processing involves separating water and perfluorinated organic carboxylic acid substances from the aqueous solution of perfluorinated organic carboxylic acid by distillation or rectification, thereby obtaining pure perfluorinated organic carboxylic acid compounds.

[0026] Preferably, the perfluorinated organic carboxylic acid compound contains a reactive double bond and can be used in reactive surfactants, polymer modification, and as a raw material for the preparation of other chemicals.

[0027] Compared with the prior art, the present invention has the following beneficial effects: (1) Environmentally friendly and no solid waste is generated: The whole process does not directly use strong acids such as sulfuric acid, and does not generate inorganic solid waste such as hydrogen sulfate from the chemical reaction stoichiometry, which fundamentally solves the environmental protection problem of waste salt treatment.

[0028] (2) Low equipment investment: The strong acid environment is avoided, the corrosion resistance requirements of the equipment are greatly reduced, and materials such as glass and plastic can be used, which significantly reduces equipment investment and maintenance costs.

[0029] (3) High product purity: The ion exchange process has good selectivity and the product effluent is basically free of inorganic salt impurities. Only simple concentration is needed to obtain high-purity products, which simplifies the purification process and improves the product yield and quality. The perfluorinated organic carboxylic acid compounds prepared by the method of this invention can reach a purity of 99.5% and a yield of 95.0%.

[0030] (4) Recyclable resources: Ion exchange resins are easy to regenerate and reuse hundreds of times, with low operating costs. Attached Figure Description

[0031] Figure 1 This is a process flow diagram of the preparation method of the present invention. Detailed Implementation

[0032] The hydrogen-form macroporous strong acid cation exchange resin (model: D001) and the hydrogen-form gel-type strong acid cation exchange resin (model: 001x7) used in the examples were both purchased from Zibo Dongda Chemical Co., Ltd.

[0033] Example 1 A method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters, such as Figure 1 As shown, it includes the following steps: (1) Preparation of perfluorinated organic carboxylate: 200g of 10% sodium hydroxide aqueous solution was added to a three-necked flask equipped with a stirrer. At 25°C, 106g of perfluorovinyl ether carboxylate methyl ester (CF2=CFOCF2CF2COOCH3) was slowly added dropwise while stirring to induce a hydrolysis reaction, and the mixture was stirred for 4 hours. After the reaction was completed, a perfluorinated organic carboxylate sodium solution containing low-boiling-point alcohol volatiles was obtained.

[0034] (2) Drying and dehydration: The obtained sodium perfluorinated organic carboxylic acid solution was transferred to a rotary evaporator and distilled under reduced pressure at 80°C to remove water and volatiles (mainly methanol) to obtain pure white waxy sodium perfluorinated organic carboxylic acid solid. (3) Preparation of salt solution: Weigh 50g of the above-mentioned dried sodium perfluorinated organic carboxylate solid, add 50g of deionized water, and prepare a sodium perfluorinated organic carboxylate aqueous solution with a mass concentration of 50%. Stir magnetically for 30 minutes at room temperature to ensure that it is fully dispersed and uniform.

[0035] (4) Ion exchange: Prepare a glass chromatography column (5 cm in diameter, 25 cm in height, aspect ratio = 5) and pack it with 500 mL of hydrogen-form macroporous strong acid cation exchange resin (model: D001). Feed the sodium perfluorinated organic carboxylic acid aqueous solution prepared in step (3) from the top of the column at a flow rate of 1 BV / h (i.e., 500 mL / h), control the column temperature at 60 °C, and collect the solution flowing out from the bottom of the column, which is the effluent.

[0036] (5) Post-processing: The collected effluent was transferred into a vacuum distillation apparatus and the water was evaporated at 85°C to obtain 42.6g of colorless and transparent perfluorinated organic carboxylic acid product.

[0037] HPLC analysis showed a purity of 98.5%, and the yield, calculated based on the obtained perfluorinated organic carboxylic acid, was 91.3%.

[0038] Example 2 A method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters includes the following steps: (1) Preparation of perfluorinated organic carboxylate: 94g of perfluorinated vinyl ether carboxylate (CF2=CFOCF2CF2CF2CF2COOC2H5) was added to a glass beaker containing 90g of 20% potassium hydroxide aqueous solution and mixed. The mixture was stirred at 25°C for 2 hours to obtain a perfluorinated organic carboxylate potassium solution.

[0039] (2) Drying and descaling: The obtained perfluoroorganic potassium carboxylate solution was dried using a spray dryer with an inlet temperature of 100°C and an outlet temperature of 60°C to obtain powdered perfluorocarboxylate solid.

[0040] (3) Preparation of salt solution: Take 20g of dried potassium perfluorinated organic carboxylate solid, dissolve it in 180g of deionized water, prepare an aqueous solution with a mass concentration of 10%, stir for 20 minutes to obtain potassium perfluorinated organic carboxylate aqueous solution.

[0041] (4) Ion exchange: An exchange column with an aspect ratio of 2 (5 cm in diameter and 10 cm in height) was packed with 200 mL of hydrogen-form gel-type strong acid cation exchange resin (model: 001x7). The aqueous solution of perfluorinated organic carboxylic acid potassium obtained in step (3) was passed through the resin column at a flow rate of 2 BV / h (200 mL / h) and the exchange was carried out at a column temperature of 55 °C. The solution flowing out from the bottom of the column was collected as the effluent.

[0042] (5) Post-processing: The effluent was distilled under reduced pressure to obtain 17.4 g of perfluorinated organic carboxylic acid product with a purity of 99.5% and a yield of 95.0%.

[0043] Example 3 A method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters includes the following steps: (1) Preparation of perfluorocarboxylate: 160g of perfluoroalkenyl ether carboxylate with the structural formula CF2=CFOCF2CF(CF3)OCF2CF2COOCH3 was mixed with 177g of 15% ammonia solution in a high-pressure reactor and reacted at 100℃ for 5 hours. After cooling, the corresponding perfluoroorganic carboxylate ammonium solution was obtained.

[0044] (2) Drying and descaling: The perfluorinated organic carboxylic acid ammonium solution was dried overnight at 80°C in a vacuum oven to obtain a viscous perfluorinated organic carboxylic acid ammonium solid.

[0045] (3) Preparation of salt solution: Weigh 30g of the above-mentioned dried perfluorinated organic carboxylic acid ammonium solid, add 70g of deionized water, prepare a perfluorinated organic carboxylic acid ammonium aqueous solution with a mass concentration of 30%, and stir for 60 minutes.

[0046] (4) Ion exchange using batch stirring method: Transfer the above-mentioned aqueous solution of perfluoroorganic carboxylic acid ammonium to a beaker. Calculate the molar amount of perfluorocarboxylic acid ammonium in the solution, and add 2.0 times the theoretical molar equivalent of hydrogen-form macroporous strong acid cation exchange resin (D001). Stir vigorously at 25°C for 6 hours. After stirring, filter using a Buchner funnel to separate the ion exchange resin, and wash the resin with a small amount of deionized water.

[0047] (5) Post-processing: Combine the filtrate and washing liquid, and perform vacuum distillation to obtain 25.1 g of perfluorinated organic ether carboxylic acid with a purity of 98.8% and a yield of 90.0%.

[0048] Example 4 A method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters includes the following steps: (1) Preparation of perfluorinated organic carboxylate: 242g of CF2=CFOCF2CF2CF2COOCH3 was added to 240g of 8% lithium hydroxide solution and stirred at 80℃ for 8 hours to obtain a perfluorinated organic carboxylate lithium solution.

[0049] (2) Drying and descaling: The obtained perfluorinated organic carboxylic acid lithium solution was dried by rotary evaporation at 110°C to obtain perfluorinated organic carboxylic acid lithium solid.

[0050] (3) Preparation of salt solution: Take 40g of dried lithium perfluorinated organic carboxylic acid solid and prepare a 10% lithium perfluorinated organic carboxylic acid aqueous solution (360g water) and stir for 15 minutes.

[0051] (4) Ion exchange: Add 3 times the theoretical molar equivalent of hydrogen-type gel-type strong acid cation exchange resin (001x7) to the aqueous solution of perfluorinated organic carboxylic acid lithium, stir at 25°C for 3 hours, filter with a Buchner funnel to separate the ion exchange resin, and wash the resin with a small amount of deionized water.

[0052] (5) Post-processing: Combine the filtrate and washing liquid, and perform vacuum distillation. After distillation, 36g of perfluorocarboxylic acid product was obtained with a purity of 99.0% and a yield of 92.7%.

[0053] Example 5 A method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters includes the following steps: (1) Preparation of perfluorinated organic carboxylate: Same as in Example 1, prepare a sodium perfluorinated organic carboxylate solution.

[0054] (2) Drying and descaling: The obtained sodium perfluorinated organic carboxylic acid solution was dried using a spray dryer with an inlet temperature of 100°C and an outlet temperature of 40°C to obtain fine sodium perfluorinated organic carboxylic acid powder.

[0055] (3) Preparation of salt solution: Mix 70g of sodium perfluorinated organic carboxylate powder with 30g of water to prepare a 70% high-concentration sodium perfluorinated organic carboxylate aqueous solution and stir for 40 minutes.

[0056] (4) Ion exchange: Using the batch stirring method, add 3 molar equivalents of hydrogen-type gel-type strong acid cation exchange resin (001x7) and stir at 80°C for 8 hours to improve the exchange efficiency. After stirring, filter with a Buchner funnel to separate the ion exchange resin and wash the resin with a small amount of deionized water.

[0057] (5) Post-processing: After separating the resin, distillation yielded a high-viscosity perfluorocarboxylic acid product with a yield of 89% and a purity of 97.5%. This proves that the method developed in this invention remains effective even at high concentrations.

[0058] Comparative Example 1: Traditional sulfuric acid acidification method: Take an aqueous solution of sodium perfluorinated organic carboxylic acid (50g solid dissolved in 50g water) of the same amount as in step 3 of Example 1. Under ice-water bath and stirring, slowly add excess 98% concentrated sulfuric acid until the pH reaches 0.5, resulting in the formation of a large amount of white precipitate (NaHSO4). The reaction solution separates into layers; the lower organic phase is collected and washed repeatedly five times with copious amounts of deionized water to remove residual acid and salt. The washed organic phase is then subjected to vacuum distillation.

[0059] Results: 41.5 g of perfluorocarboxylic acid was obtained, with a yield of 82.0% and a purity of 90.3%. Approximately 35 g of sodium bisulfate solid byproduct and over 500 g of fluoride-containing acidic wastewater were generated during the process. Product loss occurred after washing, and the process was lengthy and complex.

[0060] Comparative Example 2 The steps of Example 4 were repeated, but in step (4) ion exchange, only 0.8 times the theoretical molar equivalent of ion exchange resin was added. After stirring and reacting for 10 hours, the product obtained by filtration and distillation was small in quantity and low in purity (85%). Elemental analysis showed a large amount of lithium ion residue, indicating incomplete exchange. This shows that insufficient ion exchange resin will lead to incomplete reaction, resulting in a significant decrease in yield and purity.

[0061] The comparison between the examples and comparative examples shows that the method of the present invention is comparable to or even better than the traditional method in terms of product yield and purity, and completely avoids the generation of solid waste salt. Furthermore, the ion exchange resin used in the present invention can be reused with simple processing, making the process simpler and the environmental advantages extremely significant.

[0062] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for producing a perfluorinated organic carboxylic acid compound from a perfluorinated organic carboxylic acid ester, characterized by, The method comprises the following steps: The perfluoro organic carboxylate is hydrolyzed with an alkaline aqueous solution to generate a perfluoro organic carboxylate salt solution, the generated perfluoro organic carboxylate salt solution is dried and then prepared into a perfluoro organic carboxylate salt aqueous solution, the perfluoro organic carboxylate salt aqueous solution is converted into a perfluoro organic carboxylic acid aqueous solution through ion exchange with a hydrogen-type cation exchange resin, and the perfluoro organic carboxylic acid aqueous solution is treated to obtain a perfluoro organic carboxylic acid compound.

2. The method of producing a perfluorinated organic carboxylic acid compound from a perfluorinated organic carboxylic acid ester according to claim 1, wherein The perfluoro organic carboxylate has a structural formula as shown in formula (I). ， Formula (I) wherein x is an integer from 0 to 5, y is an integer from 1 to 5, R represents an alkyl group, and the structural formula is C n H 2n+1 , n is an integer from 1 to 5.

3. The method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters as described in claim 1, characterized in that, The alkaline aqueous solution comprises one or more of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a lithium hydroxide aqueous solution and an aqueous ammonia solution, and has a mass concentration of 1-50%; the hydrolysis reaction is performed at a temperature of 25-150 DEG C for 0-10 h under stirring.

4. The method of producing a perfluorinated organic carboxylic acid compound from a perfluorinated organic carboxylic acid ester according to claim 3, wherein The molar ratio of the perfluoro organic carboxylate to the alkaline substance in the alkaline aqueous solution is 1:1-1:5, and is further preferably 1:1-1:

2.

5. The method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters as described in claim 1, characterized in that, The drying comprises spray drying, vacuum oven drying and rotary evaporation drying.

6. The method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters as described in claim 5, characterized in that, The perfluoro organic carboxylate salt solution is dried and then mixed with pure water to prepare a perfluoro organic carboxylate salt aqueous solution with a mass concentration of 1-80%, and is stirred and dispersed at room temperature for 10-60 min; preferably, the perfluoro organic carboxylate salt solution is dried and then mixed with pure water to prepare a perfluoro organic carboxylate salt aqueous solution with a mass concentration of 10-70%; further preferably, the perfluoro organic carboxylate salt solution is dried and then mixed with pure water to prepare a perfluoro organic carboxylate salt aqueous solution with a mass concentration of 10-50%.

7. The method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters as described in claim 1, characterized in that, The hydrogen-type cation exchange resin comprises a hydrogen-type gel strong acid cation exchange resin and a hydrogen-type macroporous strong acid cation exchange resin, and is preferably a hydrogen-type macroporous strong acid cation exchange resin; the ion exchange comprises a chromatographic column exchange method and a batch stirring exchange method, and is preferably the batch stirring exchange method.

8. The method for preparing perfluorinated organic carboxylic acid compounds from perfluorinated organic carboxylic acid esters as described in claim 7, characterized in that, The chromatographic column exchange method adopts an up-down exchange mode, has a length-diameter ratio of 0.5-10, a flow rate of 0.5 BV / h-4 BV / h and a temperature of 20-100 DEG C, and is preferably a length-diameter ratio of 0.5-5, a flow rate of 0.5 BV / h-2 BV / h and a temperature of 40-80 DEG C; the batch stirring exchange method refers to that the hydrogen-type cation exchange resin is added into the perfluoro organic carboxylate salt aqueous solution, the molar equivalent ratio of the perfluoro organic carboxylate salt to the hydrogen-type cation exchange resin is 1:1-1:5, and the mixture is stirred at 25-100 DEG C for 1-10 h to separate the ion exchange resin.

9. The perfluorinated organic carboxylic acid compound produced according to the method of any one of claims 1 to 8, characterized in that, The prepared perfluoro organic carboxylic acid compound contains a reactive double bond.

10. The use of the perfluoroorganic carboxylic acid compound according to claim 9, wherein The perfluoro organic carboxylic acid compound is used in the fields of reactive surfactants, polymer modification and chemical preparation raw materials.

Images