CN114276561B - Preparation method of perfluorosulfonic acid resin dispersion liquid - Google Patents
Preparation method of perfluorosulfonic acid resin dispersion liquid Download PDFInfo
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- 239000011347 resin Substances 0.000 title claims abstract description 156
- 229920005989 resin Polymers 0.000 title claims abstract description 156
- 239000006185 dispersion Substances 0.000 title claims abstract description 89
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000007788 liquid Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 45
- 239000002904 solvent Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 27
- 238000004821 distillation Methods 0.000 claims abstract description 25
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012528 membrane Substances 0.000 abstract description 19
- 238000009826 distribution Methods 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 21
- 238000004090 dissolution Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
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Abstract
The invention discloses a preparation method of a perfluorosulfonic acid resin dispersion liquid, which comprises the following steps: a. dissolving perfluorinated sulfonic acid resin in a first solvent, and filtering to obtain a first resin dispersion liquid; b. c, carrying out reduced pressure distillation on the first resin dispersion liquid obtained in the step a to obtain gel; c. and c, dissolving the gel obtained in the step b in a second solvent to obtain a perfluorosulfonic acid resin dispersion liquid. According to the preparation method of the perfluorosulfonic acid resin dispersion liquid, high-temperature and high-pressure dispersion of solid sulfonic acid resin is not needed, the perfluorosulfonic acid resin dispersion liquid with high solid content, high viscosity, small particle size and narrow particle size distribution can be prepared under mild conditions, and the prepared dispersion liquid can be suitable for proton exchange membranes, water electrolysis membranes and fuel cell slurries.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a perfluorosulfonic acid resin dispersion liquid.
Background
A fuel cell is an energy conversion device capable of converting chemical energy into electric energy, and a proton exchange membrane is one of core components of a proton exchange fuel cell, and its performance directly determines the performance of the proton exchange fuel cell.
Whether it be a proton exchange membrane homogeneous membrane or a proton exchange membrane composite membrane, sulfonic acid resin dispersion is an important process step in the preparation of proton exchange membranes. The solvents are generally chosen on the basis of: 1. a principle of polarity similarity; 2. the principle of similar solubility parameters; 3. polymer-solvent interaction parameters. Perfluorosulfonic acid resins have predominantly a C-F backbone and an ion-containing side chain structure, which have different solubility parameters. Although many researchers have studied the dissolution of sulfonic acid resins from the standpoint of solubility parameters, perfluorosulfonic acid resins have a more complex structure, resulting in higher requirements on the solubility parameters of solvents.
Therefore, there is a need to develop a simple and easy-to-use method for preparing perfluorosulfonic acid resin dispersion.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems: the molecular chains of the crystalline polymer are closely and regularly arranged, the intermolecular forces are large, and the dissolution is far more difficult than that of the amorphous polymer. Dissolution of crystalline polymers involves two processes: 1. melting the crystalline polymer, starting movement of molecular chains, and breaking crystal lattice; 2. dissolution of the molten high polymer, the lattice-disrupted polymer reacts with the solvent. Generally, the higher the crystallinity, the lower the solubility. In the related art, CN103146001A provides a preparation method of a perfluorosulfonic acid resin solution with uniformly dispersed molecular chains, which comprises the steps of placing solid perfluorosulfonic acid resin in a mixed solvent of water and an organic solvent, stirring for 20 minutes to 5 hours, transferring the mixture into a high-temperature and high-pressure container, dissolving the mixture for 1 to 120 hours under the conditions that the temperature is 100 to 300 ℃ and the pressure is 3 to 30MPa, separating liquid from liquid, and taking out a lower solution, namely the perfluorosulfonic acid resin solution with uniformly dispersed chains. CN112608494a discloses a preparation method of perfluorosulfonic acid resin dispersion liquid, which specifically comprises the following steps: placing the perfluorosulfonic acid resin solid into a mixed solvent of water and an organic solvent for high-temperature and high-pressure dissolution to obtain perfluorosulfonic acid resin dispersion liquid; obtaining perfluorosulfonic acid resin separating liquid after liquid-liquid separation; and centrifuging and filtering the separation liquid to obtain the perfluorosulfonic acid resin dispersion liquid. CN1884352a provides a method for preparing perfluorosulfonic acid resin solution with waste ion exchange membrane of chlor-alkali industry, swelling waste ion membrane of chlor-alkali industry with lower alcohol, emulsifying it into resin particles with emulsifying machine, then adding alcohol/water solvent and resin particles which are good solvent for perfluorosulfonic acid resin and carboxylic acid resin in waste ion exchange membrane into autoclave, dissolving resin particles under the condition of high temperature and high pressure and protection of N 2; obtaining a mixture of the solid perfluorocarboxylic acid resin and the solution, and separating the mixture by a solid-liquid separation method to obtain the perfluorosulfonic acid resin solution and the solid perfluorocarboxylic acid resin. The prepared resin solution is clear and transparent, has extremely low impurity content and high purity, has the performance basically the same as that of Nafion EW 1100 solution, and can be used for repairing pinholes and other mechanical damages of ion membranes, and manufacturing various production fields of fuel cell proton exchange membranes and electrodes, chemical catalysis and the like. CN111925544A provides a high-strength water-retaining perfluorosulfonic acid proton exchange membrane, a preparation method and application, and specifically comprises the following steps: (1) preparing functionalized graphene: weighing graphene oxide, lactic acid monomer, deionized water and stannous octoate according to mass ratio, adding into an autoclave, and heating under pressure; (2) Preparing a perfluorosulfonic acid resin modified material: heating the mixed aqueous solution of the perfluorosulfonic acid resin with the end-SO 3 Na and the polyvinyl alcohol, adding the lactic acid functionalized graphene oxide, and pressurizing in an autoclave; (3) preparation of perfluorosulfonic acid resin solution: putting the perfluorinated sulfonic acid resin modified material into an autoclave, adding an isopropanol water solution, heating and stirring; (4) casting a steel belt to prepare a film: and adding the perfluorinated sulfonic acid resin solution into a storage tank of a casting machine, preserving heat of the storage tank, casting a film on a transmission steel belt through a casting knife edge, and enabling the transmission steel belt with the film to enter an oven to obtain the high-strength water-retaining perfluorinated sulfonic acid proton exchange membrane applied to a fuel cell.
In the related art, the method for preparing resin dispersion liquid by using solid perfluorinated sulfonic acid resin is mainly to disperse resin in water-alcohol mixed solution at high temperature and high pressure. The sulfonic acid resin dispersion prepared by the method has certain dehydroxylation side reaction, is easy to carry out etherification reaction, and importantly, the method needs to be realized at high temperature and high pressure, so that great potential safety hazard exists.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a preparation method of a perfluorosulfonic acid resin dispersion liquid, which can prepare the perfluorosulfonic acid resin dispersion liquid with high solid content, high viscosity, small particle size and narrow particle size distribution under mild conditions without dispersing solid sulfonic acid resin at high temperature and high pressure, and the prepared dispersion liquid can be suitable for proton exchange membranes, water electrolysis membranes and fuel cell slurries.
The preparation method of the perfluorosulfonic acid resin dispersion liquid provided by the embodiment of the invention comprises the following steps:
a. dissolving perfluorinated sulfonic acid resin in a first solvent, and filtering to obtain a first resin dispersion liquid;
b. C, carrying out reduced pressure distillation on the first resin dispersion liquid obtained in the step a to obtain gel;
c. and c, dissolving the gel obtained in the step b in a second solvent to obtain a perfluorosulfonic acid resin dispersion liquid.
The preparation method of the perfluorosulfonic acid resin dispersion liquid has the advantages and technical effects that 1, in the method of the embodiment of the invention, the perfluorosulfonic acid resin solid is dissolved to prepare the perfluorosulfonic acid resin dilute solution, so that the crystal lattice energy of the perfluorosulfonic acid resin is primarily destroyed, the crystallinity of the resin is reduced, the perfluorosulfonic acid resin dilute solution is further subjected to reduced pressure distillation treatment, the crystallinity of the resin is effectively reduced, the crystal lattice energy of the solvent to be destroyed is lower, the resin is easier to dissolve, the resin is more fully dispersed in the dispersion liquid, the perfluorosulfonic acid resin dispersion liquid is prepared by dissolving and dispersing at normal temperature and normal pressure, the preparation condition is mild, the operation is convenient, and the industrialized application is easy; 2. in the method of the embodiment of the invention, the adopted solvent can be recycled, so that the cost is effectively reduced; 3. the method of the embodiment of the invention can prepare the perfluorosulfonic acid resin dispersion liquid with high viscosity, high solid content, small particle size and narrow particle size distribution, and no ether by-product is generated; 4. the resin dispersion liquid prepared by the method provided by the embodiment of the invention can be suitable for proton exchange membranes, water electrolysis membranes and fuel cell slurry, and has a good application prospect.
In some embodiments, in step a, the dissolution pressure is normal pressure and the dissolution temperature is 20-90 ℃.
In some embodiments, in the step a, the first solvent is a mixture of water and an organic solvent, wherein the organic solvent includes at least one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, DMAc, DMSO, NMP, and the mass ratio of water to the organic solvent in the first solvent is 1:9-9:1.
In some embodiments, in the step a, the first solvent is a mixed solution of water and ethanol in a mass ratio of 1:3.
In some embodiments, in step a, the first resin dispersion has a solids content of 0.1 to 3%, preferably 0.1 to 1% by mass.
In some embodiments, in step b, the absolute pressure of the reduced pressure distillation is no greater than 0.09MPa and the temperature is 60-90 ℃.
In some embodiments, in step b, the resulting gel has a solids content of 50-80% by mass.
In some embodiments, in the step c, the second solvent is a mixture of water and an organic solvent, wherein the organic solvent includes at least one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, DMAc, DMSO, NMP, and the mass ratio of water to the organic solvent in the second solvent is 1:10-5:1.
In some embodiments, in the step c, the second solvent is a mixed solvent of water and ethanol in a mass ratio of 1:2.
In some embodiments, in step c, the dissolution pressure is normal pressure and the dissolution temperature is 20-30 ℃.
Drawings
FIG. 1 is an XRD pattern of the perfluorosulfonic acid resin in the first resin dispersion before distillation under reduced pressure in example 1;
FIG. 2 is an XRD pattern of perfluorosulfonic acid resin in the gel after distillation under reduced pressure of example 1;
FIG. 3 is a graph showing the particle size distribution of the perfluorosulfonic acid resin dispersion obtained in example 1.
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 by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The preparation method of the perfluorosulfonic acid resin dispersion liquid provided by the embodiment of the invention comprises the following steps:
a. dissolving perfluorinated sulfonic acid resin in a first solvent, and filtering to obtain a first resin dispersion liquid;
b. C, carrying out reduced pressure distillation on the first resin dispersion liquid obtained in the step a to obtain gel;
c. and c, dissolving the gel obtained in the step b in a second solvent to obtain a perfluorosulfonic acid resin dispersion liquid.
In the preparation method of the perfluorosulfonic acid resin dispersion liquid, the perfluorosulfonic acid resin solid is dissolved to prepare the perfluorosulfonic acid resin dilute solution, so that the crystal lattice energy of the perfluorosulfonic acid resin is primarily destroyed, the crystallinity of the resin is reduced, the perfluorosulfonic acid resin dilute solution is further subjected to reduced pressure distillation treatment, the crystallinity of the resin is effectively reduced, the crystal lattice energy of the solvent to be destroyed is lower, the resin is easier to dissolve, the resin is more fully dispersed in the dispersion liquid, the perfluorosulfonic acid resin dispersion liquid is prepared by dissolving and dispersing at normal temperature and normal pressure, the preparation condition is mild, the operation is convenient, and the industrial application is easy; in the method of the embodiment of the invention, the adopted solvent can be recycled, so that the cost is effectively reduced; the method of the embodiment of the invention can prepare the perfluorosulfonic acid resin dispersion liquid with high viscosity, high solid content, small particle size and narrow particle size distribution, and no ether by-product is generated; the resin dispersion liquid prepared by the method provided by the embodiment of the invention can be suitable for proton exchange membranes, water electrolysis membranes and fuel cell slurry, and has a good application prospect.
In some embodiments, in the step a, the dissolution pressure is normal pressure, the normal pressure is a standard atmospheric pressure, the dissolution temperature is 20-90 ℃, preferably 20-40 ℃, preferably, the solid content of the first resin dispersion obtained after dissolution is 0.1-3%, preferably 0.1-1% by mass, and the step may be repeated to obtain the first resin dispersion. In the method of the embodiment of the application, the perfluorosulfonic acid resin solid is dissolved under normal pressure, and a resin dispersion liquid with low solid content is prepared by adopting a mild dissolution condition. In the method of the embodiment of the application, the solid content of the first resin dispersion is not particularly required, the gel can be obtained by adopting reduced pressure distillation treatment in the subsequent steps, in practical application, the dissolution temperature can be selected according to specific production conditions, and the resin dispersion with the required solid content is obtained, preferably, the mild dissolution temperature is adopted, so that the energy consumption is reduced.
In some embodiments, in the step a, the first solvent is a mixture of water and an organic solvent, wherein the organic solvent comprises at least one of methanol, ethanol, ethylene glycol, N-propanol, isopropanol, DMAc (dimethylacetamide), DMSO (dimethylsulfoxide), and NMP (N-methylpyrrolidone), and the mass ratio of water to organic solvent in the first solvent is 1:9 to 9:1; preferably, the first solvent is a mixed solution of water and ethanol in a mass ratio of 1:3. In the embodiment of the invention, the first solvent is not particularly required, and the perfluorinated sulfonic acid resin can be dissolved and dispersed under normal pressure to form the resin dispersion liquid with low solid content, and the aqueous alcohol solution is preferably adopted, so that the cost can be effectively reduced, the post-treatment is convenient, the recycling is realized, and the environment is protected.
In some embodiments, in step b, the absolute pressure of the reduced pressure distillation is no greater than 0.09MPa and the temperature is 60-90 ℃. In the method of the embodiment of the invention, the first resin dispersion liquid is subjected to reduced pressure distillation treatment, and the preferable reduced pressure distillation condition is adopted, so that the crystallinity of the perfluorinated sulfonic acid resin can be further reduced, the dissolving difficulty of the perfluorinated sulfonic acid resin is reduced, the perfluorinated sulfonic acid resin can be dispersed and dissolved at normal temperature and normal pressure, the solid content of the resin in the dispersion liquid is further improved, the average particle size of the resin in the dispersion liquid is reduced, the stability of the resin dispersion liquid is improved, the energy consumption is obviously reduced when the perfluorinated sulfonic acid resin is dispersed and dissolved at normal temperature and normal pressure, the production difficulty is reduced, and the method is safe and reliable, and is easy to apply.
In some embodiments, in step b, the resulting gel has a solids content of 50-80% by mass. In the method of the embodiment of the invention, the solid content of the gel obtained by reduced pressure distillation is optimized, the solid content of the gel is improved, the solid content and viscosity of the compound resin dispersion liquid can be better controlled, the solid content of the gel is improved, the more fully the resin dissolved by the organic solvent compound is dissolved, the smaller the particle size of the prepared resin dispersion liquid is, and the narrower the distribution is.
In some embodiments, in the step c, the second solvent is a mixture of water and an organic solvent, wherein the organic solvent includes at least one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, DMAc, DMSO, NMP, and the mass ratio of water to the organic solvent in the second solvent is 1:10-5:1. Preferably, the second solvent is a mixed solvent of water and ethanol in a mass ratio of 1:2. In the embodiment of the invention, the second solvent is not particularly required, and can be the same as or different from the first solvent, so long as the perfluorinated sulfonic acid resin can be dissolved and dispersed at normal temperature and normal pressure to form a resin dispersion liquid, and the aqueous alcohol solution is preferably adopted, so that the cost is further reduced, the post-treatment is convenient, and the resin dispersion liquid can be recycled.
In some embodiments, in step c, the dissolution pressure is normal pressure, the dissolution temperature is 20-30 ℃, the solid content of the obtained perfluorosulfonic acid resin dispersion is 15-26%, the viscosity is 60-400 Pa.S, and the average particle diameter is 50-300nm. According to the method provided by the embodiment of the invention, the crystallinity of the perfluorosulfonic acid resin is effectively reduced, the perfluorosulfonic acid resin can be redispersed and dissolved under the conditions of normal temperature and normal pressure, and the perfluorosulfonic acid resin dispersion liquid with high viscosity, high solid content, small particle size and narrow particle size distribution can be prepared.
The invention is described in detail below with reference to the drawings and examples.
Example 1
Dissolving 200 g of perfluorosulfonic acid resin in 5L of a first solvent at 30 ℃ and normal pressure, wherein the first solvent is a mixed solvent of water and ethanol with the mass ratio of 1:3, continuously stirring at 500rpm, dispersing after stirring for 9 hours, standing for a period of time, filtering and separating, and collecting a dilute solution of an upper resin dispersion, wherein the solid content of the obtained resin dispersion is 1%; dissolving the lower solid resin remained after filtration in a mixed solvent of water and ethanol with the mass ratio of 1:3 at 30 ℃ and normal pressure, continuously stirring at 500rpm, dispersing for 9 hours, standing for a period of time, collecting the upper resin dispersion dilute solution, repeating for a plurality of times, collecting the upper resin dispersion dilute solution for a plurality of times until the solid resin is completely dissolved, and collecting all the upper resin dispersion dilute solution as a first resin dispersion, wherein the solid content of the resin dispersion is 1%;
distilling the collected first resin dispersion liquid under reduced pressure in a reduced pressure distillation apparatus, wherein the reduced pressure vacuum degree is-0.05 MPa (gauge pressure), namely the absolute pressure is 0.05MPa, the distillation temperature is 60 ℃, and gel is obtained, wherein the solid content (in mass) of the gel is 68%, and the distillation is stopped;
And (3) adding the obtained gel into a mixed solvent of water and ethanol in a mass ratio of 1:2 at normal pressure and 25 ℃ to dissolve, and continuously stirring to obtain uniformly dispersed perfluorosulfonic acid resin dispersion liquid, wherein the resin dispersion liquid is free from sedimentation or resin precipitation after standing for 60 days.
The perfluorosulfonic acid resin obtained in this example had a viscosity of 107 mPa.S, a solid content of 20.2% and an average particle diameter of 200nm.
The XRD pattern of the perfluorosulfonic acid resin in the first resin dispersion before distillation under reduced pressure in this example is shown in FIG. 1, and the XRD pattern of the perfluorosulfonic acid resin in the gel obtained after distillation under reduced pressure is shown in FIG. 2. From fig. 1 and 2, it can be seen that the crystallization signal peak of the obtained perfluorosulfonic acid resin is obviously weakened and the crystallinity is obviously reduced after the reduced pressure distillation treatment.
The particle size distribution of the perfluorosulfonic acid resin dispersion liquid prepared in this example is shown in fig. 3, and it can be seen from fig. 3 that the particle size of the resin in the perfluorosulfonic acid resin dispersion liquid prepared in this example is concentrated between 70nm and 600nm, and no large particle size of 600nm or more is present, and the particle size distribution is narrow.
The perfluorosulfonic acid resin dispersion of this example was obtained by dissolving at normal temperature and normal pressure, and it was found that the perfluorosulfonic acid resin dispersion prepared in this example was free of ether by-products.
Example 2
The same procedure as in example 1 was repeated except that the gel obtained after distillation under reduced pressure had a solids content of 80%.
The perfluorosulfonic acid resin dispersion prepared in this example had a solid content of 26%, a viscosity of 263 mPa.S, an average particle diameter of 109nm, and no sedimentation or resin precipitation after 60 days of standing.
Example 3
The same procedure as in example 1 was repeated except that the gel obtained after distillation under reduced pressure had a solids content of 50%.
The perfluorosulfonic acid resin dispersion prepared in this example had a solid content of 16%, a viscosity of 78 mPa.S, an average particle diameter of 240nm, and no sedimentation or resin precipitation after 60 days of standing.
Example 4
The same procedure as in example 1 was repeated except that the absolute pressure of reduced pressure distillation was 0.01MPa.
The perfluorosulfonic acid resin dispersion prepared in this example had a solid content of 22.3%, a viscosity of 146 mPa.S, an average particle diameter of 160nm, and no sedimentation or resin precipitation after 60 days of standing.
Example 5
The same procedure as in example 1 was repeated except that the absolute pressure of distillation under reduced pressure was 0.09 MPa.
The perfluorosulfonic acid resin dispersion prepared in this example had a solid content of 18%, a viscosity of 89 mPa.S, an average particle diameter of 260nm, and no sedimentation or resin precipitation after 60 days of standing.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (6)
1. A method for preparing a perfluorosulfonic acid resin dispersion, comprising:
a. Dissolving perfluorinated sulfonic acid resin in a first solvent, and filtering to obtain a first resin dispersion liquid, wherein the dissolving pressure is normal pressure, the dissolving temperature is 20-90 ℃, and the solid content of the first resin dispersion liquid is 0.1-3% by mass;
b. c, carrying out reduced pressure distillation on the first resin dispersion liquid obtained in the step a to obtain gel, wherein the absolute pressure of reduced pressure distillation is not higher than 0.09MPa, the temperature is 60-90 ℃, and the solid content of the obtained gel is 50-80% by mass;
c. and c, dissolving the gel obtained in the step b in a second solvent to obtain a perfluorosulfonic acid resin dispersion liquid, wherein the dissolving pressure is normal pressure, the dissolving temperature is 20-30 ℃, the solid content of the obtained perfluorosulfonic acid resin dispersion liquid is 15-26%, the viscosity is 60-400 Pa.S, and the average particle size is 50-300nm.
2. The method for preparing a perfluorosulfonic acid resin dispersion according to claim 1, wherein in the step a, the first solvent is a mixture of water and an organic solvent, wherein the organic solvent comprises at least one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, DMAc, DMSO, NMP, and the mass ratio of water to the organic solvent in the first solvent is 1:9 to 9:1.
3. The method for preparing a perfluorosulfonic acid resin dispersion according to claim 2, wherein in the step a, the first solvent is a mixed solution of water and ethanol in a mass ratio of 1:3.
4. The method for producing a perfluorosulfonic acid resin dispersion according to claim 1, wherein in the step a, the solid content of the first resin dispersion is 0.1% to 1%.
5. The method for preparing a perfluorosulfonic acid resin dispersion according to claim 1, wherein in the step c, the second solvent is a mixture of water and an organic solvent, wherein the organic solvent comprises at least one of methanol, ethanol, ethylene glycol, n-propanol, isopropanol, DMAc, DMSO, NMP, and the mass ratio of water to the organic solvent in the second solvent is 1:10-5:1.
6. The method for producing a perfluorosulfonic acid resin dispersion according to claim 5, wherein in step c, the second solvent is a mixed solvent of water and ethanol in a mass ratio of 1:2.
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| CN112608494A (en) * | 2020-12-02 | 2021-04-06 | 常熟三爱富中昊化工新材料有限公司 | Preparation method of perfluorosulfonic acid resin dispersion liquid |
| CN112993353A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-water-retention composite proton exchange membrane and preparation method thereof |
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| KR20160050870A (en) * | 2014-10-31 | 2016-05-11 | 주식회사 엘지화학 | Organic-Inorganic Complexed Polymer Gel Electrolyte and Lithium Secondary Battery Having the Same |
| CN112993353A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-water-retention composite proton exchange membrane and preparation method thereof |
| CN112608494A (en) * | 2020-12-02 | 2021-04-06 | 常熟三爱富中昊化工新材料有限公司 | Preparation method of perfluorosulfonic acid resin dispersion liquid |
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