CN116554386B - Esterification method of perfluorosulfonyl fluoride resin and preparation method of perfluorosulfonic acid resin - Google Patents
Esterification method of perfluorosulfonyl fluoride resin and preparation method of perfluorosulfonic acid resin Download PDFInfo
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- CN116554386B CN116554386B CN202310830075.1A CN202310830075A CN116554386B CN 116554386 B CN116554386 B CN 116554386B CN 202310830075 A CN202310830075 A CN 202310830075A CN 116554386 B CN116554386 B CN 116554386B
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- 239000011347 resin Substances 0.000 title claims abstract description 126
- 229920005989 resin Polymers 0.000 title claims abstract description 126
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 99
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 230000032050 esterification Effects 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 35
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 53
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 75
- 239000000243 solution Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000006460 hydrolysis reaction Methods 0.000 claims description 23
- 230000035484 reaction time Effects 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 12
- -1 2-dimethylpyridine Chemical compound 0.000 claims description 10
- 150000003460 sulfonic acids Chemical class 0.000 claims description 10
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000007514 bases Chemical class 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 53
- 238000005406 washing Methods 0.000 abstract description 40
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 abstract description 16
- 239000011775 sodium fluoride Substances 0.000 abstract description 8
- 235000013024 sodium fluoride Nutrition 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 78
- 238000006243 chemical reaction Methods 0.000 description 63
- 239000000047 product Substances 0.000 description 31
- 238000001035 drying Methods 0.000 description 27
- 239000007787 solid Substances 0.000 description 23
- 238000003756 stirring Methods 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 230000007935 neutral effect Effects 0.000 description 16
- 238000001914 filtration Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 206010042674 Swelling Diseases 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002274 desiccant Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000072 sodium resin Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The application provides an esterification method of perfluorosulfonyl fluoride resin and a preparation method of perfluorosulfonic acid resin, wherein the esterification method comprises the following steps: and mixing the perfluorosulfonyl fluoride resin, fatty alcohol and an organic alkaline compound for esterification reaction to obtain an esterification product. According to the esterification method of the perfluorinated sulfonyl fluoride resin, provided by the application, the organic alkaline compound, the fatty alcohol and the perfluorinated sulfonyl fluoride resin are mixed to perform esterification reaction, so that the introduction of water and the generation of salt substances such as sodium fluoride can be avoided, the esterification efficiency of the perfluorinated sulfonyl fluoride resin is effectively improved, meanwhile, the intermediate water washing process is simplified, and the industrial production is easy to realize.
Description
Technical Field
The application relates to the technical field of high molecular functional materials, in particular to an esterification method of perfluorosulfonyl fluoride resin and a preparation method of perfluorosulfonic acid resin.
Background
The commercial name Nafion was first developed by DuPont in 1962 in U.S.A ® The perfluorinated sulfonic acid ion polymer (PFSI, also called perfluorinated sulfonic acid ion exchange resin) is used in fuel cells for aerospace development as a high polymer solid electrolyte with extremely high chemical stability, and the application of the perfluorinated ion polymer is pioneered. The synthetic process of the perfluorosulfonic acid ion polymer (also called perfluorosulfonic acid resin) is to copolymerize tetrafluoroethylene and sulfonyl vinyl ether monomer to prepare perfluorosulfonic acid resin precursor (namely perfluorosulfonyl fluoride resin), and then sodium modification transformation and acidification transformation are carried out to obtain the perfluorosulfonic acid resin, wherein the transformation process is to convert-SO 2 The preparation method of F-transformed perfluorinated sulfonic acid resin is-SO 3 Na (sodium modification), and then converting-SO 3 Na conversion to-SO 3 H, the value of EW (1 mol of sulfonic acid group) of the resin is influenced, and the performance of the membrane after the proton exchange membrane is prepared is further influenced.
In the traditional method, sodium hydroxide aqueous solution is taken as sodium conversion agent to carry out sodium conversion on sulfonyl fluoride resin, and sulfuric acid is used for acidizing and converting the resin to obtain the perfluorinated sulfonic acid resin. On one hand, water is introduced in the reaction process, so that the reaction efficiency is reduced, on the other hand, sodium resin is required to be washed to be neutral, acid resin is required to be washed to be neutral, the washing process is complex, the washing is difficult to be neutral, and impurities such as sodium fluoride, sodium ions and the like are difficult to remove, so that the subsequent proton membrane preparation and the performance are greatly influenced.
In view of this, the present application has been made.
Disclosure of Invention
The application mainly aims to provide an esterification method of perfluorosulfonyl fluoride resin, which aims to solve the technical problems that the reaction efficiency is low and the washing process is complex in the sodium modification transformation process of the perfluorosulfonyl fluoride resin in the prior art, and the introduced impurities such as sodium fluoride and the like are difficult to remove.
In order to achieve the above object, according to one aspect of the present application, there is provided an esterification method of perfluorosulfonyl fluoride resin, comprising the steps of: and mixing the perfluorosulfonyl fluoride resin, fatty alcohol and an organic alkaline compound for esterification reaction to obtain an esterification product.
Further, the organic basic compound comprises at least one of triethylamine, liquid ammonia, ethylenediamine, aniline, diethylamine, pyrrole, N-diisopropylethylamine, 4-dimethylaminopyridine, 2-lutidine, pyridine and N-methylmorpholine.
Further, the organic basic compound comprises at least one of triethylamine, liquid ammonia, ethylenediamine and aniline.
Further, the fatty alcohol is C1-C8 fatty alcohol.
Further, the fatty alcohol is at least one of methanol, ethanol, n-propanol, ethylene glycol or isopropanol.
Further, the mass ratio of the organic alkaline compound to the fatty alcohol is 1 (10-20); and/or the mass ratio of the fatty alcohol to the perfluorosulfonyl fluoride resin is (1-3): 1.
Further, the fatty alcohol comprises a first fatty alcohol and a second fatty alcohol, and the esterification method further comprises the following steps: dispersing an organic alkaline compound in first fatty alcohol to obtain an organic alkaline compound solution, dispersing perfluorosulfonyl fluoride resin in second fatty alcohol to obtain a perfluorosulfonyl fluoride resin solution, and mixing the organic alkaline compound solution and the perfluorosulfonyl fluoride resin solution for esterification, wherein the mass ratio of the organic alkaline compound to the first fatty alcohol is (1-2): 1.
Further, the number average molecular weight of the perfluorosulfonyl fluoride resin is 20000 to 500000, and the EW value is 700 to 1500 g/mol.
Further, the temperature of the esterification reaction is 30-70 ℃ and the time is 6-12 h.
Further, the esterification reaction is carried out under the protection of inert gas, and the inert gas comprises at least one of nitrogen, helium and argon.
In order to achieve the above object, according to one aspect of the present application, there is provided a method for producing a perfluorosulfonic acid resin, comprising the steps of: providing an esterification product, and mixing the esterification product with an acidic solution to carry out hydrolysis reaction to obtain the perfluorinated sulfonic acid resin.
Further, the mass ratio of the esterification product to the acidic solution is 1 (2-6).
Further, the concentration of hydrogen ions in the acidic solution is 1-5 mol/L.
Further, the acidic solution is at least one of sulfuric acid, hydrochloric acid and nitric acid.
Further, the temperature of the hydrolysis reaction is 40-200 ℃.
Further, the temperature of the hydrolysis reaction is 40-90 ℃.
Further, the time of the hydrolysis reaction is 4-8 hours.
By adopting the technical scheme, the esterification method of the perfluorosulfonyl fluoride resin provided by the application has the advantages that the organic alkaline compound, fatty alcohol and the perfluorosulfonyl fluoride resin are mixed to perform esterification reaction, so that the introduction of water and the generation of salt substances such as sodium fluoride can be avoided, the esterification efficiency of the perfluorosulfonyl fluoride resin is effectively improved, the intermediate washing process is simplified, and the industrial production is easy to realize.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As analyzed in the background of the application, the prior art perfluorosulfonyl fluoride resin is converted into perfluorosulfonic acid resin by using sodium hydroxide solution as sodium conversion agent and then acidifying the resin with sulfuric acid to obtain perfluorosulfonic acid resin. On the one hand, water is introduced in the reaction process in the preparation process, so that the reaction efficiency is reduced, on the other hand, the sodium resin is required to be washed to be neutral, the acid resin is required to be washed to be neutral, the washing process is complex, the washing process is difficult to be washed to be neutral, impurities such as sodium fluoride and sodium ions are difficult to remove, the subsequent proton membrane preparation and the performance of the subsequent proton membrane preparation are greatly influenced, and in order to solve the problem, the application provides the esterification method of the perfluorinated sulfonyl fluoride resin.
In an exemplary embodiment of the present application, there is provided an esterification method of a perfluorosulfonyl fluoride resin, the esterification method comprising the steps of: and mixing the perfluorosulfonyl fluoride resin, fatty alcohol and an organic alkaline compound for esterification reaction to obtain an esterification product.
The esterification reaction equation of the perfluorosulfonyl fluoride resin is shown in the following formula (I):
formula (I)
In the formula (I), x, y, m and n are each independently a natural number of 1 to 6, and R-OH is fatty alcohol.
By adopting the technical scheme, the esterification method of the perfluorosulfonyl fluoride resin provided by the application has the advantages that the organic alkaline compound, the fatty alcohol and the perfluorosulfonyl fluoride resin are mixed to perform esterification reaction, so that the introduction of water and the generation of salt substances such as sodium fluoride can be avoided, the esterification efficiency of the perfluorosulfonyl fluoride resin is effectively improved, the intermediate washing process is simplified, and the industrial production is easy to realize.
The organic alkaline compound is at least one of triethylamine, liquid ammonia, ethylenediamine, aniline, diethylamine, pyrrole, N-diisopropylethylamine, 4-dimethylaminopyridine, 2-lutidine, pyridine and N-methylmorpholine, and is preferably at least one of triethylamine, liquid ammonia, ethylenediamine and aniline in order to further promote the forward direction of the esterification reaction, wherein the organic alkaline compound can be combined with hydrogen ions generated in the reaction to enable the esterification reaction to be carried out forward, and the organic alkaline compound is adopted to avoid the use of inorganic alkaline compound to introduce water into a reaction system as a solvent to cause incomplete esterification reaction, and avoid the introduction of metal ions, sodium fluoride and other impurities to cause excessive impurity content in an esterification product, so that the yield of the perfluorosulfonic acid resin is reduced.
In order to further improve the reaction efficiency of the esterification reaction, the fatty alcohol is preferably a fatty alcohol with 1 to 8 carbon atoms, preferably at least one of methanol, ethanol, n-propanol, ethylene glycol or isopropanol, wherein the fatty alcohol with 1 to 8 carbon atoms refers to a chain hydroxyl alcohol with less than 8 carbon atoms, and the fatty alcohol has the advantages of low boiling point and good solubility, so that the swelling performance of the perfluorosulfonyl fluoride resin can be improved, the esterification reaction efficiency is improved, the post-treatment of the subsequent hydrolysis reaction is facilitated, and the post-treatment process is simplified.
In order to further improve the conversion rate of the esterification reaction, the mass ratio of the organic alkaline compound to the fatty alcohol is, for example, a range value consisting of 1:10, 1:12, 1:14, 1:16, 1:18, 1:20 or any two values, the mass ratio of the organic alkaline compound to the fatty alcohol is too low, the mass ratio of the organic alkaline compound to the fatty alcohol in the esterification reaction system is too low to play a role in catalyzing the esterification reaction, the mass ratio of the organic alkaline compound to the fatty alcohol is too high, the organic alkaline compound is excessive in the esterification reaction system, the cost of the reaction is increased, the mass ratio of the fatty alcohol to the perfluorosulfonyl fluoride resin is, for example, a range value consisting of 1:1, 1.5:1, 2:1, 2.5:1, 3:1 or any two values.
In some embodiments, the fatty alcohol comprises a first fatty alcohol and a second fatty alcohol, and the esterification process further comprises the steps of: firstly dispersing an organic alkaline compound in first fatty alcohol to obtain an organic alkaline compound solution, dispersing perfluorosulfonyl fluoride resin in second fatty alcohol to obtain a perfluorosulfonyl fluoride resin solution, and then mixing the organic alkaline compound solution and the perfluorosulfonyl fluoride resin solution for esterification reaction, wherein the mass of the organic alkaline compound and the first fatty alcohol is 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1 or a range value formed by any two values.
In order to reduce the influence of moisture contained in the perfluorosulfonyl fluoride resin and the fatty alcohol on the esterification reaction, the perfluorosulfonyl fluoride resin and the fatty alcohol are preferably subjected to drying treatment before the perfluorosulfonyl fluoride resin, the fatty alcohol and the organic alkaline compound are mixed for the esterification reaction, wherein the perfluorosulfonyl fluoride resin is dried at a temperature of 80 ℃, 85 ℃, 90 ℃, 95 ℃ or 100 ℃ or in a range of values consisting of any two values, the drying time is 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours or in a range of values consisting of any two values, and the fatty alcohol is subjected to reduced pressure distillation and is dried by using a drying agent such as a molecular sieve, calcium oxide and the like, so that the water content of the fatty alcohol is 0.002-0.01% (for example, 0.005%), thereby avoiding the introduction of an aqueous solution in the esterification reaction, being favorable for the forward progress of the esterification reaction, and improving the yield and conversion rate of the esterification reaction.
In order to improve the reaction efficiency of the esterification reaction, in some embodiments, the dried perfluorosulfonyl fluoride resin and the fatty alcohol are mixed to carry out swelling treatment on the perfluorosulfonyl fluoride resin, wherein the temperature is 50-80 ℃, the stirring rotation speed is 200-500 rpm, the stirring time is 4-10 hours to obtain the swelled perfluorosulfonyl fluoride resin, in order to further improve the swelling rate, the particle size of the perfluorosulfonyl fluoride resin particles is preferably 20-500 meshes, which are commercially available, manufacturers include but are not limited to east, giant and Han dynasty, the number average molecular weight is 20000-500000, the EW value is 700-1500 g/mol, for example, the particle size of the perfluorosulfonyl fluoride resin obtained commercially available is overlarge, the particle size of the perfluorosulfonyl fluoride resin can be 20-100 meshes through a crushing mode, the crushing equipment is not particularly limited, and the crushing equipment is a high-speed crusher.
In the application, the perfluorinated sulfonyl fluoride resin swelled by fatty alcohol and the organic alkaline compound are mixed for esterification reaction, in order to further improve the conversion rate of the esterification reaction, the esterification reaction is preferably carried out under the protection of inert gas, the inert gas comprises at least one of nitrogen, helium and argon, the inert gas is introduced into a reaction container for 0.5-2 h, the flow rate of the inert gas is 10-300 mL/min, the air can be prevented from entering, the generation of byproducts is avoided, and meanwhile, the water vapor in the air is prevented from entering an esterification reaction system, so that the reaction conversion rate is reduced, and the conversion rate of the esterification reaction is improved.
In some embodiments, the esterification reaction is performed at a temperature of 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or any two values, and the reaction time is 6h, 7h, 8h, 9h, 10h, 11h, 12h or any two values, so that the esterification reaction can be performed at a lower temperature, the reaction time is shorter, the reaction temperature is easy to control, and the reaction condition is simple, thereby being beneficial to industrial production.
In order to further improve the efficiency of the esterification reaction, the stirring speed in the reaction is preferably 200-400 rpm, and the stirring speed is in the above range, so that the organic alkaline compound, the perfluorosulfonyl fluoride resin and the fatty alcohol can be fully mixed, local severe reaction caused by uneven mixing is avoided, and the promotion of the esterification reaction of the perfluorosulfonyl fluoride resin is facilitated.
In some embodiments of the present application, in order to improve the purity of the esterification product, after the esterification reaction, the solid-liquid separation is performed on the esterification reaction system, then the obtained solid is subjected to multiple water washing, the pH value of the water washing liquid is tested until the water washing liquid is neutral, which indicates that the impurities are basically washed clean, the water washing is finished, the solid obtained by water washing is dried, the drying temperature is 60-80 ℃, and the drying time is 6-12 hours, so as to obtain the esterification product. The solid-liquid separation mode is not limited, and includes, but is not limited to, normal pressure filtration, centrifugation, suction filtration, and the like.
In another exemplary embodiment of the present application, there is provided a method for preparing a perfluorosulfonic acid resin, comprising the steps of: and mixing the esterification product with an acidic solution to perform hydrolysis reaction to obtain the perfluorinated sulfonic acid resin.
The hydrolysis reaction equation of the esterification product is as follows) The following is shown:
the [ (x) ray ]）
In the formula (I), x, y, m and n are natural numbers of 1 to 6 independently.
The kind of the acidic solution is not limited, and any acidic solution commonly used in the art can provide hydrogen ions required for hydrolysis reaction. In order to further increase the hydrolysis conversion rate of the esterification product, the concentration of hydrogen ions in the acidic solution is preferably 1-5 mol/L, and the acidic solution comprises at least one of sulfuric acid, hydrochloric acid and nitric acid.
In order to further improve the conversion rate of the hydrolysis reaction, the mass ratio of the esterification product to the acid solution is preferably 1 (2-6), for example, the mass ratio is 1:2, 1:3, 1:4, 1:6 or a range of any two values, the amount of the acid solution is too small, the hydrolysis of the esterification product is incomplete, the conversion rate of the hydrolysis reaction is low, the acid solution is excessive, and a large amount of water is required in the post-treatment process to wash the perfluorinated sulfonic acid resin to be neutral, so that unnecessary waste is formed. In the range, the conversion rate of the hydrolysis reaction can be effectively improved, and the washing times in the post-treatment process can be reduced, so that the method is beneficial to industrial production.
In some embodiments of the present application, in order to further improve the purity of the perfluorosulfonic acid resin, after the hydrolysis reaction is completed, the solid-liquid separation is performed on the hydrolysis reaction system, then the obtained solid is subjected to multiple water washes, the pH value of the water wash is tested until the water wash is neutral, which indicates that the impurities are basically washed clean, the water wash is completed, the product obtained by the water wash is dried, the drying temperature is 60-80 ℃, and the drying time is 6-12 hours, so as to obtain the perfluorosulfonic acid resin. The solid-liquid separation mode is not limited, and includes, but is not limited to, normal pressure filtration, centrifugation, suction filtration, and the like.
The neutral pH refers to the condition of pH value of 7, and the pH value of 7+/-0.5 belongs to the neutral category in the application in view of different precision of different pH test paper, and the pH value of the water washing liquid is 6.5, 6.8, 7, 7.2 or 7.5.
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
Example 1
The embodiment provides a preparation method of perfluorinated sulfonic acid resin, which comprises the following steps:
(1) Crushing the commercial perfluorosulfonyl fluoride resin with the EW value of 850g/mol and the number average molecular weight of 80000 in a high-speed crusher, and then drying the perfluorosulfonyl fluoride resin in a blast drying oven at 80 ℃ for 8 hours to obtain the perfluorosulfonyl fluoride resin with the particle size of 20 meshes; the anhydrous methanol is decompressed and distilled and then dried by using a desiccant (calcium oxide), and the water content is 0.008wt%; 85g of the dried perfluorosulfonyl fluoride resin was mixed with 85g of methanol to carry out swelling treatment at a swelling temperature of 50℃and a stirring speed of 300rpm for 5 hours to obtain a mixture.
(2) Introducing nitrogen into the reactor for 1h at the flow rate of 100L/min, mixing the prepared triethylamine solution (triethylamine 5g, methanol 5 g) with the mixture under the protection of nitrogen for esterification reaction, wherein the reaction temperature is 45 ℃, the stirring speed is 250rpm, the reaction time is 7h, filtering the reaction solution after the reaction is finished to obtain a solid, and drying the solid at 70 ℃ for 10h to obtain an esterification product.
(3) Placing the esterified product in a reaction vessel, mixing with 150ml of 1mol/L sulfuric acid for hydrolysis reaction, wherein the reaction temperature is 60 ℃, the stirring rotation speed is 400rpm, the reaction time is 4 hours, filtering the reaction liquid to obtain solid after the reaction is finished, washing the solid by using water, testing the pH value of the water washing liquid until the pH value of the water washing liquid is neutral (pH value is 7+/-0.5), stopping washing by water for 3 hours, and drying the obtained washed product at 70 ℃ for 10 hours to obtain the perfluorosulfonic acid resin.
Example 2
(1) Crushing the commercial perfluorosulfonyl fluoride resin with the EW value of 850g/mol and the number average molecular weight of 100000 in a high-speed crusher, and then placing the crushed perfluorosulfonyl fluoride resin in a blast drying oven at 80 ℃ for drying for 12 hours to obtain the perfluorosulfonyl fluoride resin with the particle size of 40 meshes; the absolute methanol is decompressed and distilled and then is dried by a desiccant, and the water content is 0.009wt%; 85g of the dried perfluorosulfonyl fluoride resin was mixed with 150g of methanol to carry out swelling treatment at 50℃with a stirring speed of 300rpm for 10 hours, to obtain a mixture.
(2) Introducing nitrogen into the reactor for 1h at a flow rate of 150L/min, mixing the prepared triethylamine solution (triethylamine 15g, methanol 15 g) with the mixture under the protection of nitrogen for esterification reaction at a temperature of 50 ℃ and a stirring speed of 250rpm for 7h, filtering the reaction solution after the reaction is finished to obtain a solid, and drying the solid at 70 ℃ for 10h to obtain an esterification product.
(3) Placing the esterified product in a reaction vessel, mixing with 150ml of sulfuric acid with the concentration of 3mol/L for hydrolysis reaction, wherein the reaction temperature is 70 ℃, the stirring rotation speed is 430rpm, the reaction time is 8 hours, filtering the reaction liquid to obtain solid after the reaction is finished, washing the solid by using water, testing the pH value of the water washing liquid until the pH value of the water washing liquid is neutral (pH value of 7+/-0.5), stopping washing by water for 2.5 hours, and drying the obtained washed product at the temperature of 70 ℃ for 10 hours to obtain the perfluorosulfonic acid resin.
Example 3
(1) Crushing the commercial perfluorosulfonyl fluoride resin with the EW value of 850g/mol and the number average molecular weight of 120000 in a high-speed crusher, and then placing the crushed perfluorosulfonyl fluoride resin in a blast drying oven at 80 ℃ for drying for 12 hours to obtain the perfluorosulfonyl fluoride resin with the particle size of 20 meshes; distilling absolute ethyl alcohol under reduced pressure, and drying the absolute ethyl alcohol by using a drying agent, wherein the water content is 0.01wt%; 85g of the dried perfluorosulfonyl fluoride resin was mixed with 150g of ethanol and subjected to swelling treatment at 50℃under stirring at 300rpm for 10 hours to give a mixture.
(2) Introducing nitrogen into the reactor for 1h at the flow rate of 200L/min, mixing the prepared triethylamine solution (triethylamine 15g, ethanol 15 g) with the mixture under the protection of nitrogen for esterification reaction, wherein the reaction temperature is 60 ℃, the stirring speed is 250rpm, the reaction time is 7h, filtering the reaction solution after the reaction is finished to obtain a solid, and drying the solid at 70 ℃ for 10h to obtain an esterification product.
(3) Placing the esterified product in a reaction vessel, mixing with 150ml of sulfuric acid with the concentration of 3mol/L for hydrolysis reaction, wherein the reaction temperature is 70 ℃, the stirring rotation speed is 430rpm, the reaction time is 8 hours, filtering the reaction liquid after the reaction is finished to obtain solid, washing the solid by using water, testing the pH value of the water washing liquid until the pH value of the water washing liquid is neutral (pH value of 7+/-0.5), stopping washing by water for 4 hours, and drying the obtained water washing product at 70 ℃ for 10 hours to obtain the perfluorinated sulfonic acid resin.
Example 4
(1) Crushing the commercial perfluorosulfonyl fluoride resin with the EW value of 850g/mol and the number average molecular weight of 150000 in a high-speed crusher, and then placing the crushed perfluorosulfonyl fluoride resin in a blast drying oven at 80 ℃ for drying for 12 hours to obtain the perfluorosulfonyl fluoride resin with the particle size of 80 meshes; the anhydrous methanol is decompressed and distilled and then dried by using a desiccant, and the water content is 0.01wt%; 85g of the dried perfluorosulfonyl fluoride resin was mixed with 130g of methanol to be subjected to swelling treatment at 50℃under stirring at 300rpm for 10 hours, to obtain a mixture.
(2) Introducing nitrogen into the reactor for 1h at a flow rate of 160L/min, mixing the prepared triethylamine solution (triethylamine 8g, methanol 4 g) with the mixture under the protection of nitrogen for esterification reaction, wherein the reaction temperature is 50 ℃, the stirring speed is 250rpm, the reaction time is 7h, filtering the reaction solution after the reaction is finished to obtain a solid, and drying the solid at 70 ℃ for 10h to obtain an esterification product.
(3) Placing the esterified product in a reaction vessel, mixing with 150ml of sulfuric acid with the concentration of 2mol/L for hydrolysis reaction, wherein the reaction temperature is 65 ℃, the stirring rotation speed is 300rpm, the reaction time is 8 hours, filtering the reaction liquid to obtain solid after the reaction is finished, washing the solid by using water, testing the pH value of the water washing liquid until the pH value of the water washing liquid is neutral (pH value of 7+/-0.5), stopping washing by water for 5 hours, and drying the obtained water washing product at 70 ℃ for 10 hours to obtain the perfluorinated sulfonic acid resin.
Example 5
(1) Crushing the commercial perfluorosulfonyl fluoride resin with the EW value of 850g/mol and the number average molecular weight of 90000 in a high-speed crusher, and then drying the perfluorosulfonyl fluoride resin in a blast drying oven at 80 ℃ for 12 hours to obtain the perfluorosulfonyl fluoride resin with the particle size of 20 meshes; the absolute methanol is decompressed and distilled and then is dried by a desiccant, and the water content is 0.009wt%; 85g of the dried perfluorosulfonyl fluoride resin was mixed with 130g of methanol to be subjected to swelling treatment at 50℃under stirring at 300rpm for 10 hours, to obtain a mixture.
(2) Introducing nitrogen into the reactor for 1h at a flow rate of 130L/min, mixing the prepared triethylamine solution (triethylamine 13g, methanol 6.5 g) with the mixture under the protection of nitrogen for esterification reaction, wherein the reaction temperature is 50 ℃, the stirring speed is 250rpm, the reaction time is 7h, filtering the reaction solution after the reaction is finished to obtain a solid, and drying the solid at 70 ℃ for 10h to obtain an esterification product.
(3) Placing the esterified product in a reaction vessel, mixing with 150ml of sulfuric acid with the concentration of 2mol/L for hydrolysis reaction, wherein the reaction temperature is 70 ℃, the stirring rotation speed is 300rpm, the reaction time is 8 hours, filtering the reaction liquid to obtain solid after the reaction is finished, washing the solid by using water, testing the pH value of the water washing liquid until the pH value of the water washing liquid is neutral (pH value of 7+/-0.5), stopping washing by water for 4 hours, and drying the obtained water washing product at 70 ℃ for 10 hours to obtain the perfluorosulfonic acid resin.
Example 6
This example differs from example 1 in that ethylenediamine is used instead of triethylamine in step (2).
Example 7
This example differs from example 1 in that in step (2) aniline is used instead of triethylamine.
Example 8
This example differs from example 1 in that in step (1), ethanol is used instead of methanol.
Example 9
This example differs from example 1 in that in step (1) isopropanol is used instead of methanol.
Example 10
This example differs from example 1 in that a triethylamine solution (triethylamine 5g, methanol 5 g) was prepared from 85g of perfluorosulfonyl fluoride resin and 95g of methanol.
Example 11
This example differs from example 1 in that a triethylamine solution (triethylamine 10g, methanol 10 g) was prepared from 85g of perfluorosulfonyl fluoride resin and 90g of methanol.
Example 12
This example differs from example 1 in that a triethylamine solution (triethylamine 20g, methanol 10 g) was prepared from 85g of perfluorosulfonyl fluoride resin and 90g of methanol.
Example 13
This example differs from example 1 in that a triethylamine solution (triethylamine 5g, methanol 5 g) was prepared from 85g of perfluorosulfonyl fluoride resin and 195g of methanol.
Example 14
This example differs from example 1 in that in step (2), the reaction temperature was 30℃and the reaction time was 12 hours.
Example 15
This example differs from example 1 in that in step (2), the reaction temperature was 70℃and the reaction time was 6 hours.
Example 16
This example differs from example 1 in that in step (2), the reaction temperature was 100℃and the reaction time was 7 hours.
Comparative example 1
This comparative example differs from example 1 in that a 10% aqueous sodium hydroxide solution was used instead of the organic basic compound.
Comparative example 2
This comparative example differs from example 1 in that a mixed solution of methanol and water in a mass ratio of 1:1 was used instead of methanol.
Test example 1
The mass of the esterified product and the perfluorosulfonic acid resin obtained in the above examples and comparative examples were weighed, and the water washing time during the post-treatment was recorded, respectively, and the esterification conversion and the overall conversion were calculated, and the results are shown in Table 1 below.
Wherein, 1) the esterification conversion rate calculation method comprises the following steps: [ (m) 2 -m 1 ）/（M Alcohols -M F -1）]/（m 1 /EW）；
2) The calculation method of the overall conversion rate comprises the following steps: [ (m) 3 -m 1 ）/（M OH -M F ）]/（m 1 /EW）；
Note that: m is m 1 The charge amount of the sulfonyl fluoride resin is calculated;
m 2 is the quality of the esterified product;
m 3 the mass of the resin is perfluorosulfonic acid resin;
M alcohols Molecular weight of the corresponding reactant lower aliphatic alcohol;
M F f relative atomic mass;
EW is the EW value corresponding to the sulfonyl fluoride resin.
TABLE 1
From the above description, it can be seen that the above embodiments of the present application achieve the following technical effects: according to the esterification method of the perfluorinated sulfonyl fluoride resin, provided by the application, the organic alkaline compound, the fatty alcohol and the perfluorinated sulfonyl fluoride resin are mixed to perform esterification reaction, so that the introduction of water and the generation of salt substances such as sodium fluoride can be avoided, the esterification efficiency of the perfluorinated sulfonyl fluoride resin is effectively improved, meanwhile, the intermediate water washing process is simplified, and industrial production is easy to realize.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. An esterification method of perfluorosulfonyl fluoride resin, characterized in that the esterification method comprises the steps of: mixing the perfluorinated sulfonyl fluoride resin, fatty alcohol and an organic alkaline compound for esterification reaction to obtain an esterification product; the fatty alcohol comprises a first fatty alcohol and a second fatty alcohol, and the esterification method further comprises the following steps: dispersing the organic alkaline compound in the first fatty alcohol to obtain an organic alkaline compound solution, dispersing the perfluorosulfonyl fluoride resin in the second fatty alcohol to obtain a perfluorosulfonyl fluoride resin solution, and mixing the organic alkaline compound solution and the perfluorosulfonyl fluoride resin solution for the esterification reaction, wherein the mass ratio of the organic alkaline compound to the first fatty alcohol is (1-2): 1.
2. The method for esterifying a perfluorosulfonyl fluoride resin according to claim 1, wherein the organic basic compound comprises at least one of triethylamine, liquid ammonia, ethylenediamine, aniline, diethylamine, pyrrole, N-diisopropylethylamine, 4-dimethylaminopyridine, 2-dimethylpyridine, pyridine, and N-methylmorpholine.
3. The method for esterifying a perfluorosulfonyl fluoride resin according to claim 1, wherein the fatty alcohol is a C1 to C8 fatty alcohol.
4. The method for esterifying a perfluorosulfonyl fluoride resin according to claim 1, wherein the mass ratio of the organic basic compound to the fatty alcohol is 1 (10-20); and/or the mass ratio of the fatty alcohol to the perfluorosulfonyl fluoride resin is (1-3): 1.
5. The method for esterifying a perfluorosulfonyl fluoride resin according to any one of claims 1 to 3, wherein the perfluorosulfonyl fluoride resin has a number average molecular weight of 20000 to 500000 and an ew value of 700 to 1500 g/mol.
6. The esterification method of a perfluorosulfonyl fluoride resin according to any one of claims 1 to 3, wherein the temperature of the esterification reaction is 30 to 70 ℃ for 6 to 12 hours;
and/or the esterification reaction is carried out under the protection of inert gas, wherein the inert gas comprises at least one of nitrogen, helium and argon.
7. A method for preparing perfluorosulfonic acid resin, which is characterized by comprising the following steps: providing an esterification product, mixing the esterification product with an acidic solution for hydrolysis reaction to obtain the perfluorinated sulfonic acid resin, wherein the esterification product is the esterification product prepared by the esterification method according to any one of claims 1 to 6.
8. The method for producing a perfluorosulfonic acid resin according to claim 7, wherein the mass ratio of the esterification product to the acidic solution is 1 (2-6).
9. The method for producing a perfluorosulfonic acid resin according to claim 7, wherein the concentration of hydrogen ions in the acidic solution is 1 to 5mol/L;
and/or the temperature of the hydrolysis reaction is 40-200 ℃;
and/or the hydrolysis reaction time is 4-8 hours.
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