CN112745445B - Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin - Google Patents
Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin Download PDFInfo
- Publication number
- CN112745445B CN112745445B CN201911048878.1A CN201911048878A CN112745445B CN 112745445 B CN112745445 B CN 112745445B CN 201911048878 A CN201911048878 A CN 201911048878A CN 112745445 B CN112745445 B CN 112745445B
- Authority
- CN
- China
- Prior art keywords
- initiator
- reaction
- pressure
- perfluoro
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011347 resin Substances 0.000 title claims abstract description 84
- 229920005989 resin Polymers 0.000 title claims abstract description 84
- -1 Perfluoro sulfonyl Chemical group 0.000 title claims abstract description 61
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 97
- 239000003999 initiator Substances 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 61
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 27
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 20
- HDMTWPVKWCLZNV-UHFFFAOYSA-N sulfuryl difluoride 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FS(F)(=O)=O.FC(F)=C(F)OC(F)=C(F)F HDMTWPVKWCLZNV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000003513 alkali Substances 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006460 hydrolysis reaction Methods 0.000 claims description 11
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000003460 sulfonic acids Chemical class 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- JUTIIYKOQPDNEV-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl 2,2,3,3,4,4,4-heptafluorobutaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)F JUTIIYKOQPDNEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 claims description 4
- TUFKHKZLBZWCAW-UHFFFAOYSA-N 2-(1-ethenoxypropan-2-yloxy)ethanesulfonyl fluoride Chemical compound C=COCC(C)OCCS(F)(=O)=O TUFKHKZLBZWCAW-UHFFFAOYSA-N 0.000 claims description 4
- SVQOKUWDNBOKFD-UHFFFAOYSA-N 2-ethenoxyethanesulfonyl fluoride Chemical compound FS(=O)(=O)CCOC=C SVQOKUWDNBOKFD-UHFFFAOYSA-N 0.000 claims description 4
- YMAPWVOHBWANGL-UHFFFAOYSA-N 3-ethenoxypropane-1-sulfonyl fluoride Chemical compound C(CCOC=C)S(=O)(=O)F YMAPWVOHBWANGL-UHFFFAOYSA-N 0.000 claims description 4
- QNCZMLLIOWEJPK-UHFFFAOYSA-N 4-ethenoxybutane-1-sulfonyl fluoride Chemical compound C(CCCOC=C)S(=O)(=O)F QNCZMLLIOWEJPK-UHFFFAOYSA-N 0.000 claims description 4
- VLDKZDODNCJFGL-UHFFFAOYSA-N CC(OCCCS(=O)(=O)F)COC=C Chemical compound CC(OCCCS(=O)(=O)F)COC=C VLDKZDODNCJFGL-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229960004624 perflexane Drugs 0.000 claims description 4
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003960 organic solvent Substances 0.000 abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 9
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 5
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000005342 ion exchange Methods 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000011282 treatment Methods 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000002572 peristaltic effect Effects 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 230000001131 transforming effect Effects 0.000 description 3
- WFELVFKXQJYPSL-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl chloride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Cl)=O WFELVFKXQJYPSL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
- C08F216/14—Monomers containing only one unsaturated aliphatic radical
- C08F216/1466—Monomers containing sulfur
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/14—Organic medium
-
- 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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- 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
-
- 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
- C08F8/12—Hydrolysis
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A perfluorosulfonyl fluoride resin, its preparation method and perfluorosulfonic acid resin prepared from it, inject tetrafluoroethylene gas into perfluorovinyl ether sulfonyl fluoride and solvent, make the pressure reach 0.3-0.7MPa, add initiator at least twice, after each initiator addition, reduce the pressure of tetrafluoroethylene gas in the reactor, each reduce 0.02-0.06MPa, continue to stir and react for 0.5-2h, prepare perfluorosulfonyl fluoride resin. The invention controls the reaction rate to be stable in the whole polymerization reaction process by continuously reducing the pressure of tetrafluoroethylene in the reaction and adding the initiator in batches, so that the composition of the perfluorosulfonyl fluororesin is stable, and the solubility of the perfluorosulfonic acid resin converted by the perfluorosulfonyl fluororesin is obviously reduced in organic solvents represented by tetrahydrofuran, DMSO and DMF.
Description
Technical Field
The invention relates to a preparation technology of perfluorosulfonyl fluororesin, in particular to perfluorosulfonyl fluororesin with low solubility in an organic solvent and a preparation method thereof, belonging to the technical field of organic synthesis.
Background
The perfluorinated sulfonic acid resin has the characteristics of excellent chemical stability, thermal stability, high mass mobility, super strong acidity and the like, and has a plurality of applications in the fields of fuel cells, chlor-alkali industry and acid catalysis. The melt processability of fluorosulfonic acid resin is poor, and perfluorosulfonyl fluoride resin, which is a precursor of fluorosulfonic acid resin, is often required to be processed into perfluorosulfonyl fluoride resin with a certain morphology (film, particle, etc.), and then subjected to hydrolysis, acidification, washing, drying, etc. to obtain the usable perfluorosulfonic acid resin. In recent years, the perfluorosulfonic acid resin has been increasingly applied in the field of catalysis due to its characteristics of high catalytic activity, high thermal stability, high chemical stability, easy separation and the like, and has a remarkable advantage as a heterogeneous solid catalyst particularly in liquid phase reaction.
In the conventional reaction for preparing the perfluorosulfonyl fluoride resin, tetrafluoroethylene and a perfluorovinyl ether sulfonyl fluoride monomer are reacted, but the concentration change of each reactant in the polymerization reaction easily causes uneven structure of a product, for example, in the perfluorosulfonyl fluoride resin obtained at the early stage, the number of non-tetrafluoroethylene structural units is relatively large, and in the perfluorosulfonyl fluoride resin obtained at the later stage, the number of tetrafluoroethylene structural units is relatively large. After perfluorosulfonyl fluoride resin with more non-tetrafluoroethylene structural units is prepared into a perfluorosulfonic acid resin catalyst, the perfluorosulfonic acid resin catalyst has higher solubility in an organic solvent and poorer mechanical property, is easy to damage and cause loss, and is very unfavorable for being used as the catalyst.
Therefore, the reaction conditions need to be regulated and controlled, so as to obtain the perfluorosulfonyl fluororesin product with uniform structure and low solubility of the catalyst prepared from the perfluorosulfonyl fluororesin in an organic solvent.
Chinese patent CN200610074586.1 provides a method for preparing perfluorosulfonic acid resin. The method is characterized in that: the fluorine-containing fluorine. The patent inevitably changes sulfonyl fluoride groups in a part of polymerization products into sulfonic acid groups with an aqueous solvent, which is disadvantageous for subsequent applications, and does not evaluate the loss rate of the obtained resin.
Disclosure of Invention
The invention provides a low-solubility perfluorosulfonyl fluororesin and a preparation method thereof, aiming at solving the problem that loss is caused by larger solubility of a catalyst prepared from the perfluorosulfonyl fluoride in an organic solvent due to uneven structure of the perfluorosulfonyl fluoride resin prepared in the prior art.
The technical purpose is realized by the following technical scheme:
the technical purpose of the first aspect of the invention is to provide a preparation method of perfluorosulfonyl fluoride, which comprises the following steps: injecting perfluorovinyl ether sulfonyl fluoride and a solvent into a reaction kettle, replacing air in the reaction kettle and a pipeline with nitrogen or inert gas, vacuumizing, introducing tetrafluoroethylene gas into the reaction kettle to enable the pressure to reach 0.3-0.7MPa, adding an initiator into the reaction kettle at least twice, heating, reducing the pressure of the tetrafluoroethylene gas in the reaction kettle after adding the initiator every time except for the first time, reducing the pressure by 0.02-0.06MPa every time, continuously stirring for reaction for 0.5-2h, relieving pressure after the reaction is finished, purging the reaction kettle with nitrogen, and collecting a product to obtain the perfluorosulfonyl fluoride resin.
Further, the initiator is added to the reaction kettle 2 to 9 times, preferably 4 to 9 times.
Furthermore, after the initiator is added each time, the pressure of the tetrafluoroethylene gas in the reaction kettle is reduced by 0.03-0.04 MPa.
Further, the perfluorovinyl ether sulfonyl fluoride is at least one selected from the group consisting of perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride), perfluoro (5-oxa-6-heptene-1-sulfonyl fluoride), perfluoro (4-oxa-5-hexene-1-sulfonyl fluoride), perfluoro (3-oxa-4-pentene-1-sulfonyl fluoride) and perfluoro (4, 7-dioxa-5-methyl-8-nonene-1-sulfonyl fluoride).
Further, the solvent is selected from one of perfluorohexane, 1, 2-trifluorotrichloroethane, 1-hydroperfluorohexane and 2, 3-dihydrodecafluoropentane.
Further, the weight ratio of the perfluorovinyl ether sulfonyl fluoride to the solvent is 10-31: 100 are added.
Further, the initiator is one of benzoyl peroxide, azobisisobutyronitrile and perfluorobutyryl peroxide.
Further, the weight ratio of the total addition amount of the initiator to the perfluorovinyl ether sulfonyl fluoride is 0.1-0.5: 100.
Because the initiator is used in a small amount, in order to avoid errors generated during addition, the initiator is generally mixed with a solvent to prepare an initiator solution during use, and the solvent is the same as the solvent used for dissolving the perfluorovinyl ether sulfonyl fluoride. The concentration of the initiator in the initiator solution is 25.0-35.0 mmol/L. The effective concentration of initiator in the solution was determined by iodometric titration.
Further, the initiator is added to the reaction system in portions at intervals of 0.5 to 2 hours/time.
Further, after the initiator solution is completely added, the reaction is carried out for 0.5 to 2 hours by continuously stirring for full reaction.
Further, the temperature in the reaction process is 20-60 ℃.
Further, after the product is collected, the solid-liquid mixture is obtained, and the mixture is subjected to post-treatment steps such as centrifugation, washing, drying and the like to obtain the final product of the perfluorosulfonyl fluororesin, namely the copolymer of perfluorovinyl ether sulfonyl fluoride and tetrafluoroethylene.
Because of the tetrafluoroethylene preparation, all have explosion risk in storage, the use, in order to furthest ensure experimenter's safety, reduce the harm that probably produces in the reaction sequence in the experiment, propose this operation to go on in explosion-proof equipment, the experimenter carries out remote control.
The technical object of the second aspect of the present invention is to provide a perfluorosulfonyl fluororesin prepared by the above process.
The technical purpose of the third aspect of the invention is to provide a method for preparing perfluorosulfonic acid resin by transforming the perfluorosulfonyl fluororesin.
Further, the method for preparing the perfluorosulfonic acid resin by transforming the perfluorosulfonyl fluororesin comprises the following specific steps: mixing the perfluorinated sulfonic acid fluorine resin with alkali liquor for hydrolysis reaction to obtain alkali resin, and then soaking and acidifying for multiple times by using acid liquor to obtain the perfluorinated sulfonic acid resin.
Further, as a more specific embodiment, the method comprises the following specific steps: adding perfluorosulfonyl fluororesin into a mixed solution of deionized water, DMSO and inorganic base, stirring for hydrolysis, washing with water for multiple times to remove the base to obtain an alkali type resin, and then soaking and acidifying the alkali type resin with acid liquor for multiple times to obtain perfluorosulfonic acid resin.
More specifically, in the above method, the inorganic base is sodium hydroxide or potassium hydroxide. The mixed solution comprises, by weight, 10% -20% of inorganic base, 30% -40% of DMSO and 45% -55% of deionized water. The hydrolysis temperature is 75-85 ℃, and the hydrolysis time is 6-10 h. The acid solution is a nitric acid solution, and the concentration of the nitric acid solution is 10-20% by weight.
Further, as a second more specific embodiment, the method comprises the following specific steps: adding perfluorosulfonyl fluororesin into an aqueous solution of inorganic base, stirring for hydrolysis, washing with water for multiple times to remove the base to obtain an alkali type resin, and then soaking and acidifying the alkali type resin with acid liquor for multiple times to obtain the perfluorosulfonic acid resin.
More specifically, in the above method, the inorganic base is sodium hydroxide or potassium hydroxide. The concentration of the inorganic base in the aqueous solution of the inorganic base is 25 to 35 percent by weight percentage. The hydrolysis temperature is 90-99 ℃, and the hydrolysis time is 6-10 h. The acid solution is a nitric acid solution, and the concentration of the nitric acid solution is 10-20% by weight.
It is a technical object of the third aspect of the present invention to provide a perfluorosulfonic acid resin prepared by the above process.
The invention has the advantages that:
(1) the preparation method of the invention continuously reduces the pressure of tetrafluoroethylene in a high-pressure reaction vessel in the polymerization reaction process, reduces the concentration of tetrafluoroethylene in the solution, keeps the proportion of perfluorovinyl ether sulfonyl fluoride and tetrafluoroethylene stable, thereby leading the composition of the perfluorosulfonyl fluoride resin to be stable, and obviously reducing the solubility of the perfluorosulfonic acid resin converted by the perfluorosulfonyl fluoride resin in organic solvents represented by tetrahydrofuran, DMSO and DMF.
(2) The preparation method of the invention also keeps the relative stability of the concentration of the initiator in the solution by adding the initiator in batches, controls the reaction rate to be stable in the whole polymerization reaction process, has low cost of the required equipment, and can ensure the quality of the obtained polymerization product.
(3) The solubility of the perfluorosulfonic acid resin obtained by transforming the perfluorosulfonyl fluororesin prepared by the method of the invention in an organic solvent is reduced, and the loss rate in the use process is reduced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The initiator adopted by the invention is one of benzoyl peroxide, azobisisobutyronitrile and perfluorobutyryl peroxide, wherein the benzoyl peroxide and the azobisisobutyronitrile are commercial products. Perfluorobutyryl peroxide was prepared as follows:
mixing perfluorobutyric acid and thionyl chloride, dripping DMF (dimethyl formamide), avoiding water, stirring, reacting at 70 ℃ for 24 hours, cooling to room temperature, standing and layering. The lower colorless transparent liquid phase is the product. Distilling after separating liquid, and collecting the fraction at 39-41 ℃ to obtain the perfluorobutyryl chloride. Dissolving sodium hydroxide in 30% hydrogen peroxide aqueous solution, cooling to 0 deg.C, stirring to dissolve completely, adding 1,1, 2-trifluorotrichloroethane, stirring for 20min, rapidly adding perfluorobutyryl chloride, stirring vigorously for 2min, and separating to obtain lower liquid phase of perfluorobutyryl peroxide (CF3CF2CF2COO) 2. The initiator solution is easy to decompose, is prepared as it is and can be stored in a 0 ℃ cold bath for a short time.
The transformation method of the perfluorosulfonyl fluororesin into the perfluorosulfonic acid resin, which is referred to in the following examples, includes the following two methods:
the method comprises the following steps: adding perfluorosulfonyl fluoride resin into a mixed solution of deionized water with the mass fraction of 50%, DMSO with the mass fraction of 35% and potassium hydroxide (or sodium hydroxide) with the mass fraction of 15%, stirring and hydrolyzing for 8h at 80 ℃, then washing with water for multiple times to remove redundant alkali to obtain alkali type resin, then soaking and acidifying the alkali type resin with nitric acid with the mass fraction of 15wt%, replacing fresh nitric acid solution after 6h, continuing to soak for 6h, and washing and drying to obtain perfluorosulfonic acid resin.
The second method comprises the following steps: adding perfluorosulfonyl fluoride resin into 30wt% potassium hydroxide (or sodium hydroxide) aqueous solution, stirring and soaking for 24h at 95 ℃, then washing with water for multiple times to remove redundant alkali to obtain alkali type resin, then soaking and acidifying the alkali type resin with 15wt% nitric acid, replacing fresh nitric acid solution after 6h, continuing to soak for 6h, and washing and drying to obtain perfluorosulfonic acid resin.
The method for testing the dissolving performance of the perfluorosulfonic acid resin comprises the following steps: accurately weighing 10.00g of the obtained perfluorinated sulfonic acid resin, adding the perfluorinated sulfonic acid resin into 120mL of anhydrous tetrahydrofuran, heating to 70 ℃, refluxing for 48h, cooling to room temperature, filtering, washing a condenser pipe and the inner wall of a flask by using a small amount of tetrahydrofuran, collecting all the residual solids, transferring the collected residual solids into a beaker, vacuum-drying for 12h at 100 ℃, taking out, weighing, and calculating the mass loss rate of the perfluorinated sulfonic acid resin before and after refluxing treatment to evaluate the solubility of the perfluorinated sulfonic acid resin. The conditions for measuring mass loss rate in DMSO and DMF are consistent with those of tetrahydrofuran.
The perfluorosulfonic acid resin adopts an ion exchange method to determine the ion exchange capacity, and the ion exchange method comprises the following steps: adding a certain amount of perfluorosulfonic acid resin into a 1M sodium chloride aqueous solution, stirring for 24h at room temperature, filtering and collecting filtrate, adding filter residue into the 1M sodium chloride aqueous solution, stirring for 24h at room temperature, filtering and collecting filtrate, fully washing the filter residue with deionized water, and collecting washing liquid. Merging the two filtrates and the washing liquid, using methyl orange as an indicator, and titrating the mixture by using a sodium hydroxide aqueous solution with a calibrated concentration, wherein the solution is changed from yellow to red as an end point. The ion exchange capacity can be calculated by the concentration of the sodium hydroxide solution, the consumption volume and the mass of the perfluorinated sulfonic acid resin.
Example 1
150g of perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride) and 1400g of 1,1, 2-trifluorotrichloroethane (the mass ratio of the two is 10.7: 100) were charged into a high-pressure reaction vessel by a peristaltic pump, 60mL of a 1,1, 2-trifluorotrichloroethane solution of perfluorobutyryl peroxide as an initiator (the concentration of perfluorobutyryl peroxide in the solution is 25mmol/L and 94.2g, and the mass ratio of the initiator to perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride) was 0.43: 100) was charged into a constant flow pump feed bottle, and after the air in the reaction vessel and the line was replaced with high-purity nitrogen gas, vacuum was applied.
Charging tetrafluoroethylene into a high-pressure reaction kettle to increase the pressure in the high-pressure reaction kettle to 0.6MPa, adding 12mL of initiator solution into the high-pressure reaction kettle by using a constant flow pump, and stirring for reaction when the temperature in the high-pressure reaction kettle is increased to 40 ℃ after the initiator solution is added. The initiator solution was added every 1.5h for a total of 5 times. Except for the first time and the last time, after adding the initiator solution once, regulating the tetrafluoroethylene pressure in the high-pressure kettle to be reduced by 0.05MPa compared with the previous pressure, and maintaining the tetrafluoroethylene pressure in the high-pressure kettle to be stable in the initiator adding interval period. The 5 th time of adding the initiator is followed by stirring for 2 hours. Stopping heating and decompressing.
After the reaction is finished, the high-pressure reaction kettle is firstly purged by nitrogen for 30 minutes, a solid-liquid mixture in the high-pressure reaction kettle is collected, and the final product of the perfluorosulfonyl fluororesin, namely the copolymer of perfluorovinyl ether sulfonyl fluoride and tetrafluoroethylene, is obtained through subsequent treatments such as centrifugation, washing, drying and the like, wherein the mass of the perfluorosulfonyl fluororesin is 121.8g, and the ion exchange capacity of the copolymer is 0.92mmol/g as determined by an ion exchange method.
The specific yield of the perfluorosulfonyl fluororesin is shown in table 1, the loss rate results of the perfluorosulfonic acid resin after being treated with different organic solvents are shown in tables 2 and 3, wherein table 2 is the loss rate of the perfluorosulfonic acid resin obtained by the first conversion method after being treated with an organic solvent, and table 3 is the loss rate of the perfluorosulfonic acid resin obtained by the second conversion method after being treated with an organic solvent.
Example 2
200g of perfluoro (5-oxa-6-heptene-1-sulfonyl fluoride) and 1350g of perfluorohexane (the mass ratio of the two is 14.8: 100) are injected into a high-pressure reaction kettle by a peristaltic pump, 96mL (the concentration is 25mmol/L, 160g, and the mass ratio of the initiator to the perfluoro (5-oxa-6-heptene-1-sulfonyl fluoride) of a perfluorohexane solution of initiator benzoyl peroxide is 0.29: 100) is filled into a constant-flow pump sample injection bottle, air in the reaction kettle and a pipeline is replaced by high-purity nitrogen, and then the high-pressure reaction kettle and the pipeline are vacuumized.
Filling tetrafluoroethylene into a high-pressure reaction kettle to increase the pressure in the high-pressure reaction kettle to 0.7MPa, adding 24mL of initiator solution into the high-pressure reaction kettle by using a constant flow pump, and stirring for reaction when the temperature in the high-pressure reaction kettle is increased to 60 ℃ after the initiator solution is added. The initiator solution was added every 0.5h for a total of 4 times. Except for the first time and the last time, after adding the initiator solution once, regulating the tetrafluoroethylene pressure in the high-pressure kettle to be reduced by 0.06MPa compared with the previous pressure, and maintaining the tetrafluoroethylene pressure in the high-pressure kettle to be stable in the initiator adding interval period. The reaction is continued for 0.5h with stirring after the 4 th initiator addition. Stopping heating and decompressing.
After the reaction is finished, the high-pressure reaction kettle is firstly purged by nitrogen for 30 minutes, a solid-liquid mixture in the high-pressure reaction kettle is collected, and the final product of the perfluorosulfonyl fluororesin, namely the copolymer of perfluorovinyl ether sulfonyl fluoride and tetrafluoroethylene, is obtained through subsequent treatments such as centrifugation, washing, drying and the like, wherein the mass of the perfluorosulfonyl fluororesin is 65.2g, and the ion exchange capacity of the copolymer is 1.07mmol/g as determined by an ion exchange method.
The perfluorosulfonyl fluororesin was converted into a perfluorosulfonic acid resin by the operations described in the first and second methods, respectively, the specific yield is shown in table 1, and the results of the loss rate of the perfluorosulfonic acid resin after treatment with different organic solvents are shown in tables 2 and 3.
Example 3
300g of perfluoro (4-oxa-5-hexene-1-sulfonyl fluoride) and 1250g of 1-hydroperfluorohexane (the mass ratio of the two is 24.0: 100) are injected into a high-pressure reaction kettle by a peristaltic pump, 72mL (the concentration is 35mmol/L, 120g, the mass ratio of the initiator to the perfluoro (4-oxa-5-hexene-1-sulfonyl fluoride) of a 1-hydroperfluorohexane solution of an initiator azobisisobutyronitrile is 0.14: 100) is filled into a constant-flow pump sample injection bottle, air in the reaction kettle and a pipeline is replaced by high-purity nitrogen, and then the high-pressure reaction kettle is vacuumized.
Charging tetrafluoroethylene into a high-pressure reaction kettle to increase the pressure in the high-pressure reaction kettle to 0.35MPa, adding 9mL of initiator solution into the high-pressure reaction kettle by using a constant flow pump, and stirring for reaction when the temperature in the high-pressure reaction kettle is increased to 50 ℃ after the initiator solution is added. The initiator solution was added every 2h for a total of 8 times. Except for the first time and the last time, after adding the initiator solution once, regulating the tetrafluoroethylene pressure in the high-pressure kettle to be reduced by 0.02MPa compared with the previous pressure, and maintaining the tetrafluoroethylene pressure in the high-pressure kettle to be stable in the initiator adding interval period. After 9 th initiator addition, the reaction was continued for 2h with stirring. Stopping heating and decompressing.
After the reaction is finished, the high-pressure reaction kettle is firstly purged by nitrogen for 30 minutes, a solid-liquid mixture in the high-pressure reaction kettle is collected, and the final product of the perfluorosulfonyl fluororesin, namely the copolymer of perfluorovinyl ether sulfonyl fluoride and tetrafluoroethylene, is obtained through subsequent treatments such as centrifugation, washing, drying and the like, wherein the mass of the perfluorosulfonyl fluororesin is 85.2g, and the ion exchange capacity of the copolymer is 1.20mmol/g as determined by an ion exchange method.
The perfluorosulfonyl fluororesin was converted into a perfluorosulfonic acid resin by the operations described in the first and second methods, respectively, the specific yield is shown in table 1, and the results of the loss rate of the perfluorosulfonic acid resin after treatment with different organic solvents are shown in tables 2 and 3.
Example 4
350g of perfluoro (4, 7-dioxa-5-methyl-8-nonene-1-sulfonyl fluoride) and 1150g of 2, 3-dihydrodecafluoropentane (the mass ratio of the two is 30.4: 100) were fed into a high-pressure reaction vessel by a peristaltic pump, 110mL of a 2, 3-dihydrodecafluoropentane solution (the concentration is 28mmol/L, 176g, and the mass ratio of the initiator to perfluoro (4, 7-dioxa-5-methyl-8-nonene-1-sulfonyl fluoride) of the initiator peroxoperfluorobutyryl was fed into a constant flow pump feed bottle, the air in the reaction vessel and the piping was replaced with high-purity nitrogen gas, and then vacuum was applied.
Filling the tetrafluoroethylene into a high-pressure reaction kettle, and increasing the pressure in the high-pressure reaction kettle to 0.45 MPa. And then, adding 22mL of initiator solution into the high-pressure reaction kettle by using a constant flow pump, and stirring for reaction when the temperature in the high-pressure reaction kettle is raised to 20 ℃. The initiator solution was added every 1h for a total of 5 times. Except for the first time and the last time, after adding the initiator solution once, regulating the tetrafluoroethylene pressure in the high-pressure kettle to be reduced by 0.05MPa compared with the previous pressure, and maintaining the tetrafluoroethylene pressure in the high-pressure kettle to be stable in the initiator adding interval period. The 5 th time of adding the initiator is followed by stirring for 1 hour. Stopping heating and decompressing.
After the reaction is finished, the high-pressure reaction kettle is firstly purged by nitrogen for 30 minutes, a solid-liquid mixture in the high-pressure reaction kettle is collected, and the final product of the perfluorosulfonyl fluororesin, namely the copolymer of perfluorovinyl ether sulfonyl fluoride and tetrafluoroethylene, is obtained through subsequent treatments such as centrifugation, washing, drying and the like, wherein the mass of the perfluorosulfonyl fluororesin is 165.2g, and the ion exchange capacity of the copolymer is 0.80mmol/g as determined by an ion exchange method.
The perfluorosulfonyl fluororesin was converted into a perfluorosulfonic acid resin by the operations described in the first and second methods, respectively, the specific yield is shown in table 1, and the results of the loss rate of the perfluorosulfonic acid resin after treatment with different organic solvents are shown in tables 2 and 3.
Example 5
200g of perfluoro (3-oxa-4-pentene-1-sulfonyl fluoride) and 1350g of 1-hydroperfluorohexane (the mass ratio of the two is 14.8: 100) are injected into a high-pressure reaction kettle by a peristaltic pump, a constant flow pump sample injection bottle is filled with 80mL (the concentration is 26mmol/L, 135g, the mass ratio of the initiator to the perfluoro (3-oxa-4-pentene-1-sulfonyl fluoride) of a 1-hydroperfluorohexane solution of an initiator benzoyl peroxide is 0.25: 100), the air in the reaction kettle and a pipeline is replaced by high-purity nitrogen, and then the reaction kettle and the pipeline are vacuumized.
Filling tetrafluoroethylene into a high-pressure reaction kettle, and increasing the pressure in the high-pressure reaction kettle to 0.5 MPa. And then, adding 20mL of initiator solution into the high-pressure reaction kettle by using a constant flow pump, and stirring for reaction when the temperature in the high-pressure reaction kettle is raised to 50 ℃. The initiator solution was added every 1.5h for a total of 4 times. After adding the initiator solution once, regulating the tetrafluoroethylene pressure in the high-pressure kettle to be reduced by 0.04MPa compared with the previous pressure, and maintaining the tetrafluoroethylene pressure in the high-pressure kettle to be stable in the interval period of adding the initiator except for the first time and the last time. After the 4 th initiator addition, the reaction was continued for 2h with stirring. Stopping heating and decompressing.
After the reaction is finished, the high-pressure reaction kettle is firstly purged by nitrogen for 30 minutes, a solid-liquid mixture in the high-pressure reaction kettle is collected, and the final product of the perfluorosulfonyl fluororesin, namely the copolymer of perfluorovinyl ether sulfonyl fluoride and tetrafluoroethylene, is obtained through subsequent treatments such as centrifugation, washing, drying and the like, wherein the mass of the perfluorosulfonyl fluororesin is 91.8g, and the ion exchange capacity of the copolymer is 0.91mmol/g as determined by an ion exchange method.
The specific yields of perfluorosulfonyl fluororesin were converted into perfluorosulfonic acid resin by the operations described in the above first and second methods, respectively, are shown in table 1, and the results of the run-off rates of perfluorosulfonic acid resin treated with different organic solvents are shown in tables 2 and 3.
Comparative example 1
The initial pressure of tetrafluoroethylene in the autoclave was 0.50MPa, 50mL of the initiator (perfluorobutyryl peroxide concentration: 25 mmol/L) was added in one portion, and the pressure of tetrafluoroethylene in the autoclave was maintained as described in example 1, and the reaction was carried out for 8 hours. 122.8g of perfluorosulfonyl fluoride resin was obtained, which had an ion exchange capacity of 0.96mmol/g as measured by an ion exchange method.
Similarly, the specific yields of the perfluorosulfonyl fluororesin converted to the perfluorosulfonic acid resin by the operations described in the first and second methods are shown in table 1, and the results of the loss rates of the perfluorosulfonic acid resin after treatment with different organic solvents are shown in tables 2 and 3.
TABLE 1
Note: the first method uses mixed aqueous solution of DMSO and alkali in the treatment process, and the second method uses inorganic alkali aqueous solution.
TABLE 2
TABLE 3
The results in Table 1 show that the yields of the first process in examples 1 to 5 were slightly lower than those of the second process because DMSO was used in the transformation process in the first process and a very small portion of the perfluorosulfonyl fluororesin was dissolved in DMSO, whereas the yield of the first process was low in comparative example 1 because a large amount of loss occurred during the transformation process using the process because the perfluorosulfonyl fluoride resin was different in quality from the present invention.
As can be seen from the data in tables 2 and 3, the loss rate of the perfluorosulfonic acid resin prepared by the method of the present invention is significantly lower than that of comparative example 1.
Claims (20)
1. A preparation method of perfluorosulfonyl fluororesin comprises the following steps: injecting perfluorovinyl ether sulfonyl fluoride and a solvent into a reaction kettle, replacing air in the reaction kettle and a pipeline with nitrogen or inert gas, vacuumizing, introducing tetrafluoroethylene gas into the reaction kettle to enable the pressure to reach 0.3-0.7MPa, adding an initiator into the reaction kettle at least twice, heating, reducing the pressure of the tetrafluoroethylene gas in the reaction kettle after adding the initiator every time except for the first time, reducing the pressure by 0.02-0.06MPa every time, continuously stirring for reaction for 0.5-2h, relieving pressure after the reaction is finished, purging the reaction kettle with nitrogen, and collecting a product to obtain the perfluorosulfonyl fluoride resin.
2. The method according to claim 1, wherein the initiator is added to the reaction vessel in 2 to 9 portions.
3. The method according to claim 2, wherein the initiator is added to the reaction vessel in 4 to 9 portions.
4. The production method according to claim 1, wherein the pressure of the tetrafluoroethylene gas in the reaction vessel is reduced by 0.03 to 0.04MPa after each addition of the initiator.
5. The production method according to claim 1, wherein the perfluorovinyl ether sulfonyl fluoride is at least one selected from the group consisting of perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride), perfluoro (5-oxa-6-heptene-1-sulfonyl fluoride), perfluoro (4-oxa-5-hexene-1-sulfonyl fluoride), perfluoro (3-oxa-4-pentene-1-sulfonyl fluoride) and perfluoro (4, 7-dioxa-5-methyl-8-nonene-1-sulfonyl fluoride).
6. The method according to claim 1, wherein the solvent is one selected from the group consisting of perfluorohexane, 1, 2-trifluorotrichloroethane, 1-hydroperfluorohexane and 2, 3-dihydrodecafluoropentane.
7. The process according to claim 1, wherein the weight ratio of said perfluorovinyl ether sulfonyl fluoride to said solvent is 10 to 31: 100 are added.
8. The method according to claim 1, wherein the initiator is one of benzoyl peroxide, azobisisobutyronitrile, and perfluorobutyryl peroxide.
9. The method according to claim 1, wherein the weight ratio of the total amount of the initiator to the perfluorovinyl ether sulfonyl fluoride is 0.1 to 0.5: 100.
10. The process according to claim 1, wherein the initiator is mixed with a solvent to prepare an initiator solution, and the initiator solution is then added to the reaction system, wherein the solvent is the same as the solvent used for dissolving the perfluorovinyl ether sulfonyl fluoride.
11. The method according to claim 10, wherein the concentration of the initiator in the initiator solution is 25.0 to 35.0 mmol/L.
12. The process according to claim 1, wherein the initiator is added to the reaction system in portions at intervals of 0.5 to 2 hours/time.
13. The preparation method according to claim 1, wherein after the initiator solution is completely added, the reaction is continued for 0.5 to 2 hours with stirring to complete the reaction.
14. The method according to claim 1, wherein the temperature during the reaction is 20 to 60 ℃.
15. A perfluorosulfonyl fluororesin prepared by the process of any one of claims 1 to 14.
16. A process for producing a perfluorosulfonic acid resin by converting the perfluorosulfonyl fluororesin as claimed in claim 15.
17. The method according to claim 16, comprising the specific steps of: mixing the perfluorinated sulfonic acid fluorine resin with alkali liquor for hydrolysis reaction to obtain alkali resin, and then soaking and acidifying with acid liquor to obtain perfluorinated sulfonic acid resin.
18. The method of claim 17, comprising the following steps: adding perfluorosulfonyl fluororesin into a mixed solution of deionized water, DMSO and inorganic base, stirring for hydrolysis, washing with water for multiple times to remove the base to obtain an alkali type resin, and then soaking and acidifying the alkali type resin with acid liquor for multiple times to obtain perfluorosulfonic acid resin.
19. The method of claim 17, comprising the following steps: adding perfluorosulfonyl fluororesin into an aqueous solution of inorganic base, stirring for hydrolysis, washing with water for multiple times to remove the base to obtain an alkali type resin, and then soaking and acidifying the alkali type resin with acid liquor for multiple times to obtain the perfluorosulfonic acid resin.
20. A perfluorosulfonic acid resin prepared by the process of any one of claims 16-19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911048878.1A CN112745445B (en) | 2019-10-31 | 2019-10-31 | Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911048878.1A CN112745445B (en) | 2019-10-31 | 2019-10-31 | Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112745445A CN112745445A (en) | 2021-05-04 |
| CN112745445B true CN112745445B (en) | 2022-06-07 |
Family
ID=75641093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911048878.1A Active CN112745445B (en) | 2019-10-31 | 2019-10-31 | Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112745445B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109210B (en) * | 2022-07-27 | 2023-07-14 | 深圳市中仁能源科技有限公司 | Proton exchange resin solution for improving power generation capacity of fuel cell electrode and application method thereof |
| CN116554386B (en) * | 2023-07-07 | 2023-09-29 | 国家电投集团氢能科技发展有限公司 | Esterification method of perfluorosulfonyl fluoride resin and preparation method of perfluorosulfonic acid resin |
| CN118027275B (en) * | 2024-04-12 | 2024-07-05 | 安徽明天新能源科技有限公司 | Preparation method of short side chain perfluorinated sulfonic acid resin |
| CN118684806A (en) * | 2024-08-22 | 2024-09-24 | 江苏科润膜材料有限公司 | Preparation method of emulsion polymerization terpolymer, and product and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1955203A (en) * | 2005-10-24 | 2007-05-02 | 山东东岳神舟新材料有限公司 | Preparation method of perfluorosulphonyl resin |
| CN103159973A (en) * | 2013-03-29 | 2013-06-19 | 上海交通大学 | New process for preparing porous high polymer reinforced perfluorinated sulfonic acid resin composite membrane |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7482415B2 (en) * | 2000-02-16 | 2009-01-27 | Daikin Industries, Ltd. | Process for producing fluoroionomer, method for purification and concentration of the ionomer, and method of film formation |
-
2019
- 2019-10-31 CN CN201911048878.1A patent/CN112745445B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1955203A (en) * | 2005-10-24 | 2007-05-02 | 山东东岳神舟新材料有限公司 | Preparation method of perfluorosulphonyl resin |
| CN103159973A (en) * | 2013-03-29 | 2013-06-19 | 上海交通大学 | New process for preparing porous high polymer reinforced perfluorinated sulfonic acid resin composite membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112745445A (en) | 2021-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112745445B (en) | Perfluoro sulfonyl fluororesin, preparation method thereof and perfluoro sulfonic acid resin prepared from perfluoro sulfonyl fluororesin | |
| CN110467163B (en) | Preparation method of bis (fluorosulfonyl) imide | |
| CN109336744A (en) | A kind of preparation method of poly(perfluoropropene) alkyl ether | |
| CN101775130B (en) | Method for production and post-processing of hexafluoropropylene oxide homopolymer | |
| CN112321558B (en) | Preparation method of fluoroethylene carbonate | |
| CN103044190B (en) | Preparation method of trifluoroethylene | |
| CN114213569A (en) | Suspension polymerization preparation method of perfluorosulfonic acid resin | |
| CN111116308B (en) | Preparation method of hexafluoropropylene dimer | |
| CN1944360A (en) | Process for preparing perfluoro nonene | |
| CN116789704A (en) | Cyclic sulfate compound and preparation method and application thereof | |
| CN109535001B (en) | Method for preparing fluorocarboxylic acid ester | |
| CN111072526A (en) | Preparation method of resin monomer for ion exchange membrane | |
| EP3643728B1 (en) | Methods for producing fluorinated polymer, fluorinated polymer having functional group and electrolyte membrane | |
| CN115894433A (en) | Process for continuously synthesizing vinyl sulfate crude product | |
| CN107188777B (en) | preparation method of chloropentafluorobenzene | |
| CN102381929B (en) | Method for initiating continuous production of short-chain perfluoroalkyl iodide by using fluorine gas | |
| CN111378064B (en) | Preparation method of perfluorosulfonyl fluororesin | |
| CN113912075A (en) | Preparation method of lithium tetrafluoroborate | |
| CN104016848B (en) | The preparation method of a kind of five fluorine propionyl fluorides | |
| CN116063255B (en) | Method for preparing beta-propiolactone | |
| CN112028747A (en) | Co-production process of hexafluoroisopropyl methyl ether and pentafluoropropionic acid | |
| CN101759522A (en) | Method for preparing perfluorinated nonene by oligomerization of hexafluoropropylene | |
| EP3112345A1 (en) | Method for producing fluoroalkanesulfonic anhydride | |
| CN112500285B (en) | Continuous preparation method of trifluoroacetyl fluoride | |
| CN117624110B (en) | Synthetic method of fluoroethylene carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231101 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TR01 | Transfer of patent right |