CN113754820A

CN113754820A - Preparation method of perfluorosulfonic acid resin solid

Info

Publication number: CN113754820A
Application number: CN202111321452.6A
Authority: CN
Inventors: 张泽天; 周朝毅; 刘昊; 李道喜; 李蕴熙; 董天都; 贾雯迪; 潘丹丹; 鹿传睿; 刘品阳; 王福瑶
Original assignee: Spic Hydrogen Energy Technology Development Co Ltd
Current assignee: Spic Hydrogen Energy Technology Development Co Ltd
Priority date: 2021-11-09
Filing date: 2021-11-09
Publication date: 2021-12-07
Anticipated expiration: 2041-11-09
Also published as: CN113754820B

Abstract

The invention discloses a preparation method of perfluorosulfonic acid resin solid, which comprises the following steps: a. dispersing perfluorosulfonic acid resin in a solvent to obtain perfluorosulfonic acid resin dispersion liquid; b. adding the perfluorosulfonic acid resin dispersion liquid obtained in the step a into an organic precipitator, precipitating a precipitate, and filtering to obtain a solid product, wherein the organic precipitator is selected from at least one of a first precipitator, a second precipitator and a third precipitator, and the solvent in the step a is mutually soluble with the precipitator; c. and c, drying the solid product obtained in the step b to obtain a perfluorosulfonic acid resin solid. The method can obtain pure perfluorosulfonic acid resin solid, can improve the product purity in the production process, reduces sewage generated by the fluorine industry, and improves the stability of batches.

Description

Preparation method of perfluorosulfonic acid resin solid

Technical Field

The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of a perfluorosulfonic acid resin solid.

Background

Perfluorosulfonic acid resin (PFSA) is a top material of the fluorine material industry as an ion exchange resin, and the commercially available perfluorosulfonic acid resin is almost evolved based on Nafion resin from DuPont. The use of Nafion resins in the sixties of the last century in polyelectrolyte membranes for the chlor-alkali industry, and their use in fuel cells in the eighties of the last century, accelerated the development of fuel cell technology by the Ballard company of canada. All the ion exchange membranes of the vehicle fuel cells which are actually put into use at present are prepared on the basis of perfluorinated sulfonic acid resin.

The ion exchange membrane prepared from the perfluorinated sulfonic acid resin is not only applied to the chlor-alkali industry and fuel cells, but also widely applied to flow battery diaphragms, separation membranes, water electrolysis hydrogen production, humidifier membranes, electrodialysis membranes and membrane reactors. In addition, perfluorosulfonic acid resin is widely studied as a solid super acid to replace the conventional liquid acid catalyst. The non-crosslinked structure and good stability of the perfluorosulfonic acid resin endow the perfluorosulfonic acid resin with good recovery performance, and the perfluorosulfonic acid resin is considered to be a green and environment-friendly catalyst.

The perfluorosulfonic acid resin requires a suitable purification scheme during the manufacturing process to obtain a product of high purity. The preparation of the perfluorosulfonic acid resin needs to consider many factors, including the selection of the base ether monomer, the purification process, the screening and distribution of molecular weight in the synthesis process, and the like, and needs to have relatively deep experience accumulation. At present, commercially available perfluorosulfonic acid resins are available abroad, and mainly include gore, kemu, 3M in the united states, suwei in belgium, and asahi in japan. In China, a few fluorine chemical enterprises in the east kingdom, such as the hydrogen energy, the megachemical group and the Shanghai Sanai Rich, can produce the commercial perfluorosulfonic acid resin. From the technical index, the difference of the domestic perfluorinated sulfonic acid resin compared with the imported perfluorinated sulfonic acid resin is not large, and the difference is mainly reflected in the stability of the quality of the product batch.

The impurity residues in the ion exchange resin have a great direct influence on the optical properties, the application properties and the product batch stability of the resin. For perfluorosulfonic acid resins, impurities are introduced during various manufacturing processes. During the polymerization stage, initiators, catalysts, emulsifiers or other auxiliaries can remain in the polymer matrix as impurities. The sulfonyl fluoride resin prepared by polymerization can introduce inorganic salt and micromolecule acidic impurities into the product in the processes of sodium treatment and acidification. Solid perfluorosulfonic acid resin products are usually sold in powder or granular form, and therefore require the pulverization of the bulk perfluorosulfonic acid resin solid into powder in a post-treatment process, and the tools used for mechanical pulverization are usually made of metal materials, which can lead to the occurrence of metal impurities in the resin powder. Regarding the appearance and appearance of the perfluorosulfonic acid resin, the presence of impurities causes yellowing of the perfluorosulfonic acid resin product, and the yellowing phenomenon exists in perfluorosulfonic acid resin ion exchange membranes, dispersions and other solid products. Treatment of perfluorosulfonic acid resin articles with nitric acid and hydrogen peroxide can temporarily remove color, however, this "bleaching" approach does not completely remove impurities and the perfluorosulfonic acid resin article can yellow again after a period of time or heating. Partial discoloration is also difficult to remove using nitric acid treatment. The existence of impurities has a great influence on the durability of the perfluorosulfonic acid resin product, and taking a fuel cell proton exchange membrane made of the perfluorosulfonic acid resin as an example, the existence of small-molecular acidic impurities and low-molecular weight perfluorosulfonic acid resin can cause the performance of the cell to be unstable, and the performance can be rapidly reduced along with the loss of the small-molecular acid and the low-molecular weight perfluorosulfonic acid resin. The existence of metal ion impurities can reduce the proton transmission capability, poison a catalytic system, and reduce the service life and the service performance of the fuel cell. At present, researches on the influence of impurities on perfluorosulfonic acid resin are relatively few, the residue of auxiliaries such as an emulsifier, an initiator and a catalyst can cause yellowing phenomenon, and the influence on the performance is not clear, but the improvement of the product purity is an inevitable measure on the premise of allowing the cost to obtain a commercial product with good stability.

At present, in the literature disclosing the preparation of perfluorosulfonic acid resins, purification for post-treatment is generally a scheme using water washing. The limitations of rinsing with water are: (1) the perfluorinated sulfonic acid resin has strong adsorbability on partial impurities, and has limited water washing and cleaning effects; (2) lipophilic and hydrophobic impurities are difficult to remove; (3) the yield of the perfluorinated sulfonic acid resin is reduced; (4) a large amount of sewage is generated. Further, a perfluorosulfonic acid resin having a high partial ion exchange capacity or a low crystallinity is water-soluble at room temperature, and it is apparently impossible to purify it by washing with water. At present, no public report about the post-treatment of the water-soluble perfluorosulfonic acid resin exists. Other types of ion exchange resins, such as styrenic cation exchange polymers, have some published reports on water soluble ion exchange polymer post-treatment schemes.

The purification and purification of water-soluble sulfonated polystyrene and sulfonated styrene thermoplastic elastomer can not be carried out by washing with water. The water-soluble sulfonated polymer can be prepared by a method of sulfonation first and then neutralization, namely, an organic solvent can be volatilized by boiling water, an acidic substance is neutralized by a basic substance, and the generated inorganic salt exists in the aqueous dispersion as a new impurity. This solution results in aqueous dispersions of sulfonated polymers containing inorganic salt impurities, which are not clean solid products, thus limiting the range of applications of the products. The method can remove small molecular impurities in the sulfonated polymer aqueous dispersion by dialysis, but the method has low efficiency, high cost and large water consumption, and is difficult to be applied to large-scale industrial production.

The perfluorosulfonic acid resin has higher requirements on purity in a plurality of application scenes, and ensuring high product purity is a necessary measure for improving the product stability in the production process. In the published reports, the purification of the post-treatment of the preparation process of the perfluorosulfonic acid resin is completed by water washing, and the scheme has the defects of low product purity, more generated sewage, low efficiency, low yield and inapplicability to the water-soluble perfluorosulfonic acid resin.

In addition, because of the high cost, environmental hazard, and good stability of perfluorosulfonic acid resins, recycling perfluorosulfonic acid resin products is a very necessary and profitable job. In the recovery scheme disclosed and reported in the current stage, insoluble substances are mostly separated and removed, and then a drying and volatilizing method is adopted to change the dispersion liquid into solid.

At present, the unit price of the perfluorosulfonic acid resin solid exceeds 2 ten thousand yuan/kg, the production process is not environment-friendly, and the waste has great harm to the environment. Under the dual push of economy and environmental protection, numerous researchers have been driving the recovery of perfluorosulfonic acid resins and other valuable materials from perfluorosulfonic acid resin articles. The perfluorosulfonic acid resin has good stability, the chemical structure of the perfluorosulfonic acid resin before and after recovery is not changed, and the performance difference of the finished product prepared again is small. Meanwhile, the perfluorinated sulfonic acid resin has more purposes, and the recycled perfluorinated sulfonic acid resin can be applied to application scenes with low performance requirements. Taking the application of a proton exchange membrane fuel cell as an example, the service life of a Nafion membrane applied to the fuel cell exceeds 6 ten thousand hours, however, the generation of membrane pinholes and the inactivation of a catalyst in the use process of the fuel cell can cause great negative effects on the performance and the service life, which limit the single service life of an ion exchange membrane and aggravate the defect of high cost of the perfluorosulfonic acid resin. In addition, proton exchange membrane fuel cells require expensive platinum as a catalyst, which is bound to the proton exchange membrane during use. It is necessary to recover the valuable materials of the fuel cell which is scrapped. The mechanical stripping of the catalyst during recovery is difficult, and the recovery of both perfluorosulfonic resin and precious metal material is achieved by dissolving and re-separating the fuel cell proton exchange membrane from the catalyst, which is considered to be the most promising recovery method (Moghaddam J A, Parian M J, Rowshanzer S. Preparation, chromatography, and electrochemical properties information of recycled proton exchange membrane for fuel cell applications [ J ] Energy, 2018, 161: 699-.

The perfluorosulfonic acid resin, as an ion exchange resin, has a very strong adsorption property as other types of ion exchange resins. This adsorptivity is typical of ion exchange resins, but for perfluorosulfonic acid resin products, strong adsorptivity means that various impurities are introduced during use, which should be considered and designed for a corresponding purification scheme during recovery. However, the prior art mainly recovers the perfluorosulfonic acid resin by purifying solid, has less purification to the dispersion, and adopts a drying scheme to obtain the solid perfluorosulfonic acid resin from the dispersion.

Currently, publicly reported recovery reagents for perfluorosulfonic acid resin products mainly include a mixed solvent of water and a lower aliphatic alcohol, and high-boiling organic reagents such as dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), Dimethylformamide (DMF), Ethylene Glycol (EG), and N-methylpyrrolidone (NMP). Concentrated sulfuric acid can also be used as a recycling agent, but is considered to have no application value because of environmental pollution. The recovery scheme provided is also similar and different, and the basic idea is to dissolve and disperse the perfluorosulfonic acid resin product by using a solvent under certain conditions, and obtain insoluble substances and a dispersion liquid by separation means such as filtration or centrifugation. And drying the dispersion liquid to obtain the recovered perfluorosulfonic acid resin solid. This type of recovery method has an insurmountable problem in that the solid product obtained is not pure. The filtration method can remove only insoluble impurities, and cannot separate impurities dissolved and dispersed in the recovery reagent. Such impurities include inorganic salts, high boiling point organic small molecules, low molecular weight organics that readily adsorb to the resin, surfactants, free radical quenchers, small molecule acids, and recovery reagents, among others. The impurities are characterized by good dissolution and dispersion in a recovery reagent, difficult volatilization or easy adsorption to the perfluorosulfonic acid resin, thereby mixing with the perfluorosulfonic acid resin in the drying process, leading the recovered product to have more impurities and reduced value. Meanwhile, the method directly dries the dispersion liquid into solid, which is a typical scheme with high energy consumption and low efficiency.

The crystallinity and the micro-morphology of the perfluorosulfonic acid resin have a decisive influence on the solubility, and the crystallization of the perfluorosulfonic acid resin can be promoted by drying the perfluorosulfonic acid resin dispersion liquid at high temperature or annealing the perfluorosulfonic acid resin solid at high temperature. Such crystalline perfluorosulfonic acid resins would be difficult to dissolve in liquid solvents, and generally would require high temperatures to be dissolved with a particular solvent. Therefore, the solid obtained by using the perfluorosulfonic acid resin dispersion dried at high temperature has high crystallinity, is difficult to redissolve, and has limited application.

Therefore, it is necessary to develop a method for preparing perfluorosulfonic acid resin solid, so as to solve the problems of difficult solid preparation, purification, and dissolution and dispersion of crystalline polymer in a liquid solvent during the production and recovery of perfluorosulfonic acid resin.

Disclosure of Invention

The present invention is based on the discovery and recognition by the inventors of the following facts and problems: 1. at present, solid products are obtained by drying and volatilizing solvents in the preparation of solids from perfluorosulfonic acid resin dispersion liquid, so that the problems of long time consumption, low efficiency, high energy consumption, high pollution and the like exist, and the unremoved solvents can also become impurities and exist in the perfluorosulfonic acid resin solids. 2. For recovering perfluorosulfonic acid resin and other high-value materials from perfluorosulfonic acid resin products, a dispersion liquid and insoluble substances are separated after the materials to be recovered are dissolved, and the recovered dispersion liquid is dried to obtain a solid recovered perfluorosulfonic acid resin containing impurities. The recovered dispersion liquid and solid recovered substance obtained by the method have many impurities and low purity. And the process of removing the solvent is time-consuming, high in energy consumption and large in pollution, and the impurities which are difficult to volatilize cannot be completely removed, and the solvent which is not removed can also become impurities and exist in the recovered perfluorosulfonic acid resin solid. 3. In the purification process stage of perfluorosulfonic acid resins, the purification is currently achieved mainly with water washing of the product. The water washing method is difficult to remove hydrophobic impurities and impurities with strong adsorption of the perfluorinated sulfonic acid resin, and simultaneously can cause the loss of water-soluble perfluorinated sulfonic acid resin products and generate a large amount of fluorine-containing wastewater. The method of water washing is adopted, so that the purification effect is limited, the cost is high, and the method is not environment-friendly. And the scheme can not be applied to the purification of the water-soluble perfluorosulfonic acid resin, and has great limitation. The perfluorosulfonic acid resin can also be purified by a dialysis method, but the dialysis method has the defects of low efficiency, high cost, small scale and the like which cannot be overcome. 4. The prior commercially available perfluorosulfonic acid resin powder product is mainly obtained by mechanically crushing a prepared perfluorosulfonic acid resin solid product. The mechanical crushing method can inevitably introduce metal impurities, and the metal ion impurities which are difficult to remove influence various performances of the perfluorosulfonic acid resin product. 5. In the prior art, the improvement of the solubility of perfluorosulfonic acid resin in a solvent is to prepare high-crystallinity perfluorosulfonic acid resin into a dilute dispersion liquid under a high-temperature condition to destroy perfluorosulfonic acid resin crystals, and dry the high-crystallinity perfluorosulfonic acid resin in a lower temperature to obtain low-crystallinity and easily-soluble perfluorosulfonic acid resin solid. The method is only suitable for preparing dilute dispersion liquid of the perfluorosulfonic acid resin by selecting the low-boiling-point alcohol solvent at high temperature and high pressure, is not suitable for using the high-boiling-point solvent, and has limitation. And the low-temperature drying of the diluted dispersion liquid of the perfluorosulfonic acid resin takes long time, has low efficiency and large pollution, and the unremoved solvent can also be an impurity existing in the solid of the perfluorosulfonic acid resin.

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a preparation method of perfluorosulfonic acid resin solid, which adopts low-polarity organic precipitator, and can obtain pure perfluorosulfonic acid resin solid by virtue of low adsorption or no adsorption of the organic precipitator in perfluorosulfonic acid resin, so that the pure perfluorosulfonic acid resin solid can not be introduced into perfluorosulfonic acid resin as new impurities, the product purity can be improved in the production process, the sewage generated in the fluorine industry is reduced, and the batch stability is improved.

The preparation method of the perfluorosulfonic acid resin solid provided by the embodiment of the invention comprises the following steps:

a. dispersing perfluorosulfonic acid resin in a solvent to obtain perfluorosulfonic acid resin dispersion liquid;

b. adding the perfluorinated sulfonic acid resin dispersion liquid obtained in the step a into an organic precipitator, precipitating a precipitate, and filtering to obtain a solid product, wherein the organic precipitator is selected from at least one of a first precipitator, a second precipitator or a third precipitator, the first precipitator is selected from at least one of carbon pentaalkane, carbon hexaalkane, carbon heptaalkane, carbon octaalkane, carbon nonaalkane, carbon decaalkane, perfluoro-n-hexane or petroleum ether, and the second precipitator is selected from carbon disulfide, dichloromethane, carbon tetrachloride, trichloromethane, chloroethane, C₂H₄Cl₂、C₂H₃Cl₃、C₃H₇Cl、C₄H₉Cl or C₅H₁₀At least one of Cl, the third precipitating agent is selected from at least one of tetrahydrofuran, acetone or butanone, and the solvent in the step a is mutually soluble with the organic precipitating agent;

c. and c, drying the solid product obtained in the step b to obtain a perfluorosulfonic acid resin solid.

The preparation method of the perfluorosulfonic acid resin solid provided by the embodiment of the invention has the advantages and technical effects that 1, in the method provided by the embodiment of the invention, a solvent is adopted to dissolve and disperse the perfluorosulfonic acid resin, and a resin dispersion liquid is added into an organic precipitator, so that the solvent and the organic precipitator can be mutually dissolved to form a homogeneous liquid, and the perfluorosulfonic acid resin is precipitated; 2. compared with the method for directly drying the dispersion liquid in the prior art, the method provided by the embodiment of the invention has the advantages that the efficiency is higher, the generated waste gas and waste liquid are less, and the method is more environment-friendly and efficient; 3. in the method of the embodiment of the invention, the adopted organic precipitator has low adsorption capacity with the perfluorinated sulfonic acid resin, is not easy to be adsorbed by the perfluorinated sulfonic acid resin to become new impurities, and is easy to be desorbed from the perfluorinated sulfonic acid resin; 4. in the method of the embodiment of the invention, the requirement on the raw material of the organic precipitator is wide, which is beneficial to further reducing the cost; 5. in the method of the embodiment of the invention, strong-acid, strong-oxidizing and strong-corrosive chemical reagents are not used, the purification process is mild, and the used reagents are industrial common reagents, so that the large-scale industrial production is easy to realize; 6. compared with the dialysis purification method, the method provided by the embodiment of the invention has the advantages that the purification effect is equivalent, the efficiency is higher, the cost is lower, and the expanded production is easy to realize; 7. in the method of the embodiment of the invention, the requirement on the solvent is low, except concentrated sulfuric acid, all kinds of solvents which can dissolve and disperse the perfluorinated sulfonic acid resin and are reported in the disclosure can be used, and in the selection of the solvent, the solvent can be mixed with the adopted organic precipitator to form a homogeneous solution; 8. the method provided by the embodiment of the invention can effectively remove various impurities in the preparation process of the perfluorosulfonic acid resin, can effectively remove various impurities of the waste perfluorosulfonic acid resin, and the prepared perfluorosulfonic acid resin does not contain free small molecular acid, has low yellowness index, good optical performance, no discoloration after a period of high-temperature heat treatment, no reduction in optical performance and excellent performance, and can improve the batch stability of the production of the perfluorosulfonic acid resin and reduce the cost.

In some embodiments, in step a, the solvent comprises at least one of a high boiling point organic solvent, water, or a lower aliphatic alcohol.

In some embodiments, the high boiling point organic solvent in step a is selected from at least one of ethylene glycol, propylene glycol, glycerol, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or N-methylpyrrolidone; the lower aliphatic alcohol is selected from at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol and isobutanol.

In some embodiments, in step b, when the organic precipitating agent comprises: when the weight percentage of the first precipitator is more than 90 wt% and less than or equal to 100wt%, the weight percentage of the second precipitator is more than or equal to 0wt% and less than 10wt% and the weight percentage of the third precipitator is more than or equal to 0wt% and less than 10wt%, the solvent in the step a comprises at least one of ethanol, isopropanol or n-propanol, the sum of the weight percentages of the ethanol, the isopropanol or the n-propanol in the solvent is not less than 40%, and the weight percentage of water in the solvent is not more than 30%; alternatively, the first and second electrodes may be,

when the organic precipitating agent comprises: when the weight percentage of the first precipitator is more than 70% and less than or equal to 90% and the weight percentage of the second precipitator is more than or equal to 10% and less than 30%, the solvent in the step a comprises at least one of ethanol, isopropanol or n-propanol, the sum of the mass percentages of the ethanol, the isopropanol or the n-propanol in the solvent is not less than 30%, and the mass percentage of water in the solvent is not more than 30%; alternatively, the first and second electrodes may be,

when the organic precipitating agent comprises: when the first precipitator is more than or equal to 0 and less than or equal to 70 weight percent and the second precipitator is more than or equal to 30 weight percent and less than or equal to 100 weight percent, the mass percentage of water in the solvent in the step a is not more than 30 percent; alternatively, the first and second electrodes may be,

when the organic precipitating agent comprises: when the weight percentage of the first precipitator is more than 70 percent and less than or equal to 90 percent, the weight percentage of the second precipitator is more than or equal to 0 and less than or equal to 20 percent, and the weight percentage of the third precipitator is more than or equal to 10 percent and less than 30 percent, the mass percentage of water in the solvent in the step a is not more than 70 percent; alternatively, the first and second electrodes may be,

when the organic precipitating agent comprises: when the first precipitator is more than or equal to 0 and less than or equal to 70 weight percent, the second precipitator is more than or equal to 0 and less than or equal to 70 weight percent and the third precipitator is more than or equal to 30 and less than or equal to 100 weight percent, the solvent in the step a comprises at least one of high-boiling-point organic solvent, water or lower aliphatic alcohol; alternatively, the first and second electrodes may be,

when the organic precipitating agent comprises: and (b) when the weight percentage of the first precipitator is more than or equal to 70 wt% and less than or equal to 90 wt% and the weight percentage of the third precipitator is more than or equal to 0 and less than or equal to 10wt%, the mass percentage of water in the solvent in the step a is not more than 30%.

In some embodiments, in the step a, the mass content of the perfluorosulfonic acid resin in the perfluorosulfonic acid resin dispersion liquid is 0.1% to 50%.

In some embodiments, in the step a, the perfluorosulfonic acid resin dispersion contains no more than 20% by mass of non-solvent substances other than the perfluorosulfonic acid resin and the solvent.

In some embodiments, in step a, the perfluorosulfonic acid resin is selected from at least one of a metal ion type perfluorosulfonic acid resin, an acid type perfluorosulfonic acid resin, an ammonium ion type perfluorosulfonic acid resin, a quaternary ammonium salt ion type perfluorosulfonic acid resin, an imidazole ion type perfluorosulfonic acid resin, or a waste containing perfluorosulfonic acid resin.

In some embodiments, in step a, the used material containing perfluorosulfonic acid resin comprises a perfluorosulfonic acid resin ion exchange membrane, a membrane electrode assembly, a perfluorosulfonic acid resin catalyst, or an ionomer-metal composite.

In some embodiments, the mass of the organic precipitant in the step b is 1.5 to 10 times of the mass of the solvent in the perfluorosulfonic acid resin dispersion liquid obtained in the step a.

In some embodiments, in the step b, during the process of adding the perfluorosulfonic acid resin dispersion into the organic precipitant to precipitate, stirring and filtering to obtain a solid product, wherein,

when the stirring processing speed is 1200-2000 rpm and the mass content of the solvent in the solid product obtained by filtering is not more than 15%, drying in the step c to obtain 150-300-mesh perfluorosulfonic acid resin powder; alternatively, the first and second electrodes may be,

when the stirring processing speed is 800-1500 rpm, the stirring processing speed is 800 rmp, and the solvent mass content in the solid product obtained by filtering is 15-20%, the solvent mass content is 15%, and the perfluorosulfonic acid resin powder with the particle size of 80-150 meshes is obtained after drying in the step c; alternatively, the first and second electrodes may be,

when the stirring processing speed is 200-800 rpm and the mass content of the solvent in the solid product obtained by filtering is 15-20%, the solvent does not contain 20%, and the perfluorosulfonic acid resin particles with the particle size of 50-80 meshes are obtained after drying in the step c; alternatively, the first and second electrodes may be,

when the stirring processing speed is 200-600 rpm and does not contain 200 rpm, and the mass content of the solvent in the solid product obtained by filtering is 20-50%, the solvent does not contain 50%, and the perfluorosulfonic acid resin particles with the particle size of 10-50 meshes are obtained after the drying in the step c; alternatively, the first and second electrodes may be,

when the stirring processing speed is 50-200 rpm and the mass content of the solvent in the solid product obtained by filtering is 40-90%, drying in the step c to obtain 2-10-mesh perfluorinated sulfonic acid resin blocky solid; alternatively, the first and second electrodes may be,

and c, when the stirring processing speed is 10-3000 rpm and the mass content of the solvent in the solid product obtained by filtering is not less than 95%, drying in the step c to obtain flocculent or blocky solid of the perfluorosulfonic acid resin.

In some embodiments, prior to step c, the steps a and b are repeated and then dried to produce a perfluorosulfonic acid resin solid.

In some embodiments, in the step c, the solid product obtained in the step b is subjected to agitation rinsing treatment by using a rinsing agent, and perfluorosulfonic acid resin solids with different sizes are obtained after drying by controlling the agitation rate during rinsing and the content of the solvent in the rinsed solid.

In some embodiments, in the step c, the rinsing agent comprises a first component with a mass content of 70-100% and a second component with a mass content of 0-30%, wherein the first component is selected from at least one of carbon pentaalkane, carbon hexaalkane, tetrahydrofuran or dichloromethane; the second component is selected from ethanol, isopropanol, n-propanol, dichloromethane, tetrahydrofuran, chloroform, chloroethane, C₂H₄Cl₂、C₂H₃Cl₃、C₃H₇Cl、C₄H₉Cl、C₅H₁₀At least one of Cl, acetone or butanone.

In some embodiments, in step c, the rinsing times are not less than 3 times, and in the first rinsing, the mass content of the first component in the rinsing agent is 70-100%, and the mass content of the second component in the rinsing agent is 0-30%; during the second rinsing, the mass content of the first component in the rinsing agent is 85-100%, and the mass content of the second component is 0-15%; and during rinsing for the third time or more, the mass content of the first component is 95-100%, and the mass content of the second component is 0-5%.

In some embodiments, in the step c, the mass of the rinsing agent is 3 to 50 times of the mass of the solvent in the solid product obtained in the step b.

In some embodiments, in the step c, when the stirring speed is 1200-2000 rpm and the mass content of the solvent in the solid product after rinsing treatment is not more than 15%, 150-300 mesh perfluorosulfonic acid resin powder is obtained after drying; alternatively, the first and second electrodes may be,

when the stirring speed is 800-1500 rpm and 800 rpm is not contained, and the mass content of the solvent in the rinsed solid product is 15-20%, 15% is not contained, and the perfluorosulfonic acid resin powder with the particle size of 80-150 meshes is obtained after drying; alternatively, the first and second electrodes may be,

when the stirring speed is 200-800 rpm and the mass content of the solvent in the rinsed solid product is 15-20%, the solvent does not contain 20%, and perfluorinated sulfonic acid resin particles with 50-80 meshes are obtained after drying; alternatively, the first and second electrodes may be,

when the stirring speed is 200-600 rpm and does not contain 200 rpm, and the mass content of the solvent in the rinsed solid product is 20-50%, the solvent is not contained by 50%, and the perfluorosulfonic acid resin particles with 10-50 meshes are obtained after drying; alternatively, the first and second electrodes may be,

and when the stirring speed is 50-200 rpm and the mass content of the solvent in the rinsed solid product is 40-90%, drying to obtain 2-10-mesh perfluorinated sulfonic acid resin blocky solid.

In some embodiments, in the step c, the solid product obtained in the step b is dried at-80 ℃ to 60 ℃ and 0 to 0.2 MPa to obtain a perfluorosulfonic acid resin solid.

Drawings

FIG. 1 is an IR spectrum of perfluorosulfonic acid resin A and product A-6 of example 1;

FIG. 2 is a GPC curve of perfluorosulfonic acid resin A in example 1;

FIG. 3 is a GPC curve for product A-6 of example 1;

FIG. 4 is a DSC temperature rise curve of perfluorosulfonic acid resin A in example 1;

FIG. 5 is a DSC temperature rise profile of product A-6 of example 1;

FIG. 6 is an IR spectrum of the perfluorosulfonic acid resin B and the product B-2 of example 2;

FIG. 7 is a GPC curve of perfluorosulfonic acid resin B in example 2;

FIG. 8 is a GPC curve of product B-2 of example 2.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

According to the preparation method of the perfluorosulfonic acid resin solid, the perfluorosulfonic acid resin is dissolved and dispersed by adopting a solvent, the resin dispersion liquid is added into an organic precipitator, and the solvent and the precipitator can be mutually dissolved to form a homogeneous liquid, so that the perfluorosulfonic acid resin is precipitated and separated out; in the method of the embodiment of the invention, the perfluorosulfonic acid resin solid is prepared from the perfluorosulfonic acid resin dispersion liquid by a precipitation method, and compared with the method for directly drying the dispersion liquid in the prior art, the method has the advantages of higher efficiency, less waste gas and waste liquid, environmental protection and high efficiency; in the method of the embodiment of the invention, the adopted organic precipitator has low adsorption capacity with the perfluorinated sulfonic acid resin, is not easy to be adsorbed by the perfluorinated sulfonic acid resin to become new impurities, and is easy to be desorbed from the perfluorinated sulfonic acid resin; in the method of the embodiment of the invention, the requirement on the raw material of the organic precipitator is wide, which is beneficial to further reducing the cost; in the method of the embodiment of the invention, strong-acid, strong-oxidizing and strong-corrosive chemical reagents are not used, the purification process is mild, and the used reagents are industrial common reagents, so that the large-scale industrial production is easy to realize; compared with the dialysis purification method, the method provided by the embodiment of the invention has the advantages that the purification effect is equivalent, the efficiency is higher, the cost is lower, and the expanded production is easy to realize; in the method of the embodiment of the invention, the requirement on the solvent is low, except concentrated sulfuric acid, all kinds of solvents which can dissolve and disperse the perfluorinated sulfonic acid resin and are reported in the disclosure can be used, and in the selection of the solvent, the solvent can be mixed with the adopted organic precipitator to form a homogeneous solution; the method provided by the embodiment of the invention can effectively remove various impurities in the preparation process of the perfluorosulfonic acid resin, can effectively remove various impurities of the waste perfluorosulfonic acid resin, and the prepared perfluorosulfonic acid resin does not contain free small molecular acid, has low yellowness index, good optical performance, no discoloration after a period of high-temperature heat treatment, no reduction in optical performance and excellent performance, and can improve the batch stability of the production of the perfluorosulfonic acid resin and reduce the cost.

In some embodiments, in step a, the solvent comprises at least one of a high boiling point organic solvent, water, or a lower aliphatic alcohol. Wherein the high boiling point organic solvent is at least one selected from ethylene glycol, propylene glycol, glycerol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; the lower aliphatic alcohol is selected from at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol and isobutanol. In the method of the embodiment of the present invention, the solvent is not particularly limited, and any of a high boiling point organic solvent, water, and a lower alcohol or a mixed solvent including a high boiling point organic solvent, water, and a lower alcohol may be used as long as it can dissolve the perfluorosulfonic acid resin to form a dispersion and can dissolve the perfluorosulfonic acid resin mutually with the organic precipitant used to form a homogeneous solution.

In some embodiments, in step b, when the organic precipitating agent comprises: when the weight percentage of the first precipitator is more than 90 wt% and less than or equal to 100wt%, the weight percentage of the second precipitator is more than or equal to 0wt% and less than 10wt% and the weight percentage of the third precipitator is more than or equal to 0wt% and less than 10wt%, the solvent in the step a comprises at least one of ethanol, isopropanol or n-propanol, the sum of the mass percentages of the ethanol, the isopropanol or the n-propanol in the solvent is not less than 40%, and the mass percentage of water in the solvent is not more than 30%. In the embodiment of the invention, because the first precipitator is too different in polarity from solvents such as water, methanol, propylene glycol, glycerol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone and the like, and is almost immiscible, and the immiscible characteristic is hardly influenced by perfluorosulfonic acid resin, when the mass content of the first precipitator in the organic precipitator is more than 90%, miscible homogeneous liquid can be obtained only by introducing ethanol, isopropanol or N-propanol into the solvents. If the solvent and the organic precipitator are not mutually soluble, the precipitator and the solvent are mixed to be layered into 2 phases, and the perfluorinated sulfonic acid resin is dispersed in a liquid phase mainly containing the solvent, so that precipitation cannot be carried out. Therefore, when the mass content of the first precipitant in the organic precipitant is greater than 90%, the solvent preferably includes at least one of ethanol, isopropanol or n-propanol, and the sum of the mass percentages of ethanol, isopropanol or n-propanol in the solvent is not less than 40%, and the mass percentage of water in the solvent is not more than 30%.

In some embodiments, in step b, when the organic precipitating agent comprises: when the weight percentage of the first precipitator is more than 70% and less than or equal to 90% and the weight percentage of the second precipitator is more than or equal to 10% and less than 30%, the solvent in the step a comprises at least one of ethanol, isopropanol or n-propanol, the sum of the mass percentages of the ethanol, the isopropanol or the n-propanol in the solvent is not less than 30%, and the mass percentage of water in the solvent is not more than 30%. In the embodiment of the invention, when the content of the first precipitator in the organic precipitator is reduced to be below 90% and higher than 70%, the dosage of the second precipitator is increased to be above 10% and lower than 30%, and the second precipitator is mutually soluble with the solvents except water and is also mutually soluble with other organic precipitants, so that the sum of the mass percentages of ethanol, isopropanol or n-propanol in the solvents can be controlled to be not less than 30%, and the organic precipitator and the solvents are mutually soluble to form a uniform solution, so that the perfluorosulfonic acid resin is separated out.

In some embodiments, in step b, when the organic precipitating agent comprises: and when the first precipitator is more than or equal to 0 and less than or equal to 70 weight percent and the second precipitator is more than or equal to 30 and less than or equal to 100 weight percent, the mass percentage of water in the solvent in the step a is not more than 30 percent. In the embodiment of the invention, when the content of the second precipitator in the organic precipitator is not less than 30%, the second precipitator is mutually soluble with the solvents except water and is also mutually soluble with other organic precipitants, so that the mutual dissolution of the organic precipitator and the solvents can be realized to form a uniform solution only by controlling the water content in the solvents to be not more than 30%, and the perfluorosulfonic acid resin is separated out.

In some embodiments, in step b, when the organic precipitating agent comprises: when the weight percentage of the first precipitator is more than 70 percent and less than or equal to 90 percent, the weight percentage of the second precipitator is more than or equal to 0 and less than or equal to 20 percent, and the weight percentage of the third precipitator is more than or equal to 10 percent and less than 30 percent, the mass percentage of the water in the solvent in the step a is not more than 70 percent. In the embodiment of the invention, when the content of the first precipitator in the organic precipitator is reduced to below 90% and above 70%, and when the third precipitator is contained in an amount of above 10% and below 30%, the third precipitator is mutually soluble with all solvents and also mutually soluble with other precipitants, so that the organic precipitator and the solvents can be mutually dissolved to form a uniform solution only by limiting the mass percentage of water in the solvents to be not more than 70% so as to separate out the perfluorosulfonic acid resin.

In some embodiments, in step b, when the organic precipitating agent comprises: when the first precipitator is more than or equal to 0 and less than or equal to 70 weight percent, the second precipitator is more than or equal to 0 and less than or equal to 70 weight percent and the third precipitator is more than or equal to 30 and less than or equal to 100 weight percent, the solvent in the step a comprises at least one of high-boiling-point organic solvent, water or lower aliphatic alcohol. In the embodiment of the invention, when the content of the third precipitator in the organic precipitator is not less than 30%, the third precipitator is mutually soluble with all solvents and also mutually soluble with other precipitants, so that the solvent is not limited at all, and any solvent capable of dispersing and dissolving the perfluorosulfonic acid resin can be adopted, and can form a uniform solution with the organic precipitator, so that the perfluorosulfonic acid resin is precipitated.

In some embodiments, in step b, when the organic precipitating agent comprises: when the first precipitator is more than or equal to 70 wt% and less than or equal to 90 wt% and the third precipitator is more than or equal to 0 and less than or equal to 10wt%, the solvent in the step a comprises at least one of ethanol, isopropanol or n-propanol, the sum of the mass percentages of the ethanol, the isopropanol or the n-propanol in the solvent is not less than 20%, and the mass percentage of water in the solvent is not more than 30%. The second precipitator or the third precipitator in the precipitator of the embodiment of the invention improves the compatibility of the non-aqueous solvent and the precipitator, so that the uniform solution can be formed when the dosage of ethanol, isopropanol and n-propanol in the dispersion reaches more than 20 percent, and the perfluorinated sulfonic acid resin is precipitated.

In the embodiment of the present invention, the contents of the first precipitator, the second precipitator, and the third precipitator in the organic precipitator, and the solvent used for dispersing the perfluorosulfonic acid resin may be adjusted according to the property that the first precipitator, the second precipitator, and the third precipitator are compatible with the solvent, so long as the organic precipitator and the solvent are mutually soluble to separate out the perfluorosulfonic acid resin.

In the method of the embodiment of the invention, the organic precipitator and the solvent are preferably selected, the solvent and the precipitator are completely mutually soluble, the phase number is 1, the liquid cannot be layered, the perfluorosulfonic acid resin is separated out, the adopted organic precipitator and the perfluorosulfonic acid resin have low adsorption capacity and are not easily adsorbed by the perfluorosulfonic acid resin, after the organic precipitator and the solvent form a uniform solution, the impurity removal of the perfluorosulfonic acid resin is effectively realized, the impurity content of the perfluorosulfonic acid resin is reduced, the yellowness index is reduced, and the thermal stability and the optical performance are excellent.

In some embodiments, in the step a, the mass content of the perfluorosulfonic acid resin in the perfluorosulfonic acid resin dispersion liquid is preferably 0.1% to 50%; in the perfluorosulfonic acid resin dispersion, the mass content of the perfluorosulfonic acid resin and non-solvent substances other than the solvent is not more than 20%. According to the method provided by the embodiment of the invention, the requirement on the purity of the solvent is low, and the perfluorosulfonic acid resin can be dissolved even if the mass content of the precipitator in the dispersion liquid is not more than 20% so as to prepare the perfluorosulfonic acid resin dispersion liquid.

In some embodiments, in step a, the perfluorosulfonic acid resin is selected from at least one of metal ion type perfluorosulfonic acid resin, acid type perfluorosulfonic acid resin, ammonium ion type perfluorosulfonic acid resin, small molecule organic cation type perfluorosulfonic acid resin, or waste containing perfluorosulfonic acid resin. Metal ion type perfluorosulfonic acid resins include, but are not limited to: alkali metal ions, iron ions, vanadium ions, titanium ions, cobalt ions, chromium ions, nickel ions, copper ions, aluminum ions, silver ions, zinc ions, calcium ions, magnesium ions, manganese ions, tin ions, and the like. Small molecule organic cation type perfluoro sulfonic acid resin such as quaternary ammonium salt cation, imidazolium cation type perfluoro sulfonic acid resin. The method of the embodiment of the invention has no limitation on the type of the perfluorosulfonic acid resin, and the method of the embodiment of the invention can be used for purifying the perfluorosulfonic acid resin to prepare the perfluorosulfonic acid resin solid.

In some embodiments, the alkali metal perfluorosulfonic acid resin is of the formula:

wherein M = 0-2, n = 2-5, and M is lithium, sodium, potassium, rubidium or cesium.

In some embodiments, the acid-type perfluorosulfonic acid resin is of the formula:

wherein m =0 ~ 2, n = 2~ 5.

Preferably, the alkali metal type perfluorosulfonic acid resin and the acid type perfluorosulfonic acid resin are prepared by the following methods:

(1) synthesis of sulfuryl fluoride resin

Tetrafluoroethylene monomer and sulfonyl fluoride vinyl ether monomer are copolymerized to synthesize sulfonyl fluororesin.

(2) Preparation of alkali metal type perfluorosulfonic acid resin

And soaking the synthesized sulfonyl fluorine resin in 0.1-5 mol/L alkali metal hydroxide aqueous solution for hydrolysis, and washing away redundant alkali liquor to obtain the alkali metal type perfluorosulfonic acid resin. The temperature of the alkali metal hydroxide aqueous solution is between room temperature and 100 ℃, and the soaking time is 0.1 to 48 hours. Preferably, the alkali metal hydroxide comprises one of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, or cesium hydroxide.

(3) Preparation of acid type perfluorosulfonic acid resin

Soaking the prepared alkali metal type perfluorosulfonic acid resin in 0.1-5 mol/L of inorganic strong acid aqueous solution, and washing away redundant acid solution to obtain the acid type perfluorosulfonic acid resin. The temperature of the inorganic strong acid aqueous solution is between room temperature and 100 ℃, and the soaking time is 0.1 to 48 hours. Preferably, the strong inorganic acid comprises one of hydrochloric acid, nitric acid or sulfuric acid.

Preferably, the waste containing perfluorosulfonic acid resin comprises a perfluorosulfonic acid resin ion exchange membrane, a membrane electrode assembly, a perfluorosulfonic acid resin catalyst, a supported perfluorosulfonic acid resin catalyst or an ionic polymer-metal composite. The method provided by the embodiment of the invention can be used for recycling the waste containing the perfluorinated sulfonic acid resin by using the prepared perfluorinated sulfonic acid resin as a raw material and waste containing the perfluorinated sulfonic acid resin as a raw material, recovering and obtaining clean perfluorinated sulfonic acid resin solid from the waste containing the perfluorinated sulfonic acid resin, changing the dispersibility of the perfluorinated sulfonic acid resin solid in a solvent, reducing the production difficulty and cost of products such as an ion exchange membrane, a membrane electrode, an ionic polymer-metal composite (IPMC) and a catalyst, and improving the purity to further improve the performance stability of the products such as the ion exchange membrane, the membrane electrode, the IPMC and the catalyst.

In some embodiments, the mass of the organic precipitant in step b is preferably 1.5 to 10 times, more preferably 2 to 8 times, and even more preferably 2 to 5 times of the mass of the solvent in the perfluorosulfonic acid resin dispersion obtained in step a. In the method of the embodiment of the present invention, the amount of the organic precipitant is not particularly limited, as long as the resin in the perfluorosulfonic acid resin dispersion can be sufficiently precipitated, if the amount of the organic precipitant is too small, the perfluorosulfonic acid resin cannot be sufficiently precipitated, and if the amount of the organic precipitant is too large, the organic precipitant is wasted.

In some embodiments, in the step b, preferably, in the process of precipitating the precipitate by adding the perfluorinated sulfonic acid resin dispersion into an organic precipitant, stirring, filtering to obtain a solid product, continuously stirring during the formation of the precipitate, and preventing the resin solid from agglomerating during the precipitation by the shearing action of stirring, wherein the stirring rate is 10 to 3000 rpm, preferably 50 to 2500 rpm, and more preferably 50 to 2000 rpm.

Preferably, when the stirring processing speed is 1200-2000 rpm and the mass content of the solvent in the solid product obtained by filtering is not more than 15%, 150-300 mesh perfluorosulfonic acid resin powder is obtained after drying in the step c;

preferably, when the stirring processing speed is 800-1500 rpm, 800 rmp is not contained, and the mass content of the solvent in the solid product obtained by filtering is 15-20%, 15% is not contained, and the perfluorosulfonic acid resin powder with 80-150 meshes is obtained after drying in the step c;

preferably, when the stirring processing speed is 200-800 rpm and the mass content of the solvent in the solid product obtained by filtering is 15-20%, the solvent does not contain 20%, and the perfluorosulfonic acid resin particles with the particle size of 50-80 meshes are obtained after drying in the step c;

preferably, when the stirring processing speed is 200-600 rpm and does not contain 200 rpm, and the mass content of the solvent in the solid product obtained by filtering is 20-50%, the solid product does not contain 50%, and the perfluorosulfonic acid resin particles with 10-50 meshes are obtained after drying in the step c;

preferably, when the stirring processing speed is 50-200 rpm and the mass content of the solvent in the solid product obtained by filtering is 40-90%, drying in the step c to obtain 2-10-mesh perfluorosulfonic acid resin blocky solid;

In the embodiment of the invention, the size of the prepared perfluorosulfonic acid resin solid can be regulated and controlled by controlling the stirring rate and the amount of the solvent adsorbed in the solid product obtained by precipitation in the process of separating out the perfluorosulfonic acid resin. However, if the solvent content in the solid product reaches more than 95%, the stirring speed will not affect the product size any more, and even if the stirring speed is increased, only flocculent or blocky perfluorosulfonic acid resin solid can be obtained after drying. In practical application, the size of the perfluorosulfonic acid resin product can be flexibly regulated according to the requirement on the perfluorosulfonic acid resin product, the method is simple and convenient, the application is easy, and meanwhile, the problem of introducing metal impurities when mechanical crushing treatment is subsequently adopted is avoided.

In some embodiments, prior to step c, the steps a and b are repeated and then dried to produce a perfluorosulfonic acid resin solid. In the embodiment of the invention, the step a and the step b can be repeated for a plurality of times according to the impurity condition of the raw material of the perfluorosulfonic acid resin, so as to further improve the purity of the prepared perfluorosulfonic acid resin solid.

In some embodiments, in the step c, the solid product obtained in the step b is subjected to agitation rinsing treatment by using a rinsing agent, the solvent and impurities in the step a adsorbed in the solid product are extracted, and perfluorosulfonic acid resin solids with different sizes are obtained after drying by controlling the agitation rate in the rinsing process and the content of the solvent in the rinsed solid. Preferably, the rinsing agent comprises a first component and a second component, wherein the first component comprises 70-100% by mass and 0-30% by mass, and the first component is at least one of carbon pentaalkane, carbon hexaalkane, tetrahydrofuran or dichloromethane; the second component is selected from ethanol, isopropanol, n-propanol, dichloromethane, tetrahydrofuran, chloroform, C₂H₄Cl₂、C₂H₃Cl₃、C₃H₇Cl、C₄H₉Cl、C₅H₁₀At least one of Cl, acetone or butanone. Further preferably, the rinsing frequency is not less than 3, and during the first rinsing, the mass content of the first component in the rinsing agent is 70-100%, and the mass content of the second component is 0-30%; in the second rinsing, the rinsing agentThe mass content of the first component is 85-100%, and the mass content of the second component is 0-15%; and during rinsing for the third time or more, the mass content of the first component is 95-100%, and the mass content of the second component is 0-5%. Preferably, the mass of the rinsing agent used in each rinsing is 3-50 times, more preferably 5-30 times, and even more preferably 5-20 times of the mass of the solvent in the solid product obtained in the step b. The content of the solvent in the step a adsorbed in the solid product is continuously reduced along with the increase of the rinsing times, the volume and the mass of the solid product are continuously reduced, the mass of the rinsing agent can be kept unchanged, and the mass of the rinsing agent can also be reduced along with the reduction of the volume and the mass of the solid product, and preferably, the mass of the rinsing agent is not less than 2 times of the mass of the perfluorosulfonic acid resin in the solid product. In the method of the embodiment of the invention, the solid product obtained in the step b is stirred and rinsed by using the rinsing agent, so that the size of the dried perfluorosulfonic acid resin solid is regulated and controlled, and compared with the method of controlling the stirring speed and the solvent adsorption amount in the solid in the precipitation process, the use amount of the organic precipitator can be effectively reduced. In a specific application, when a smaller-sized perfluorosulfonic acid resin solid is desired to be obtained, and the stirring rate and the solid solvent adsorption amount are controlled in a precipitation process for size control, the solvent content in the solid product obtained after filtration in the step b needs to be controlled at a lower level, and at the moment, more organic precipitant needs to be added to reduce the solvent content in the solid product.

Preferably, the time of each rinsing is 1-60 min, and too short time can cause insufficient extraction, solvent in the solid product is not sufficiently extracted, and too long time can not change the extraction effect, but can reduce the efficiency.

In some embodiments, in the step c, preferably, the stirring speed during rinsing is controlled to be 50-3000 rpm, and the mass content of the solvent in the solid product after rinsing treatment is controlled to be 5-95%. Preferably, when the stirring speed is 1200-2000 rpm and the mass content of the solvent in the solid product after rinsing treatment is not more than 15%, drying to obtain 150-300-mesh perfluorosulfonic acid resin powder; when the stirring speed is 800-1500 rpm and 800 rpm is not contained, and the mass content of the solvent in the rinsed solid product is 15-20%, 15% is not contained, and the perfluorosulfonic acid resin powder with 80-150 meshes is obtained after drying; when the stirring speed is 200-800 rpm and the mass content of the solvent in the rinsed solid product is 15-20%, not containing 20%, and drying to obtain 50-80-mesh perfluorosulfonic acid resin particles; or when the stirring speed is 200-600 rpm and does not contain 200 rpm, and the mass content of the solvent in the rinsed solid product is 20-50%, the solvent is not contained by 50%, and the perfluorosulfonic acid resin particles with 10-50 meshes are obtained after drying; or when the stirring speed is 50-200 rpm and the mass content of the solvent in the solid product after rinsing treatment is 40-90%, drying to obtain 2-10-mesh perfluorinated sulfonic acid resin blocky solid.

In the method of the embodiment of the invention, the solid product obtained in the step b is further rinsed by using a rinsing agent to extract the solvent in the step a adsorbed in the solid product, so that the mass content of the solvent in the solid product is reduced to a specific range, and the macroscopic size of the perfluorosulfonic acid resin solid can be effectively regulated and controlled by controlling the stirring rate in the rinsing process and the content of the solvent in the solid product obtained after the last rinsing, and meanwhile, the impurity content of the perfluorosulfonic acid resin can be further reduced. In the rinsing process, the perfluorosulfonic acid resin solid powder with smaller size can be obtained by controlling the faster stirring speed and the lower solvent content in the solid product, so that the solvent content is further increased or the stirring speed is reduced, and the perfluorosulfonic acid resin solid with larger size can be obtained due to the agglomeration of the polymer. According to the requirements of specific applications, powdery solids, granular solids or blocky solids with different particle sizes can be obtained by regulating and controlling the stirring speed in the rinsing process and the content of the solvent in the solid product obtained after the last rinsing, and the problem that metal impurities are inevitably introduced by adopting a mechanical crushing method in the prior art is effectively solved.

In some embodiments, in the step c, the solid product obtained in the step b is dried at-80 ℃ to 60 ℃ and 0 to 0.2 MPa for 1 h to 72 h to obtain the low-crystallinity perfluorosulfonic acid resin solid. In the method provided by the embodiment of the invention, a low drying temperature is adopted, and a low-crystallinity and easily-soluble dry product can be obtained. The method of the embodiment of the invention can adopt the perfluorinated sulfonic acid resin with high crystallinity to prepare the perfluorinated sulfonic acid resin solid with low crystallinity, so that the solubility of the perfluorinated sulfonic acid resin is changed and the perfluorinated sulfonic acid resin can be dissolved in the solvent at a lower temperature (not more than 100 ℃); the low-crystallinity perfluorosulfonic acid resin solid obtained by drying at the medium and low temperature can be used for preparing a high-concentration perfluorosulfonic acid resin dispersion, so that the production difficulty of a membrane preparation solution is reduced, the solvent consumption is reduced, and the large-scale industrial production of the perfluorosulfonic acid resin ion exchange membrane is facilitated; in the method of the embodiment of the invention, the perfluorosulfonic acid resin solid with low crystallinity and good solubility is obtained by adopting a process of dissolving firstly and precipitating secondly, compared with the method of dissolving firstly and then drying and removing the solvent at low temperature in the prior art, the solvent for dissolving the perfluorosulfonic acid resin is not limited to the low-boiling-point solvent, and the high-boiling-point solvent and the low-boiling-point solvent except sulfuric acid can be selected, so that the solid product has less liquid reagent to be removed in the drying process, high efficiency and less waste gas, and the purification of the perfluorosulfonic acid resin is realized while the crystallinity of the perfluorosulfonic acid resin is reduced; in the method provided by the embodiment of the invention, the perfluorosulfonic acid resin dry solids with different solubilities can be obtained by adjusting the drying temperature, so that the method is suitable for different application scenes.

The present invention is described in detail below with reference to the drawings and examples.

In the embodiment of the invention, the chemical structure of the sample iS tested by adopting a Sammer fly Nicolet iS20 Fourier transform infrared spectrometer, and the instrument iS 400-4000 cm^-1In the scanning range of 4 cm^-1The resolution of (2).

Molecular weight distribution of perfluorosulfonic acid resin samples was measured by Gel Permeation Chromatography (GPC) using a Waters1525-2414, column: agilent PLGel 5um MIXED-C (made in GB), mobile phase: DMF, flow rate: 1 mL/min, sample: 2 mg/mL, temperature: 35 ℃, standard sample: PMMA. Sample preparation: the sample was dissolved in DMF and the solution was tested by sonication for 12 h.

Ion exchange equivalent (EW value): the Ion Exchange Equivalent Weight (EW) is the mass of the perfluorosulfonic acid resin solid contained per mole of ionic group, and is in the unit of g/mol, and is in reciprocal relation with the Ion Exchange Capacity (IEC) indicating the size of Ion Exchange Capacity, and represents the acid concentration in the perfluorosulfonic acid resin solid. The change of the EW value of the perfluorosulfonic acid resin before and after purification can reflect the change of the content of the small molecular acid impurities. The EW value of the perfluorosulfonic acid resin was measured using a Titrino plus automatic potentiometric titrator.

The detection method of the small molecule free acid in the perfluorosulfonic acid resin sample comprises the following steps: 0.5 g of the solid sample was dissolved in 4.5 g of DMF and added to 10 mL of deionized water, and the mixture was dialyzed in a dialysis bag at 60 ℃ for 24 hours in 300 mL of deionized water. And testing the pH value of the liquid outside the dialysis bag by using a pH test paper, wherein if the pH value is 7, the small molecule free acid does not exist in the sample, and if the pH value is less than 7, the small molecule free acid exists in the sample.

Thermal properties of perfluorosulfonic acid resin solids: the DSC performance curve of the perfluorosulfonic acid resin solid was tested using a differential scanning calorimeter (model number DSC 3) of Mettler-Toridol. The heating rate is 10 ℃/min, the heating temperature range is determined according to the properties of the sample, and the sample is prevented from generating decomposition phenomenon.

Yellowness index testing of perfluorosulfonic acid resin solids and perfluorosulfonic acid resin dispersions: non-volatile impurities are present in the perfluorosulfonic acid resin that cause yellowing of the perfluorosulfonic acid resin solids and dispersions. The yellowness index of a perfluorosulfonic acid resin solid sample and a perfluorosulfonic acid resin dispersion liquid is characterized by adopting an UltraScan VIS type spectrocolorimeter of HunterLab company, and the change of the impurity content is judged by comparing the change of the yellowness index.

Determination of solid content of perfluorosulfonic acid resin solid sample and liquid sample: the solid content and volatile content were determined using a HX204 moisture meter from Mettler-Toritods. Test methods refer to the determination of the nonvolatile content of the adhesive in GBT 2793-1995. And (3) determining the non-volatile matter amount of the perfluorinated sulfonic acid resin according to the solid content, wherein the ratio of the non-volatile matter amount of the treated perfluorinated sulfonic acid resin to the non-volatile matter amount of the perfluorinated sulfonic acid resin before treatment is yield.

Determination of the Water content of the solid sample of Perfluorosulfonic acid resin: the water content in the perfluorosulfonic acid resin solid sample was determined by volumetric KF915 water titration using a V20S Karl Fischer moisture meter from Mettler-Tollido.

Optical properties of perfluorosulfonic acid resin film: the optical performance of the perfluorosulfonic acid resin film is measured by a Shanghai apparatus electronic light transmittance haze measuring instrument WGT-S, and the test is carried out according to GB/T2410-2008 standard. The higher the transmission, the better the transparency of the film, and the lower the haze the better the optical effect of the film. The difference of the optical properties of the film can reflect the purity of the perfluorosulfonic acid resin sample to a certain extent, and the higher the purity is, the less impurities are, and the better the optical properties are.

In the examples, Nafion117 ion exchange membranes were purchased from kemu corporation; the G12 composite ion exchange membrane is purchased from Goll company, and the perfluorinated sulfonic acid resin A and the perfluorinated sulfonic acid resin B are commercial products. Dialysis bags were purchased from united states carbonization, MD77,Mw: 3500. The carbon hexaalkane is analytically pure and purchased from Beijing Guang Fine chemical company; perfluoro-n-hexane, analytically pure, purchased from morel, shanghai; the industrial hexane contains 86% of n-hexane and 14% of other hexaalkanes. Tetrafluoroethylene monomer, self-made in laboratory. Sulfonyl fluoride vinyl ether monomers were purchased from Sanming hassfu. All other solvents, dispersants, chemicals needed for synthesis and testing were analytically pure and purchased from the alatin reagent.

EXAMPLE 1 Perfluorosulfonic acid resin solid prepared by dissolving and dispersing Perfluorosulfonic acid resins in different solvents

1 g of perfluorosulfonic acid resin A is weighed and put into 9 g of solvent, and the mixture is dissolved under certain conditions to obtain clear and transparent dispersion liquid. The dispersion was added to 25 g of n-hexane to obtain a precipitate. And (3) drying the precipitate at 180 ℃ for 4 h in vacuum, and obtaining perfluorosulfonic acid resin solid after drying.

The structural formula of the perfluorosulfonic acid resin A in this example is:

the solvent used for the resin dissolution and dispersion in this embodiment includes at least one of water, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone (NMP).

In order to prevent metal ion impurity pollution, the high-temperature and high-pressure dissolving process is carried out in a corrosion-resistant high-pressure reaction kettle.

The solvent, temperature, pressure used in the dissolution dispersion process and the yield of the perfluorosulfonic acid resin solid obtained in this example are shown in Table 1.

TABLE 1

FIG. 1 is the IR spectra of perfluorosulfonic acid resin A and product A-6, which shows that the chemical structure of perfluorosulfonic acid resin is unchanged before and after treatment by the method of this example.

FIG. 2 and FIG. 3 are GPC curves of perfluorosulfonic acid resin A and product A-6, respectively, and it can be seen from FIG. 2 that, in the results of GPC measurement of perfluorosulfonic acid resin A,Mn: 81659，Mw/Mn=1.983389, as can be seen from fig. 3, in the GPC test result of the product a-6,Mn: 82429，Mw/Mn= 1.994489. It can be seen that the molecular weight distribution of the perfluorosulfonic acid resin was substantially consistent before and after treatment using the method of this example.

FIG. 4 and FIG. 5 are DSC curves of perfluorosulfonic acid resin A and product A-6, respectively, and it can be seen from FIG. 4 that the glass transition temperature of perfluorosulfonic acid resin A is 130.76 ℃ and that a disordered decomposition thermal effect curve appears after 180 ℃. As can be seen from FIG. 5, the DSC curve of the product A-6 has a glass transition temperature of 123.03 deg.C, which is very close to 130.76 deg.C of perfluorosulfonic acid resin A. The minor deviations are mainly due to the early appearance of the cold crystallization peak of product A-6, resulting in an early endpoint for its glass transition. It is shown that the heat resistance of the samples before and after the treatment by the method of this example is substantially the same. The cold crystallization peak to peak temperature of the product A-6 in the DSC test curve was 171.72 deg.C, indicating that the product A-6 had a reduced crystallinity compared to the perfluorosulfonic acid resin A. No decomposition peak was observed on the DSC curve of product A-6, indicating that treatment by the method of this example increased the purity of product A-6.

In the embodiment of the invention, the dispersion liquid of the perfluorinated sulfonic acid resin A is prepared by adopting solvents with different components, and all the dispersion liquid can be precipitated by adding an organic precipitator, and higher yield can be obtained. Particularly, in the process of preparing the product a-7 by using the method of this example, the solvent used is n-hexane, i.e., DMAc =1:2:1, that is, the solvent contains 25 wt% of organic precipitant n-hexane, the mass content of the precipitant in the dispersion of the perfluorosulfonic acid resin a is 20%, but a stable dispersion is still obtained, and the yield of the prepared perfluorosulfonic acid resin solid can reach 86.5%. Therefore, the method provided by the embodiment of the invention has low requirement on the solvent, and as long as the mass content of the perfluorosulfonic acid resin and the non-solvent substances except the solvent in the perfluorosulfonic acid resin dispersion liquid is not more than 20%, the method provided by the embodiment of the invention can recycle the recovered solvent, thereby being beneficial to further reducing the production cost.

Example 2: preparing perfluorosulfonic acid resin solid by adopting organic precipitator containing first precipitator

Weighing 80 g of perfluorosulfonic acid resin B, putting the perfluorosulfonic acid resin B into 320 g of solvent, wherein the adopted solvent is dimethyl sulfoxide and isopropanol with the mass ratio of 1:2, and dissolving the mixture for 1 hour at the temperature of 60 ℃ and under the normal pressure condition to obtain 400 g of clear and transparent dispersion liquid W. 5g of dispersion W were added to 15 g of different types of precipitants to obtain a precipitate. And drying the precipitate at 220 ℃ by blowing for 0.5 h to obtain a perfluorosulfonic acid resin solid.

The structural formula of the perfluorosulfonic acid resin B in the embodiment is as follows:

the organic precipitant adopted in the embodiment includes a first precipitant, specifically n-pentane, n-hexane, cyclohexane, perfluoro-n-hexane, a mixture of two kinds of hexaalkanes, petroleum ether, industrial hexane, industrial heptane and a mixture of 6-10 alkanes. Wherein: the composition of the mixture of carbon hexaalkanes X-1 is n-hexane: cyclohexane: 2, 2-dimethylbutane: 2-methylpentane: 2, 3-dimethylbutane 3-methylpentane =10:4:2:1:1: 1; the composition of the mixture of hexaalkanes X-2 is2, 2-dimethylbutane, 2-methylpentane, 2, 3-dimethylbutane, 3-methylpentane =1:1:1: 1; petroleum ether is a light petroleum product, is a mixture of hydrocarbons with low relative molecular mass, and mainly comprises carbon pentaalkane and carbon hexaalkane; commercial hexane to C₆H₁₄And cyclohexane, wherein the mass percent of n-hexane is about 86%; industrial heptane contains n-heptane, iso-heptane and cycloheptane as main components, and small amount of C₈H₁₈And C₆H₁₄(ii) a The component of the mixture of the C6-10 alkanes is industrial heptane: n-nonane: n-decane =1:1: 1.

The yields of perfluorosulfonic acid resin solids obtained by precipitating dispersion W with different organic precipitants in this example are shown in Table 2.

TABLE 2

FIG. 6 is an infrared spectrum of the perfluorosulfonic acid resin B and the product B-2, and the chemical structures of the perfluorosulfonic acid resin before and after the treatment are not changed.

FIG. 7 and FIG. 8 are GPC curves of perfluorosulfonic acid resin B and product B-2, respectively, and it can be seen from FIG. 5 that, in the results of GPC measurement of perfluorosulfonic acid resin B,Mn: 86071，Mw/Mn= 2.029104, as can be seen from fig. 6, in the GPC test result of the product B-2,Mn: 86418，Mw/Mn= 1.954755. It can be seen that the method of the present embodiment is used before and after treatmentThe molecular weight distribution of the perfluorosulfonic acid resin is substantially uniform.

In the method of the embodiment of the invention, organic precipitants with different components are added into the perfluorosulfonic acid resin dispersion liquid W, so that perfluorosulfonic acid resin can be precipitated to obtain precipitates, and higher yield can be obtained. Particularly, in the process of preparing the products B-5, B-6, B-7 and B-8, the mixture of the carbon five and the carbon hexaalkane is used as a precipitator, the mixture of the carbon five and the carbon hexaalkane has excellent precipitation effect, and the yield of the obtained perfluorosulfonic acid resin solid reaches more than 98 percent. Therefore, in industrial production, the cost can be further reduced by adopting a carbon five and carbon six alkane mixture or an industrial product with the main component of the carbon five and carbon six alkane as a precipitating agent.

Example 3 Perfluorosulfonic acid resin solids were prepared using an organic precipitant containing a second precipitant

50 g of perfluorosulfonic acid resin A (the same perfluorosulfonic acid resin as used in example 1) was dissolved in 500 g of DMF solvent at 60 ℃ to give a dispersion, and 10 g of the dispersion was added to 40 g of the second type precipitant or mixed precipitant to give a precipitate. And (3) drying the precipitate at 100 ℃ for 4 h in vacuum, and obtaining perfluorosulfonic acid resin solid after drying.

The second precipitator is carbon disulfide and C1-C5 halogenated alkane, and is mutually soluble with all solvents of the perfluorinated sulfonic acid resin dispersion liquid except water, and is also mutually soluble with the first precipitator and the third precipitator. The kind of precipitant and the yield of solid perfluorosulfonic acid resin obtained in this example are shown in Table 3. Wherein C is₂H₄Cl₂、C₂H₃Cl₃、C₃H₇Cl、C₄H₉Cl、C₅H₁₀Cl is a mixture of isomers, the different isomers having the same mass in the mixture. C₂H₄Cl₂Is a mixture of 1, 2-dichloroethane and 1, 1-dichloroethane; c₂H₃Cl₃Is a mixture of 1,1,2 trichloroethane and 1,1,1 trichloroethane; c₃H₇Cl is a mixture of chloropropane and isopropyl chloride; c₄H₉Cl is chlorobutane, 2-chlorobutane or 1-a mixture of chloro-2-methylpropane and 2-chloro-2-methylpropane; c₅H₁₀Cl is chloropentane and is a mixture of various monochlorides of pentane and isopentane.

TABLE 3

When the mass percentage content of the second precipitator in the precipitator is not lower than 30%, the content of ethanol, isopropanol and n-propanol in the solvent is not required to be limited, and the perfluorosulfonic acid resin dispersion liquid dissolved in the high-boiling-point organic solvent can be mutually dissolved with the solvent to form a uniform solution without additionally adding ethanol, isopropanol and n-propanol, so that the perfluorosulfonic acid resin is separated out.

Example 4 Perfluorosulfonic acid resin solids were prepared using an organic precipitant containing a third precipitant

5g of perfluorosulfonic acid resin A (the same perfluorosulfonic acid resin as used in example 1) was dissolved in 45 g of an aqueous solvent at 60 ℃ to obtain a dispersion, and 10 g of the dispersion was added to 40 g of the third type precipitant or mixed precipitant to obtain a precipitate. And (3) drying the precipitate at 100 ℃ for 4 h in vacuum, and obtaining perfluorosulfonic acid resin solid after drying.

The third precipitator is tetrahydrofuran, acetone and butanone, and is mutually soluble with all solvents of the perfluorinated sulfonic acid resin dispersion liquid and also mutually soluble with the first precipitator and the second precipitator. The kind of precipitant and the yield of solid perfluorosulfonic acid resin obtained in this example are shown in Table 4.

TABLE 4

And when the mass content of the third precipitator contained in the precipitator is not less than 30%, the composition of the solvent is not required, and particularly the water content in the solvent is not limited. Therefore, a suitable organic precipitant containing not less than 30% of the third precipitant can be designed to precipitate the perfluorosulfonic acid resin dispersion of any solvent component, and the solid yield of the obtained perfluorosulfonic acid resin can reach more than 94%.

Example 5

Adding 50 g of perfluorosulfonic acid resin A (the perfluorosulfonic acid resin adopted in the same example 1) into 100 g of solvent, namely dimethyl sulfoxide and isopropanol (solvent T for short) in a mass ratio of 1:1, dissolving and dispersing at room temperature to obtain a perfluorosulfonic acid resin dispersion liquid, dropwise adding the dispersion liquid into 1000 g of n-hexane for precipitation, wherein the stirring speed in the precipitation process is 900 rpm, filtering to obtain a solid product with the mass content of the solvent of 18%, and performing vacuum drying on the precipitation product at 80 ℃ for 24 hours to obtain a powdery solid product A-11 with the granularity of 100-130 meshes, wherein the yield is 92.41%.

The product A-11 obtained had a solids content of 99.45%, a water content of 0.54%, a content of other volatile substances of less than 0.01% and an EW value of 899.43 g/mol. And (5) detecting small molecular free acid, wherein the pH value of the water dispersion liquid outside the dialysis bag is 7, and the water dispersion liquid does not contain small molecular acid impurities. The yellowness index of the solid was 0.13. And dissolving the product A-11 in a solvent (referred to as solvent N for short) consisting of water and isopropanol in a mass ratio of 1:1 to obtain a perfluorosulfonic acid resin dispersion liquid, wherein the solid content of the dispersion liquid is20 percent, and the yellowness index of the dispersion liquid is 0.01.

And (3) drying the product A-11 at 80 ℃ for 24 h in vacuum to obtain the product A-11-80. The yellowness index of the product A-11-80 solid was 0.66. The product A-11-80 was dissolved in solvent N, the solids content of the dispersion was 20%, and the yellowness index of the dispersion was 0.01.

10 g of the product A-11 was dissolved in 30 g of the solvent T at room temperature to obtain a perfluorosulfonic acid resin dispersion, the dispersion was dropped into 120 g of n-hexane for precipitation, and the precipitated product was vacuum-dried at 80 ℃ for 24 hours to obtain a powdery solid product A-12 with a yield of 99.16%.

The product A-12 had a solid content of 99.55%, a water content of 0.45%, a content of other volatile substances of less than 0.01%, and an EW value of 897.89 g/mol. And (5) detecting small molecular free acid, wherein the pH value of the water dispersion liquid outside the dialysis bag is 7, and the water dispersion liquid does not contain small molecular acid impurities. The yellowness index of the solid was 0. And dissolving the product A-12 in a solvent N to obtain a perfluorosulfonic acid resin dispersion liquid, wherein the solid content of the dispersion liquid is 20%, and the yellowness index of the dispersion liquid is 0.

And (3) drying the product A-12 at 80 ℃ for 24 h in vacuum to obtain the product A-12-80. The yellowness index of the product A-12-80 solid was 0. And dissolving the product A-12-80 in a solvent N, wherein the solid content of the dispersion liquid is 20%, and the yellowness index of the dispersion liquid is 0.

And (3) drying the product A-12 at 220 ℃ for 0.5 h in vacuum to obtain the product A-12-220. 12-220 of the product A, the solid content is more than 99.99%, the water content is less than 0.01%, the content of other volatile substances is less than 0.01%, and the EW value is 900.03 g/mol. And (5) detecting small molecular free acid, wherein the pH value of the water dispersion liquid outside the dialysis bag is 7, and the water dispersion liquid does not contain small molecular acid impurities. The yellowness index of the solid was 0. The product A-12-220 was dissolved in solvent N, the solids content of the dispersion was 20%, and the yellowness index of the dispersion was 0.

In the embodiment, acidic small molecular impurities and non-volatile impurities in the perfluorosulfonic acid resin can be effectively removed through two times of dissolving and reprecipitation, the yield of the prepared perfluorosulfonic acid resin solid A-12 can reach 99.16%, the yellowness index of the product A-12 solid and a dispersion liquid formed by dispersing in a solvent N is as low as 0, after the A-12 is subjected to temperature rise drying treatment again, the yellowness index of the perfluorosulfonic acid resin solid and the dispersion liquid formed by dissolving in the solvent can still keep 0, the performance is stable, and the high-purity perfluorosulfonic acid resin A-12-220 is prepared after high-temperature drying.

EXAMPLE 6 preparation of perfluorosulfonic acid resin solids of different macroscopic sizes

Weighing 10 g of perfluorosulfonic acid resin B, wherein the solvent is isopropanol and NMP with the mass ratio of 6:4, stirring and dissolving the mixture in 70 g of solvent at 60 ℃ to obtain perfluorosulfonic acid resin dispersion, adding the dispersion into 220 g of industrial hexane to separate out perfluorosulfonic acid resin precipitate, wherein the stirring speed in the precipitation process is 300 rpm, the precipitate is floccule, and the solvent content in the precipitate is 96%. And after precipitation, rinsing for 1-5 times by using 50 g of rinsing agent, and stirring for 30 min, wherein the first rinsing agent is 80% of industrial hexane and 20% of isopropanol, the second rinsing agent is 97% of industrial hexane and 3% of tetrahydrofuran, the third rinsing agent is 0.3% of dichloromethane and 99.7% of industrial hexane, and the fourth rinsing agent and the fifth rinsing agent are both n-hexane. And (3) carrying out vacuum drying treatment on the rinsed solid product at 80 ℃ for 24 h, and drying to obtain a perfluorosulfonic acid resin solid. The rinse precipitation protocol and the size distribution of the perfluorosulfonic acid resin solids after drying used in this example are shown in Table 5.

TABLE 5

In the embodiment, the macroscopic size of the dried perfluorosulfonic acid resin solid can be effectively regulated and controlled by controlling the stirring rate in the rinsing process and the mass content of the solvent in the rinsed solid product.

The product J-1 was obtained in 99.1% yield. The solid content was 99.31%, the water content was 0.66%, the content of other volatile substances was 0.02%, and the EW value was 1047.54 g/mol. And (5) detecting small molecule free acid, wherein the pH value of the water solution outside the dialysis bag is 7, and the water solution does not contain small molecule acid impurities. The yellowness index of the solid was 0.63. The product J-1 is dissolved in a solvent (referred to as solvent N) consisting of water and isopropanol with the mass ratio of 1:1, the solid content of the solution is20 percent, and the yellowness index of the solution is 0.05.

And (3) drying the product J-1 at 80 ℃ for 24 h in vacuum to obtain the product J-1-80. The yellowness index of the product J-1-80 solids was 0.64. The product J-1-80 was dissolved in solvent N at a solids content of 20% and a yellowness index of 0.05.

Example 7 Synthesis of sodium-type perfluorosulfonic acid resin and acid-type perfluorosulfonic acid resin

(1) Sulfonyl fluororesin

At the temperature of 18-20 ℃, an emulsion polymerization method is adopted, and a redox system initiates binary copolymerization to synthesize the sulfonyl fluoride resin. The redox system is sodium persulfate (Na)₂S₂O₈) With sodium bisulfite (NaHSO)₃) In combination with (1). Sodium perfluorooctanoate (C)₇F₁₅C (O) ONa) as emulsifier, disodium hydrogen phosphate heptahydrate (Na)₂HPO₃·7H₂O) is a buffering agent.

Preparing an emulsifier, a buffering agent and a redox system into dispersion liquid, adding sulfonyl fluoride vinyl ether for emulsification, transferring the emulsion into a corrosion-resistant reaction kettle, filling a tetrafluoroethylene monomer in the reaction process and keeping the pressure, and terminating the copolymerization when the consumption rate of the tetrafluoroethylene monomer is stable and reaches the maximum value. After coagulation, the polymer was washed with water and freeze-dried to obtain a sulfonyl fluoride resin.

(2) Sodium type perfluorosulfonic acid resin

And (2) soaking the sulfonyl fluorine resin in 2 mol/L sodium hydroxide dispersion liquid, hydrolyzing for 24 h at 80 ℃, and washing excess alkali liquor with water to obtain the sodium type perfluorinated sulfonic acid resin.

(3) Acid type perfluorosulfonic acid resin

And (3) soaking the sodium type perfluorosulfonic acid resin prepared in the step (2) in 2 mol/L nitric acid dispersion, performing ion replacement for 24 h at 80 ℃, washing the redundant acid liquor with water, and performing vacuum drying for 24 h at 80 ℃ to obtain the dried acid type perfluorosulfonic acid resin.

EXAMPLE 8 purification of sodium perfluorosulfonic acid resin

Dissolving 1 g of the sodium-type perfluorosulfonic acid resin prepared in example 7 in 11 g of dimethyl sulfoxide to form a perfluorosulfonic acid resin dispersion, dropwise adding the prepared dispersion into 61.6 g of n-hexane and 26.4 g of chloroform to obtain powdery precipitate, wherein the stirring speed in the precipitation process is 400 rpm, the solvent content in the solid product obtained by filtration is 18%, and the precipitate is dried in vacuum at 180 ℃ for 1 h to obtain a powdery product with the size of 50-80 meshes.

The product obtained in this example had a solids content of 99.91%, a water content of 0.05%, a content of other volatile substances of 0.03%, and a yellowness index of the solids of 0.80.

Example 9 purification of acid Perfluorosulfonic acid resin

Dissolving 1 g of the acid perfluorosulfonic acid resin prepared in example 7 in 10 g of a solvent to form a perfluorosulfonic acid resin dispersion, wherein the solvent is dimethyl sulfoxide and isopropanol in a mass ratio of 1:1, dropwise adding the prepared dispersion into 46 g of n-pentane, 2 g of chloropropane and 2 g of tetrahydrofuran to obtain flocculent precipitate, stirring at a speed of 800 rpm during precipitation, filtering to obtain a solid product with a solvent content of 97%, and vacuum-drying the precipitate at 180 ℃ for 2 hours to obtain a blocky product.

The solid content of the product was 99.85%, the water content was 0.07%, the content of other volatile substances was 0.08%, and the yellowness index of the solid was 0.68.

Example 10 preparation of Low crystallinity Nafion resin

The Nafion117 ion exchange membrane is prepared by high-temperature melt extrusion, and has high crystallinity and good mechanical and thermal properties. Crystallization of perfluorosulfonic acid resin articles depends on thermal history, and whether melt processing or dispersion drying processing, crystallization of perfluorosulfonic acid resin is almost completely destroyed in the melt and dispersion state and recrystallized during solidification or drying molding. For perfluorosulfonic acid resin articles, high crystallinity is generally sought to improve the stability, mechanical properties, electrochemical properties and solvent resistance of the article, but for perfluorosulfonic acid resin raw materials, low crystallinity perfluorosulfonic acid resin solids are more convenient for melt processing and dispersion preparation. The acid type high-crystallinity Nafion117 ion exchange membrane cannot be completely dissolved in a solvent under normal pressure.

Weighing 5g of an acid Nafion117 ion exchange membrane, adding the acid Nafion117 ion exchange membrane into 100 g of a solvent to form a dispersion, dissolving the solvent which is a mixed solvent of water and isopropanol in a mass ratio of 1:2 for 12 hours at 240 ℃ under the protection of argon at 10 MPa to obtain a Nafion resin dispersion R-1. And adding 50 g of isopropanol into the dispersion liquid R-1, and uniformly stirring to obtain a dispersion liquid R-2. And adding the dispersion liquid R-2 into 750 g of industrial hexane to separate out a precipitate, wherein the stirring speed in the precipitation process is 500rpm, the solvent content in the solid product obtained by filtering is 18%, and drying the precipitate in a vacuum oven at 50 ℃ for 72 hours to obtain a granular solid product S-1 with the size of 55-75 meshes. In this example, isopropanol was added to dispersion R-1 to form dispersion R-2, and increasing the isopropanol content in the dispersion allowed more isopropanol and water to be miscible with industrial hexane, to reduce the mass content of adsorbed water and isopropanol in the filtered solid product.

The product S-1 is Nafion resin with low crystallinity, 10 g of the product S-1 is put into 15 g of N, N-Dimethylformamide (DMF), and stirred at 80 ℃, after 4 h, the solid of the product S-1 is completely dissolved to form uniform and transparent dispersion liquid. The dispersion was knife-coated with a spatula and dried at 180 ℃ for 4 hours to give an ion exchange membrane S-1-M having a thickness of 50 μ M.

The ion exchange membrane S-1-M has the yellowness index of 0, the transmittance of 100 percent, the haze of 0 percent and the EW value of 1098.55 g/mol.

And (2) vacuum-drying the ion exchange membrane S-1-M at 180 ℃ for 1 h, wherein the yellowness index is 0, the transmittance is 100%, and the haze is 0%. The film does not turn yellow by high-temperature heat treatment, and the optical performance is not reduced.

EXAMPLE 11 recovery of spent Goll G12 ion exchange membranes

The Gole G12 ion exchange membrane mainly comprises perfluorosulfonic acid resin and an insoluble expanded polytetrafluoroethylene support layer. The recovery process recovers the perfluorosulfonic acid resin by dissolution and filters to remove the insoluble support layer. The mass of the recoverable perfluorosulfonic acid resin is the mass of the ion exchange membrane minus the mass of the support layer, and the recovery rate is the ratio of the mass of the perfluorosulfonic acid resin product to the mass of the recoverable perfluorosulfonic acid resin.

Dissolving 5G of waste G12 ion exchange membrane in 50G of dimethyl sulfoxide (DMSO) at 120 ℃, filtering and separating the support layer and the resin dispersion liquid by using a sand core funnel with a G3 aperture after 12 h, and washing the support layer and the funnel by using 50G of water to fully separate the resin from the support layer to obtain the resin dispersion liquid. And adding the resin dispersion liquid into a mixed precipitator of 75 g of acetone and 125 g of n-hexane to separate out a precipitate, wherein the stirring speed in the precipitation process is 1200 rpm, so that a blocky precipitate is obtained, and the solvent content in a solid product obtained after filtration is 96%.

The resulting cake precipitate was divided into two equal portions by mass.

And (3) drying one part of the blocky precipitate for 1 h under vacuum at 160 ℃ to obtain a blocky product S-2, wherein the recovery rate is 94.7%, the solid content is 99.77%, the water content is 0.17%, the content of other volatile substances is 0.06%, and the yellowness index is 0.08.

Another portion of the cake was rinsed 4 times with agitation at 1200 rpm for 5 min each rinse. The first rinse was 100 g of dichlorohexane, the second 45 g of n-hexane and 5g of dichloromethane, the third 20 g of n-hexane and the fourth 10 g of n-hexane. And (3) stirring at 1500 rmp in the rinsing process, obtaining powdery solid after rinsing, wherein the content of the solvent in the solid is 13%, and performing vacuum drying at 160 ℃ for 1 h to obtain a powdery product S-2-P with the size of 150-250 meshes. The recovery rate of the product S-2-P is 95.2%, the solid content is 99.95%, the water content is less than 0.02%, the content of other volatile substances is 0.03%, and the yellowness index is 0.02.

In this embodiment, the cake product obtained by the precipitation is rinsed and dried to obtain a powdery final product S-2-P, and the purity of the final product S-2-P obtained by rinsing is further improved as compared with the cake product S-2.

Example 12

A resin dispersion was obtained by treating a spent G12 ion exchange membrane in the same manner as in example 11, except that half of the resin dispersion was added to a mixed precipitant of 187.5G of acetone and 312.5G of n-hexane to precipitate out a precipitate, the stirring rate during the precipitation was 1500rpm, and the solvent content in the solid product obtained by filtration was 13%, whereby a powdery precipitate was obtained. And (3) drying the powdery precipitate at 160 ℃ for 1 h in vacuum to obtain a powdery perfluorosulfonic acid resin product with the size of 150-250 meshes. The product recovery rate is 95.3%, the solid content is 99.95%, the water content is less than 0.02%, the content of other volatile substances is 0.03%, and the yellowness index is 0.04.

Comparative example 1

Perfluorosulfonic acid resin a was not treated by the method of example 3. The perfluorosulfonic acid resin A was measured to have a solid content of 94.63%, a water content of 5.33%, a content of other volatile substances of 0.04%, and an EW value of 748.33 g/mol. And (5) detecting small molecule free acid, wherein the pH value of the water dispersion liquid outside the dialysis bag is 5, which indicates that small molecule acid impurities exist in the resin. The yellowness index of the solid was 9.63, indicating that the resin contained a certain amount of non-volatile impurities. Dissolving the perfluorosulfonic acid resin A in a solvent N, wherein the solid content of the dispersion is20 percent, and the yellowness index of the dispersion is 0.86.

The perfluorosulfonic acid resin A was vacuum dried at 80 ℃ for 24 h to obtain sample A-80. The yellowness index of the solids of sample A-80 was 36.54. Sample a-80 was dissolved in solvent N, the solids content of the dispersion was 20%, and the yellowness index of the dispersion was 3.36. And (4) detecting the micromolecule free acid of the sample A-80, wherein the pH value of the water dispersion liquid at the outer side of the dialysis bag is 5, which indicates that micromolecule acid impurities exist in the resin.

Example 3 compared with comparative example 1, the perfluorosulfonic acid resin A was purified to obtain perfluorosulfonic acid resin solid, and then small-molecule acid impurities were removed, and the EW value of the product was increased. The yellowness of the solid and the dispersion of the treated product A-11 and the product A-12 are both obviously reduced, and the yellowness is not obviously changed after vacuum drying, which shows that the non-volatile impurities are obviously reduced. Therefore, the method of example 3 effectively improves the purity of the perfluorosulfonic acid resin A, and the product can maintain stable performance.

Comparative example 2

Perfluorosulfonic acid resin a was not treated by the method of example 3, and the perfluorosulfonic acid resin a solids were rinsed with deionized water, which dissolved in water. Because the perfluorinated sulfonic acid resin A is water-soluble perfluorinated sulfonic acid resin, the perfluorinated sulfonic acid resin A cannot be purified by adopting a water washing method.

The method of the embodiment of the invention is not limited by water-soluble resin and has wide application.

Comparative example 3

Perfluorosulfonic acid resin a was not treated by the method of example 3.

Dissolving the perfluorosulfonic acid resin A in water to obtain a perfluorosulfonic acid resin dispersion solution U. The dispersion had a solids content of 20% and a yellowness index of 0.72. 50 g of the perfluorosulfonic acid resin dispersion U was poured into a dialysis bag, dialyzed in an environment of deionized water, and the deionized water outside the dialysis bag was replaced until the outside liquid maintained pH = 7. Obtaining the dispersed solution U-1 of the perfluorinated sulfonic acid resin A after dialysis, wherein the solid content of the dispersed solution U-1 is 3.56 percent, and the yellowness index is 0.17.

The dispersion U-1 was dried under vacuum at 80 ℃ for 2 weeks to give the solid product U-2. The product U-2 has a solids content of 99.63%, a water content of 0.36%, a content of other volatile substances of less than 0.01% and an EW value of 904.54 g/mol. And (5) detecting small molecule free acid, wherein the pH value of the water dispersion liquid outside the dialysis bag is 7, and the water dispersion liquid does not contain acidic small molecule impurities. The yellowness index of the solid was 7.75, containing a certain amount of non-volatile impurities. The product U-2 was dissolved in solvent N, the solids content of the dispersion was 20% and the yellowness index of the dispersion was 0.59.

Compared with the method adopting deionized water dialysis purification in the comparative example 3, the method in the example does not generate a large amount of fluorine-containing sewage, can directly obtain a pure solid product, has a shorter drying process, can remove hydrophobic impurities, has higher purity of the product, lower yellowness index and higher efficiency, and can be applied to large-scale industrial production.

Comparative example 4

Perfluorosulfonic acid resin a was not treated by the method of example 3.

The perfluorosulfonic acid resin A was dissolved in dimethyl sulfoxide (DMSO) to obtain a perfluorosulfonic acid resin dispersion V. The dispersion V had a solids content of 20% and a yellowness index of 0.80. Pouring 50 g of the dispersion V into a dialysis bag, dialyzing in a DMSO environment, replacing DMSO outside the dialysis bag until the yellowness of the dispersion in the dialysis bag is less than 0.02, consuming 2.7 kg of analytical pure DMSO in total and generating corresponding quality waste liquid to obtain the perfluorinated sulfonic acid resin dispersion V-1 after dialysis, wherein the solid content of the dispersion V-1 is 2.87%, and the yellowness index is 0.01.

The dispersion V-1 was dried under vacuum at 80 ℃ for 2 weeks to give a solid product V-2. The product V-2 had a solids content of 98.37%, a water content of 1.03%, other volatiles 0.60% and an EW value of 905.52 g/mol. And (5) detecting small molecule free acid, wherein the pH value of the water dispersion liquid outside the dialysis bag is 7, and the water dispersion liquid does not contain acidic small molecule impurities. The yellowness index of the solid was 0.02, containing a certain amount of non-volatile impurities. And dissolving the product V-2 in a solvent N, wherein the solid content of the dispersion liquid is 20%, and the yellowness index of the dispersion liquid is 0.

Compared with the DMSO dialysis purification in the comparative example 4, the method in the embodiment 3 has the advantages that the purification effect of the two is equivalent, less organic solvent is used for purifying the perfluorosulfonic acid resin A with the same quality, a pure solid product can be directly obtained, the drying process is shorter, the efficiency is higher, and the method can be applied to large-scale industrial production.

Comparative example 5

The perfluorosulfonic acid resin dispersion of example 4 was poured into a beaker and dried at 60 deg.C, 80 deg.C, 120 deg.C and 180 deg.C, respectively, to give a solid monolithic product.

Example 4 compared with comparative example 5, perfluorosulfonic acid resin solids with different sizes can be obtained after drying by controlling the stirring rate during rinsing and the solvent content in the solid product after rinsing, while in comparative example 5, the solvent is directly dried, only blocky solids can be obtained, and further processing is needed to obtain granular or powdery solid products.

Comparative example 6

Perfluorosulfonic acid resin B was not treated by the method of example 4. The perfluorosulfonic acid resin B was measured to have a solids content of 95.21%, a water content of 4.62%, a content of other volatile substances of 0.16%, and an EW value of 897.69 g/mol. And (4) detecting small molecular free acid, wherein the pH value of the water dispersion liquid outside the dialysis bag is 5, and small molecular acid impurities exist in the resin. The yellowness index of the solid was 2.63, containing a certain amount of non-volatile impurities. Dissolving the perfluorosulfonic acid resin B in a solvent N, wherein the solid content of the dispersion liquid is20 percent, and the yellowness index of the dispersion liquid is 0.24.

The perfluorosulfonic acid resin B was vacuum dried at 80 ℃ for 24 h to obtain sample B-80. The yellowness index of the solids of sample B-80 was 53.37. Sample B-80 was dissolved in solvent N, the solids content of the dispersion was 20%, and the yellowness index of the dispersion was 2.74. And (4) detecting the micromolecular free acid of the sample B-80, wherein the pH value of the water dispersion liquid at the outer side of the dialysis bag is 5, and micromolecular acid impurities exist in the resin.

In example 4, compared with comparative example 6, after dispersing and precipitating the perfluorosulfonic acid resin B, small-molecule acid impurities were removed, and the EW value was increased. The yellowness of the solid and the solution of the product J-1 after treatment is obviously reduced, and the yellowness is not obviously changed after vacuum drying, which shows that the non-volatile impurities are obviously reduced, and the purity of the perfluorosulfonic acid resin is improved.

Comparative example 7

The sodium perfluorosulfonic acid resin was not treated by the method of example 6. The sodium perfluorosulfonic acid resin of example 6 was rinsed with deionized water until the rinse was neutral. Vacuum drying at 180 deg.C for 2 hr to obtain 96.63% solid content, 2.05% water content, 1.32% other volatile substances, and 64.62% solid yellowness index.

Compared with the method of the comparative example 7, the method of the example 6 has the advantages that the purity of the product obtained by drying after precipitation is higher, impurities which cannot be removed by washing can be removed, and the generated fluorine-containing wastewater is less.

Comparative example 8

The acid form perfluorosulfonic acid resin was not treated by the method of example 7. The acid form perfluorosulfonic acid resin of example 7 was rinsed with deionized water until the rinse was neutral. Vacuum drying at 180 deg.C for 2 hr to obtain 92.55% solid content, 7.05% water content, 0.40% other volatile substances, and a solid yellowness index of 67.38.

Compared with the comparative example 8, the product obtained by drying after precipitation has higher purity, can remove impurities which cannot be removed by washing, consumes less clean water and generates less fluorine-containing wastewater.

Comparative example 9

The acid form Nafion117 ion exchange membrane was not treated by the method of example 8. The untreated acid Nafion117 ion exchange membrane is stirred and dissolved by DMF at 60 ℃, 90 ℃, 120 ℃ and 150 ℃ under the protection of nitrogen, and can not be completely dissolved after being dissolved for 24 hours.

The process of example 8 compared to comparative example 9, precipitation followed by low temperature drying yielded a low crystallinity Nafion resin in acid form, which was completely soluble in DMF at atmospheric pressure.

Comparative example 10:

the acid form Nafion117 ion exchange membrane was not treated by the method of example 8. The untreated acid type Nafion117 ion exchange membrane was subjected to performance testing: the EW value was 1098.90 g/mol, the yellowness index was 1.10, the transmission was 99.42%, and the haze was 0.09%. Treating the acidic Nafion117 ion exchange membrane with 3% hydrogen peroxide at 60 deg.C for 30 min, and treating with deionized water at 60 deg.C for 30 min to remove residual hydrogen peroxide. Vacuum drying at 60 deg.C for 2 h to obtain dried acidic Nafion117 ion exchange membrane S-3. The EW value was 1098.75 g/mol, the yellowness index of S-3 was 0, the transmittance was 100%, and the haze was 0%. And (3) drying the S-3 at 180 ℃ for 1 h in vacuum, wherein the yellowness index is 0.08, the transmittance is 99.89% and the haze is 0.06%.

Compared with the method of the comparative example 10, the ion exchange membrane S-1-M prepared in the example 8 has the same optical performance and EW value as the Nafion117 ion exchange membrane treated by hydrogen peroxide in the comparative example 10, and the yellowness index is 0. However, after high temperature treatment, the optical performance of the Nafion117 ion exchange membrane bleached by hydrogen peroxide in the comparative example 10 is reduced, and the yellowness index is increased, while the optical performance and the yellowness index of the S-1-M ion exchange membrane in the example 8 are not changed.

Comparative example 11

The same procedure as in example 9, except that the resin dispersion obtained by separation was directly subjected to vacuum drying at 160 ℃ for 8 hours without adding it to n-hexane, was carried out to obtain a bulk product S-4 in a recovery rate of 97.3%.

The product S-4 obtained in comparative example 11 had a solid content of 98.65%, a water content of 0.97%, other volatile substances content of 0.38%, and a yellowness index of 1.41.

Compared with the solid product S-4 obtained by directly drying the dispersion liquid in the comparative example 11, the product S-2 obtained in the example 9 has the advantages of short drying time, less waste gas generation and high product purity, and is a more efficient and environment-friendly recovery method.

In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. A method for preparing a perfluorosulfonic acid resin solid, comprising:

2. The method for preparing perfluorosulfonic acid resin solid according to claim 1, wherein in the step a, the solvent comprises at least one of a high-boiling organic solvent, water or a lower aliphatic alcohol.

3. The method for preparing perfluorosulfonic acid resin solid according to claim 2, wherein in the step a, the high-boiling organic solvent is at least one selected from the group consisting of ethylene glycol, propylene glycol, glycerin, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, and N-methylpyrrolidone; the lower aliphatic alcohol is selected from at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol and isobutanol.

4. The method for preparing perfluorosulfonic acid resin solid according to claim 1, wherein in the step b, when the organic precipitant comprises: when the weight percentage of the first precipitator is more than 90 wt% and less than or equal to 100wt%, the weight percentage of the second precipitator is more than or equal to 0wt% and less than 10wt% and the weight percentage of the third precipitator is more than or equal to 0wt% and less than 10wt%, the solvent in the step a comprises at least one of ethanol, isopropanol or n-propanol, the sum of the weight percentages of the ethanol, the isopropanol or the n-propanol in the solvent is not less than 40%, and the weight percentage of water in the solvent is not more than 30%; alternatively, the first and second electrodes may be,

when the organic precipitating agent comprises: when the first precipitator is more than or equal to 70 wt% and less than or equal to 90 wt% and the third precipitator is more than or equal to 0 and less than or equal to 10wt%, the solvent in the step a comprises at least one of ethanol, isopropanol or n-propanol, the sum of the mass percentages of the ethanol, the isopropanol or the n-propanol in the solvent is not less than 20%, and the mass percentage of water in the solvent is not more than 30%.

5. The method according to claim 1, wherein in the step a, the mass content of the perfluorosulfonic acid resin in the perfluorosulfonic acid resin dispersion liquid is 0.1 to 50%.

6. The method according to claim 1 or 5, wherein in the step a, the mass content of the non-solvent substance other than the perfluorosulfonic acid resin and the solvent in the perfluorosulfonic acid resin dispersion liquid is not more than 20%.

7. The method according to claim 1, wherein in the step a, the perfluorosulfonic acid resin is at least one selected from the group consisting of a metal ion type perfluorosulfonic acid resin, an acid type perfluorosulfonic acid resin, an ammonium ion type perfluorosulfonic acid resin, a quaternary ammonium salt cation type perfluorosulfonic acid resin, an imidazole ion type perfluorosulfonic acid resin, and a waste containing perfluorosulfonic acid resin.

8. The method for preparing perfluorosulfonic acid resin solid according to claim 7, wherein in the step a, the used material containing perfluorosulfonic acid resin comprises a perfluorosulfonic acid resin ion-exchange membrane, a membrane electrode assembly, a perfluorosulfonic acid resin catalyst, or an ionomer-metal composite.

9. The method for producing a perfluorosulfonic acid resin solid according to claim 1, wherein the mass of the organic precipitant in the step b is 1.5 to 10 times the mass of the solvent in the perfluorosulfonic acid resin dispersion liquid obtained in the step a.

10. The method for preparing perfluorosulfonic acid resin solid according to claim 1, wherein in the step b, the dispersion of perfluorosulfonic acid resin is stirred while an organic precipitant is added to precipitate, and the solid product is obtained by filtration,

11. The method for producing a perfluorosulfonic acid resin solid according to claim 1, wherein said steps a and b are repeated before said step c, and then dried to produce a perfluorosulfonic acid resin solid.

12. The method for preparing solid perfluorosulfonic acid resin according to claim 1, wherein in step c, the solid product obtained in step b is subjected to agitation rinsing treatment by using a rinsing agent, and the solid perfluorosulfonic acid resin with different sizes is obtained after drying by controlling the agitation rate during rinsing and the solvent content in the rinsed solid.

13. The method for preparing solid perfluorosulfonic acid resin according to claim 12, wherein in step c, the rinsing agent comprises 70% to 100% by mass of a first component and 0% to 30% by mass of a second component, wherein the first component is at least one selected from the group consisting of carbon pentaalkane, carbon hexaalkane, tetrahydrofuran and dichloromethane; the second component is selected from ethanol, isopropanol, n-propanol, dichloromethane, tetrahydrofuran, chloroform, chloroethane, C₂H₄Cl₂、C₂H₃Cl₃、C₃H₇Cl、C₄H₉Cl、C₅H₁₀At least one of Cl, acetone or butanone.

14. The method for preparing the perfluorosulfonic acid resin solid according to claim 13, wherein in the step c, the number of times of rinsing is not less than 3, and in the first rinsing, the first component is 70-100% by mass and the second component is 0-30% by mass; during the second rinsing, the mass content of the first component in the rinsing agent is 85-100%, and the mass content of the second component is 0-15%; and during rinsing for the third time or more, the mass content of the first component is 95-100%, and the mass content of the second component is 0-5%.

15. The method for preparing perfluorosulfonic acid resin solid according to claim 12 or 13, wherein the mass of the rinsing agent in the step c is 3 to 50 times the mass of the solvent in the solid product obtained in the step b.

16. The method for preparing perfluorosulfonic acid resin solid according to claim 12 or 13, wherein in step c, 150 to 300 mesh perfluorosulfonic acid resin powder is obtained after drying when the stirring speed is 1200 to 2000 rpm and the solvent content in the solid product after rinsing treatment is not more than 15% by mass; alternatively, the first and second electrodes may be,

17. The method for preparing solid perfluorosulfonic acid resin according to claim 1, wherein in step c, the solid product obtained in step b is dried at-80 ℃ to 60 ℃ and 0 to 0.2 MPa to obtain solid perfluorosulfonic acid resin.