CN111378064B - Preparation method of perfluorosulfonyl fluororesin - Google Patents
Preparation method of perfluorosulfonyl fluororesin Download PDFInfo
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- CN111378064B CN111378064B CN201811622977.1A CN201811622977A CN111378064B CN 111378064 B CN111378064 B CN 111378064B CN 201811622977 A CN201811622977 A CN 201811622977A CN 111378064 B CN111378064 B CN 111378064B
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- fluoride
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- sulfonyl fluoride
- perfluorosulfonyl
- fluorocarbon oil
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- -1 perfluorosulfonyl Chemical group 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims description 26
- 239000006227 byproduct Substances 0.000 claims abstract description 56
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920005989 resin Polymers 0.000 claims abstract description 34
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 238000009835 boiling Methods 0.000 claims description 20
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 20
- LUYQYZLEHLTPBH-UHFFFAOYSA-N perfluorobutanesulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O LUYQYZLEHLTPBH-UHFFFAOYSA-N 0.000 claims description 18
- 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 10
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- HSDJWNJDPDJOEV-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O HSDJWNJDPDJOEV-UHFFFAOYSA-N 0.000 claims description 7
- BHFJBHMTEDLICO-UHFFFAOYSA-N Perfluorooctylsulfonyl fluoride Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)S(F)(=O)=O BHFJBHMTEDLICO-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 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 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 4
- 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 3
- 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 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007171 acid catalysis Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000000446 fuel Substances 0.000 abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000003014 ion exchange membrane Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 238000005868 electrolysis reaction Methods 0.000 description 14
- 229910006095 SO2F Inorganic materials 0.000 description 10
- NHGWSCVQFRCBSV-UHFFFAOYSA-N butane-1-sulfonyl fluoride Chemical compound CCCCS(F)(=O)=O NHGWSCVQFRCBSV-UHFFFAOYSA-N 0.000 description 10
- 239000012043 crude product Substances 0.000 description 10
- 238000005342 ion exchange Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- DNCIDNCRBAKPTP-UHFFFAOYSA-N hexane-1-sulfonyl fluoride Chemical compound CCCCCCS(F)(=O)=O DNCIDNCRBAKPTP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- HMRWGKIZOBXNRB-UHFFFAOYSA-N octane-1-sulfonyl fluoride Chemical compound CCCCCCCCS(F)(=O)=O HMRWGKIZOBXNRB-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 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 description 1
- TXGPGHBYAPBDAG-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluoro-4,4-bis(trifluoromethyl)cyclobutane Chemical compound FC(F)(F)C1(C(F)(F)F)C(F)(F)C(F)(F)C1(F)F TXGPGHBYAPBDAG-UHFFFAOYSA-N 0.000 description 1
- LMHAGAHDHRQIMB-UHFFFAOYSA-N 1,2-dichloro-1,2,3,3,4,4-hexafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(Cl)C1(F)Cl LMHAGAHDHRQIMB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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
-
- 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
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing perfluorosulfonyl fluoride resin comprises the steps of taking fluorocarbon oil as a solvent, and taking tetrafluoroethylene and sulfonyl fluoride-based perfluoroalkyl vinyl ether as raw materials to carry out copolymerization reaction to prepare perfluorosulfonyl fluoride resin; wherein the fluorocarbon oil is a nonpolar component of a byproduct generated in the production of organic fluoride through electrolytic fluorination. The method for preparing the perfluorosulfonyl fluoride resin has the advantages that the fluorocarbon oil is used as the solvent, the solvent cost of the traditional production method is reduced, the waste utilization is realized, and the prepared perfluorosulfonyl fluoride resin can be used as a solid super acidic catalyst in the field of acid catalysis after being processed and can also be used for preparing perfluorosulfonic acid ion exchange membranes used in the fields of chlor-alkali industry, fuel cells and the like.
Description
Technical Field
The invention relates to a preparation method of perfluorosulfonyl fluororesin, in particular to a method for preparing perfluorosulfonyl fluororesin by using fluorocarbon oil as a solvent.
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 perfluorosulfonic acid resin has poor mechanical processing performance, and the precursor, namely the perfluorosulfonyl fluoride resin, is processed into a perfluorosulfonic acid resin with a certain shape (such as a film, a particle and the like) and then is subjected to hydrolysis, acidification, washing, drying and other steps to obtain the perfluorosulfonic acid resin which can be directly used. The perfluorosulfonyl fluororesin is prepared by using perfluoroalkyl vinyl ether with sulfonyl fluoride group and Tetrafluoroethylene (TFE) as monomers through solution polymerization, emulsion polymerization and the like, wherein the solution polymerization is widely applied due to the modes of large production, simple and convenient post-treatment and the like. For a long time, perfluorosulfonyl fluororesins have been supplied from foreign sources such as: DuPont, 3M, Asahi glass company, Asahi chemical Co., Ltd. Perfluorosulfonyl fluoride resins and their derivatives (perfluorosulfonic acid resins, perfluorosulfonic acid proton exchange membranes, etc.) are expensive. In recent years, the production of perfluorosulfonyl fluoride resin in China has also been primarily developed. The method realizes the production of the domestic low-cost perfluorosulfonyl fluororesin, and has great significance for breaking the monopoly abroad and promoting the development of the industries such as domestic fuel cells, chlor-alkali industry, acid catalysis and the like.
U.S. Pat. No. 3,3282875 3282875A earlier proposed the use of perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride) (formula CF2=CFOCF2CF(CF3)OCF2CF2SO2F, PSVE for short) and tetrafluoroethylene (formula CF)2=CF2TFE for short) as a raw material, perfluorodimethylcyclobutane (boiling point of 45 ℃) as a solvent, reacting for 1 hour at 5.5 MPa and 80 ℃ under the action of an initiator to obtain a copolymer, and hydrolyzing and acidifying the copolymer to obtain the perfluorosulfonic acid resin. For recent decades, solvents used for similar copolymerization reactions include: 1, 1, 2-trifluoro-trichloroethane (boiling point 47-48 ℃), 1, 2-dichloro-hexafluorocyclobutane (boiling point 59 ℃, Odinokov AS et al Synthesis, properties and applications of F-4SF copolymer. Fluorine Notes 2011, 2(75): 1), 2, 3-dihydro-decafluoropentane (boiling point 55 ℃, Uematsu N et al Synthesis of novel fluorinated monomers and their applications, Journal of Fluorine Chemistry 2006, 137: 1087-, 4-tetrachlorohexafluorobutane (boiling point 133-. These solvents all contain fluorocarbon chains (trifluoromethyl-CF)3Or difluoromethylene-CF2-) structure, has good dissolving capacity for PSVE and TFE, and is beneficial to polymerization reaction. But also has the defects of high cost, high production difficulty and the like, and limits the development of the production of the perfluorosulfonyl fluororesin.
Fluorocarbon oil is a by-product of electrolytic fluorination. During the electrolysis, the conversion of the alkylsulfonyl fluoride (or the alkylsulfonyl fluoride) is usually 30 to 60%, and a large amount of by-products are generated. The electrolytic fluorination by-product is treated as chemical waste at present, and the persistent environmental pollution is serious. The electrolytic fluorination by-product is the residual component of the rectified main product (perfluoroalkyl sulfonyl fluoride, perfluoroalkyl acyl fluoride and the like) of the electrolytic fluorination crude product, and the nonpolar fluorocarbon oil can be obtained after a series of treatments. The fluorocarbon oil has a wide boiling range, has good dissolving capacity for organic fluoride monomers (sulfonyl fluoride perfluoroalkyl vinyl ether, TFE and the like), and is very suitable for replacing a high-valence solvent to be used for producing the perfluorinated sulfonic acid resin.
At present, no public report of fluorocarbon oil used for polymerization reaction solvent of perfluorosulfonyl fluoride resin exists.
Disclosure of Invention
In order to solve the defects of high solvent price and large production difficulty in the solution polymerization process for producing the perfluorosulfonyl fluororesin in the prior art, the invention provides a preparation method of the perfluorosulfonyl fluororesin, which takes fluorocarbon oil as a solvent. The method has the advantages of low production cost, high yield and stable quality of the obtained perfluorosulfonyl fluoride resin.
In order to realize the technical purpose, the invention provides a preparation method of perfluorosulfonyl fluororesin, which takes fluorocarbon oil as a solvent and tetrafluoroethylene and sulfonyl fluoride-based perfluoroalkyl vinyl ether as raw materials to carry out copolymerization reaction to prepare perfluorosulfonyl fluororesin; wherein the fluorocarbon oil is a nonpolar component of a byproduct generated in the production of organic fluoride through electrolytic fluorination.
In the preparation method, the fluorocarbon oil is one or a mixture of more of nonpolar components in a byproduct of producing perfluorobutanesulfonyl fluoride through electrolytic fluorination, nonpolar components in a byproduct of producing perfluorohexylsulfonyl fluoride through electrolytic fluorination and nonpolar components in a byproduct of producing perfluorooctylsulfonyl fluoride through electrolytic fluorination. Among them, the most preferable is the nonpolar component in the by-product of the production of perfluorobutanesulfonyl fluoride by electrolytic fluorination.
In the above preparation method, as will be understood by those skilled in the art, the fluorocarbon oil is a nonpolar component of a by-product of electrolytic fluorination using anhydrous hydrogen fluoride and alkylsulfonyl fluoride or anhydrous hydrogen fluoride and alkanoyl fluoride as raw materials, and its main components are perfluoroepoxy ether, perfluoroalkane, partially fluorinated alkane, and the like. The fluorocarbon oil obtained along with different electrolytic fluorination main products has different carbon chain lengths and different boiling ranges. Wherein the nonpolar component in the byproduct of the production of the perfluorobutanesulfonyl fluoride by the electrolytic fluorination is a product with a boiling range of 50-90 ℃ separated by rectification from the byproduct; the nonpolar component in the byproduct of producing perfluorohexyl sulfonyl fluoride by electrolytic fluorination is a product with the boiling range of 90-130 ℃ separated from the byproduct by rectification; the nonpolar component in the byproduct of the production of perfluorooctylsulfonyl fluoride by electrolytic fluorination is the product with the boiling range of 130-180 ℃ separated by rectification from the byproduct.
In the above production method, as a specific embodiment, a specific reaction process for obtaining by-products by electrolytic fluorination is as follows: the method comprises the steps of taking alkyl sulfonyl fluoride and anhydrous hydrogen fluoride as raw materials, placing the raw materials in a Simons electrolytic tank, and electrolyzing the raw material mixture by low-voltage direct current (DC 4-8V) to obtain a byproduct in the process of producing the perfluoroalkyl sulfonyl fluoride. More specific embodiments are as follows: pumping anhydrous hydrogen fluoride and alkyl sulfonyl fluoride into an electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the alkyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 5-10: 100. and (3) applying 4-8V direct current to the mixed solution for reaction, stopping electrifying after electrolysis, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking the lower layer of brown yellow product as a crude product, and rectifying and separating to obtain a product and a byproduct.
In the preparation method, the mixing mass ratio of the fluorocarbon oil to the sulfonyl fluoride-based perfluoroalkyl vinyl ether is 1: 0.1-5, preferably 1: 0.5 to 2.
In the above production process, the sulfonyl fluoride-based perfluoroalkyl vinyl ether is selected from perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride) (CF)2=CFO CF2CF(CF3) OCF2CF2SO2F) Perfluoro (5-oxa-6-heptene-1-sulfonyl fluoride) (CF2=CFO(CF2)4SO2F) Perfluoro (4-oxa-5-hexene-1-sulfonyl fluoride) (CF2=CFO(CF2)3SO2F) Perfluoro (3-oxa-4-pentene-1-sulfonyl fluoride) (CF)2=CFO(CF2)2SO2F) And perfluoro (4, 7-dioxa-5-methyl-8-nonene-1-sulfonyl fluoride) (CF2=CFOCF2CF(CF3)O(CF2)3SO2F) One kind of (1).
In the preparation method, an initiator is added into the copolymerization reaction system, and the initiator is selected from one of perfluorobutyryl peroxide, dibenzoyl peroxide and azobisisobutyronitrile.
In the above production method, as one of specific embodiments, the perfluorosulfonyl fluororesin is produced by the following specific means:
(1) mixing fluorocarbon oil and sulfonyl fluoride perfluoroalkyl vinyl ether, sealing, vacuumizing, and charging tetrafluoroethylene;
(2) adding an initiator into a reaction system, stirring, heating, starting a polymerization reaction, supplementing tetrafluoroethylene to maintain pressure, and reacting to obtain a polymer solution;
(3) adding a poor solvent into the polymer solution to precipitate the copolymer, and filtering, washing and drying to obtain the perfluorosulfonyl fluororesin.
The perfluorosulfonyl fluoride resin prepared by the method can be used as a solid super acidic catalyst in the field of acid catalysis after being processed and can also be used for preparing perfluorosulfonic acid ion exchange membranes used in the fields of chlor-alkali industry, fuel cells and the like.
The method for preparing the perfluorosulfonyl fluoride resin takes the fluorocarbon oil as the solvent, reduces the solvent cost of the traditional production method, realizes waste utilization, and has higher raw material conversion rate compared with the traditional solvent.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an infrared spectrum of a perfluorosulfonyl fluororesin of example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
Fluorocarbon oils used in the examples were prepared in the following manner: preparing a crude product of perfluorobutanesulfonyl fluoride by electrolytic fluorination, rectifying to obtain perfluorobutanesulfonyl fluoride (a main product) and a byproduct, rectifying the byproduct, and collecting a fraction at 50-90 ℃ to obtain the required fluorocarbon oil. The method for preparing fluorocarbon oil from the byproduct of perfluorohexyl sulfonyl fluoride and the byproduct of perfluorooctyl sulfonyl fluoride produced by electrolytic fluorination is similar to that of perfluorobutyl sulfonyl fluoride, and fractions at 90-130 ℃, 130-180 ℃ are respectively collected in the rectification process.
Example 1
(1) Preparation of fluorocarbon oil (nonpolar component of perfluorobutanesulfonyl fluoride byproduct produced by electrolytic fluorination): pumping anhydrous hydrogen fluoride and butyl sulfonyl fluoride into a Simons electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the butyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 10: 100. applying 5-7V direct current to the mixed solution to start electrolysis, stopping electrifying after the electrolysis is finished, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking the lower layer of brown yellow product as a crude product, and rectifying and separating to obtain the product and a byproduct. Rectifying the by-product after the perfluorobutanesulfonyl fluoride is separated out, and collecting the product with the boiling range of 50-90 ℃ to obtain the fluorocarbon oil.
(2) Preparation of perfluorosulfonyl fluororesin: mixing 150g of perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride) and 150g of fluorocarbon oil prepared in the step (1), adding the mixture into a 1L stainless steel high-pressure reaction kettle, stirring at room temperature, vacuumizing, filling tetrafluoroethylene to gauge pressure of 1atm, heating to 45 ℃, and continuously filling the tetrafluoroethylene to 5 atm. 40mL of perfluorobutyryl peroxide (structural formula (CF) is pressed in by a constant flow pump3CF2CF2COO)2) And (2%) adding tetrafluoroethylene continuously to keep the pressure at 5atm when the reaction is started, stopping introducing the tetrafluoroethylene after the reaction is carried out for 12 hours, stopping heating after the reaction is carried out for 1 hour, cooling to room temperature, and releasing the pressure to obtain a polymer mixed solution. To the mixture was added 300g of chloroform to produce a white precipitate, which was collected by filtration, washed with chloroform and then filtered, and dried under vacuum at 100 ℃ to obtain 72.4g of white granular polymer perfluorosulfonyl fluororesin. The conversion was 19.4% based on perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride).
The prepared perfluorosulfonyl fluororesin was subjected to infrared spectrum test, and the obtained infrared spectrum is shown in fig. 1: 1470cm-1Is SO2Vibration peak, 1060-1320cm-1Is a C-F vibration peak (including CF)3、-CF2-、-CF(CF3)-），986cm-1Is C-O-C vibration peak, 810cm-1Is the S-F vibration peak at 600--1C-F vibration peaks. The infrared test result is consistent with the structure of the perfluorosulfonyl fluoride resin.
The ion exchange capacity of the prepared perfluorosulfonyl fluororesin was measured by the following method:
3.75g of potassium hydroxide, 12.50g of deionized water and 8.75g of dimethyl sulfoxide are mixed and cooled to obtain hydrolysate containing DMSO. Adding 1.3622g perfluorosulfonyl fluoride resin into the hydrolysate, heating and stirring for 8 hours at 80 ℃, cooling, filtering, collecting filter residue, repeatedly washing the filter residue with deionized water until the eluate is neutral, and filtering to obtain the potassium resin. Adding the potassium resin into 50mL of nitric acid aqueous solution with the mass fraction of 13%, stirring for 2 hours at 80 ℃, cooling, standing, and pouring out the liquid phase. And adding 50mL of nitric acid solution with the mass fraction of 13%, stirring for 2 hours at 80 ℃, cooling, filtering and collecting filter residues, washing the filter residues with deionized water until the eluate is neutral, and vacuum-drying the filter residues for 8 hours at 100 ℃ to obtain the perfluorosulfonic acid resin. Adding the perfluorinated sulfonic acid resin into 50mL of 1mol/L sodium chloride solution, stirring at room temperature for 24 hours, and pouring out a liquid phase; then adding 50mL of 1mol/L sodium chloride solution, stirring for 24 hours at room temperature, pouring out the liquid phase, and combining the liquid phase with the previous liquid phase; the remaining solid was washed 2 times with 20mL of deionized water and incorporated into the aforementioned liquid phase to give a test solution containing hydrogen ions obtained by ion exchange from a perfluorosulfonic acid resin. And (3) titrating the hydrogen ion concentration in the test solution by using a sodium hydroxide solution with a determined concentration as a titration solution and phenolphthalein as an indicator, and calculating to obtain that the ion exchange capacity of the perfluorinated sulfonic acid resin is 0.90 mmol/g.
Example 2
(1) Preparation of fluorocarbon oil (nonpolar component of perfluorooctyl sulfonyl fluoride byproduct produced by electrolytic fluorination): pumping anhydrous hydrogen fluoride and octyl sulfonyl fluoride into a Simons electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the octyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 5: 100. applying 5-8V direct current to the mixed solution to start electrolysis, stopping electrifying after the electrolysis is finished, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking the lower layer of brown yellow product as a crude product, and rectifying and separating to obtain the product and a byproduct. Rectifying the by-product after the perfluorooctyl sulfonyl fluoride is separated out, and collecting the product with the boiling range of 130-180 ℃ to obtain the fluorocarbon oil.
(2) Preparation of perfluorosulfonyl fluororesin: 100g of perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride) and 150g of the fluorocarbon oil prepared in the step (1) were mixed and then charged into a 1L stainless steel autoclave, and polymerization was conducted under the same conditions as in example 1 to obtain 56.2g of a perfluorosulfonyl fluoride resin in the form of a white block. The conversion was 18.7% based on perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride).
The ion exchange capacity of the resulting perfluorosulfonyl fluororesin was measured to be 0.75mmol/g in the same manner as in example 1.
Example 3
(1) Preparation of fluorocarbon oil (nonpolar component of perfluorohexyl sulfonyl fluoride by-product produced by electrolytic fluorination): pumping anhydrous hydrogen fluoride and hexyl sulfonyl fluoride into a Simons electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the hexyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 8: 100. applying direct current of 4-7V to the mixed solution to start electrolysis, stopping electrifying after the electrolysis is finished, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking the lower layer of brown yellow product as a crude product, and rectifying and separating to obtain the product and a byproduct. Rectifying the by-product after the perfluorohexyl sulfonyl fluoride is separated, and collecting the product with the boiling range of 90-130 ℃ to obtain the fluorocarbon oil.
(2) Preparation of perfluorosulfonyl fluororesin: 280g of perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride) and 150g of the fluorocarbon oil prepared in the step (1) were mixed and then charged into a 1L stainless steel autoclave, and polymerization was conducted under the same conditions as in example 1 to obtain 69.4g of perfluorosulfonyl fluoride resin in the form of a white block. The conversion was 13.3% based on perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride).
The ion exchange capacity of the resulting perfluorosulfonyl fluororesin was measured to be 1.20mmol/g in the same manner as in example 1.
Example 4
(1) Preparation of fluorocarbon oil (nonpolar component of perfluorobutanesulfonyl fluoride byproduct produced by electrolytic fluorination):
pumping anhydrous hydrogen fluoride and butyl sulfonyl fluoride into a Simons electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the butyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 10: 100. applying 5-7V direct current to the mixed solution to start electrolysis, stopping electrifying after the electrolysis is finished, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking the lower layer of brown yellow product as a crude product, and rectifying and separating to obtain the product and a byproduct. Rectifying the by-product after the perfluorobutanesulfonyl fluoride is separated out, and collecting the product with the boiling range of 50-90 ℃ to obtain the fluorocarbon oil.
(2) Preparation of perfluorosulfonyl fluororesin: 150g perfluoro (5-oxa-6-heptene-1-sulfonyl fluoride) (CF2=CFO(CF2)4SO2F) And 150g of the fluorocarbon oil prepared in the step (1) were mixed and then charged into a 1L stainless steel autoclave, and polymerization was carried out under the same conditions as in example 1 to obtain 61.2g of a perfluorosulfonyl fluoride resin in the form of a white block. The conversion was 13.6% based on perfluoro (5-oxa-6-heptene-1-sulfonyl fluoride).
The ion exchange capacity of the resulting perfluorosulfonyl fluororesin was measured to be 0.88 mmol/g in the same manner as in example 1.
Example 5
(1) Preparation of fluorocarbon oil (nonpolar component of perfluorobutanesulfonyl fluoride byproduct produced by electrolytic fluorination): pumping anhydrous hydrogen fluoride and butyl sulfonyl fluoride into a Simons electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the butyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 10: 100. applying 5-7V direct current to the mixed solution to start electrolysis, stopping electrifying after the electrolysis is finished, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking the lower layer of brown yellow product as a crude product, and rectifying and separating to obtain the product and a byproduct. Rectifying the by-product after the perfluorobutanesulfonyl fluoride is separated out, and collecting the product with the boiling range of 50-90 ℃ to obtain the fluorocarbon oil.
(2) Preparation of perfluorosulfonyl fluororesin: 150g perfluoro (4-oxa-5-hexene-1-sulfonyl fluoride) (CF2=CFO(CF2)3SO2F) And 150g of the fluorocarbon oil prepared in the step (1) were mixed and then charged into a 1L stainless steel autoclave, and polymerization was carried out under the same conditions as in example 1 to obtain 62.5g of perfluorosulfonyl fluoride resin in the form of white blocks. The conversion was 13.2% based on perfluoro (4-oxa-5-hexene-1-sulfonyl fluoride).
The ion exchange capacity of the resulting perfluorosulfonyl fluororesin was measured to be 0.96mmol/g in the same manner as in example 1.
Example 6
(1) Preparation of fluorocarbon oil (nonpolar component of perfluorobutanesulfonyl fluoride byproduct produced by electrolytic fluorination): pumping anhydrous hydrogen fluoride and butyl sulfonyl fluoride into a Simons electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the butyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 10: 100. and (3) applying 5-7V direct current to the mixed solution for reaction, stopping electrifying after electrolysis, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking a brown-yellow product at the lower layer as a crude product, and rectifying and separating to obtain a product and a byproduct. Rectifying the by-product after the perfluorobutanesulfonyl fluoride is separated out, and collecting the product with the boiling range of 50-90 ℃ to obtain the fluorocarbon oil.
(2) Preparation of perfluorosulfonyl fluororesin: 150g perfluoro (3-oxa-4-pentene-1-sulfonyl fluoride) (CF2=CFO(CF2)2SO2F) And150g of the fluorocarbon oil prepared in the step (1) was mixed and added into a 1L stainless steel autoclave, and 40mL of dibenzoyl peroxide (structural formula (Ph-COO)2) The fluorocarbon oil solution (mass fraction: 2%) as described above was used as an initiator, and polymerization was carried out under the same conditions as in example 1 to obtain 68.2g of a perfluorosulfonyl fluoride resin in the form of a white block. The conversion was 11.8% based on perfluoro (3-oxa-4-pentene-1-sulfonyl fluoride).
The ion exchange capacity of the resulting perfluorosulfonyl fluororesin was measured to be 0.93mmol/g in the same manner as in example 1.
Example 7
(1) Preparation of fluorocarbon oil (nonpolar component of perfluorobutanesulfonyl fluoride byproduct produced by electrolytic fluorination): pumping anhydrous hydrogen fluoride and butyl sulfonyl fluoride into a Simons electrolytic cell with a nickel polar plate under a nitrogen environment, wherein the weight ratio of the butyl sulfonyl fluoride to the anhydrous hydrogen fluoride is 10: 100. and (3) applying 5-7V direct current to the mixed solution for reaction, stopping electrifying after electrolysis, discharging electrolyte from the bottom of the electrolytic cell, standing for layering, taking a brown-yellow product at the lower layer as a crude product, and rectifying and separating to obtain a product and a byproduct. Rectifying the by-product after the perfluorobutanesulfonyl fluoride is separated out, and collecting the product with the boiling range of 50-90 ℃ to obtain the fluorocarbon oil.
(2) Preparation of perfluorosulfonyl fluororesin: 150g perfluoro (4, 7-dioxa-5-methyl-8-nonene-1-sulfonyl fluoride) (CF2=CFOCF2CF(CF3)O(CF2)3SO2F) Mixing with 150g of the fluorocarbon oil prepared in the step (1), adding the mixture into a 1L stainless steel high-pressure reaction kettle, and adding 40mL of azodiisobutyronitrile (with a structural formula of (CH)3)2C(CN)-N=N-C(CN)(CH3)2) The fluorocarbon oil solution (mass fraction: 2%) as described above was used as an initiator, and polymerization was carried out under the same conditions as in example 1 to obtain 61.8g of a perfluorosulfonyl fluoride resin in the form of a white block. The conversion was 16.8% based on perfluoro (4, 7-dioxa-5-methyl-8-nonene-1-sulfonyl fluoride).
The ion exchange capacity of the resulting perfluorosulfonyl fluororesin was measured to be 0.82mmol/g in the same manner as in example 1.
Comparative example 1
The same procedures used in example 1 were repeated except that 1, 1, 2-trifluoro-trichloroethane was used in place of the fluorocarbon oil to give 33.0g of perfluorosulfonyl fluoride resin in the form of white particles. The conversion was 8.3% based on perfluoro (4-methyl-3, 6-dioxa-7-octene-1-sulfonyl fluoride).
The ion exchange capacity of the perfluorosulfonyl fluororesin was measured to be 0.85mmol/g in the same manner as in example 1.
Claims (7)
1. A preparation method of perfluorosulfonyl fluororesin is characterized in that fluorocarbon oil is used as a solvent, tetrafluoroethylene and sulfonyl fluoride perfluoroalkyl vinyl ether are used as raw materials to carry out copolymerization reaction, and perfluorosulfonyl fluoride resin is prepared; wherein the fluorocarbon oil is selected from one or a mixture of more of nonpolar components in a byproduct of producing perfluorobutanesulfonyl fluoride through electrolytic fluorination, nonpolar components in a byproduct of producing perfluorohexylsulfonyl fluoride through electrolytic fluorination and nonpolar components in a byproduct of producing perfluorooctylsulfonyl fluoride through electrolytic fluorination; wherein the nonpolar component in the byproduct of the production of the perfluorobutanesulfonyl fluoride by the electrolytic fluorination is a product with a boiling range of 50-90 ℃ separated from the byproduct by rectification; the nonpolar component in the byproduct of producing the perfluorohexyl sulfonyl fluoride by the electrolytic fluorination is a product with a boiling range of 90-130 ℃ separated from the byproduct by rectification; the nonpolar component in the byproduct of the production of perfluorooctylsulfonyl fluoride by the electrolytic fluorination is a product with the boiling range of 130-180 ℃ which is separated from the byproduct by rectification.
2. The method according to claim 1, wherein the specific reaction process for obtaining the by-product by the electrolytic fluorination is as follows: the method comprises the steps of taking alkyl sulfonyl fluoride and anhydrous hydrogen fluoride as raw materials, placing the raw materials in a Simons electrolytic tank, electrolyzing the raw material mixture by using low-voltage direct current DC 4-8V, and obtaining a byproduct in the process of producing perfluoroalkyl sulfonyl fluoride.
3. The preparation method according to claim 1, wherein the weight ratio of the fluorocarbon oil to the sulfonyl fluoride-based perfluoroalkyl vinyl ether is 1: 0.1-5.
4. The preparation method according to claim 3, wherein the fluorocarbon oil and the sulfonyl fluoride-based perfluoroalkyl vinyl ether are mixed in a mass ratio of 1: 0.5 to 2.
5. The production method according to claim 1, wherein the sulfonyl fluoride-based perfluoroalkyl vinyl ether is 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 an initiator is further added to the copolymerization reaction system, and the initiator is selected from one of perfluorobutyryl peroxide, dibenzoyl peroxide and azobisisobutyronitrile.
7. The production method according to claim 1, wherein the perfluorosulfonyl fluororesin is produced by a specific method comprising:
(1) mixing fluorocarbon oil and sulfonyl fluoride perfluoroalkyl vinyl ether, sealing, vacuumizing, and charging tetrafluoroethylene;
(2) adding an initiator into a reaction system, stirring, heating, starting a polymerization reaction, supplementing tetrafluoroethylene to maintain pressure, and reacting to obtain a polymer solution;
(3) adding a poor solvent into the polymer solution to precipitate the copolymer, and filtering, washing and drying to obtain the perfluorosulfonyl fluororesin.
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