CN117586107A - Catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer - Google Patents
Catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer Download PDFInfo
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- CN117586107A CN117586107A CN202311543187.5A CN202311543187A CN117586107A CN 117586107 A CN117586107 A CN 117586107A CN 202311543187 A CN202311543187 A CN 202311543187A CN 117586107 A CN117586107 A CN 117586107A
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- Prior art keywords
- methyl
- fluorine
- parts
- ether
- perfluorobutyl ether
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- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229940104873 methyl perfluorobutyl ether Drugs 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 38
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000013638 trimer Substances 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 32
- FSDLLONBRLBIBL-UHFFFAOYSA-N 1,3,3,3-tetrafluoro-1-methoxy-2-(trifluoromethyl)prop-1-ene Chemical compound COC(F)=C(C(F)(F)F)C(F)(F)F FSDLLONBRLBIBL-UHFFFAOYSA-N 0.000 claims abstract description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011737 fluorine Substances 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000003622 immobilized catalyst Substances 0.000 claims abstract description 8
- 239000000919 ceramic Substances 0.000 claims description 46
- 229940070527 tourmaline Drugs 0.000 claims description 46
- 229910052613 tourmaline Inorganic materials 0.000 claims description 46
- 239000011032 tourmaline Substances 0.000 claims description 46
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 42
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 229910052787 antimony Inorganic materials 0.000 claims description 16
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 16
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910021645 metal ion Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000003446 ligand Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- -1 1-vinyl-3-ethylimidazole hexafluorophosphate Chemical compound 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- ZXWNFKKVGPYFRR-UHFFFAOYSA-N 3-ethenyl-2-methylpyridine Chemical compound CC1=NC=CC=C1C=C ZXWNFKKVGPYFRR-UHFFFAOYSA-N 0.000 claims description 7
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- VXQOFNJETKUWLT-UHFFFAOYSA-N [dimethoxy(methyl)silyl]methanethiol Chemical compound CO[Si](C)(CS)OC VXQOFNJETKUWLT-UHFFFAOYSA-N 0.000 claims description 2
- RPCGDCYHXWVDNM-UHFFFAOYSA-N [dimethoxy(methyl)silyl]oxymethanethiol Chemical compound CO[Si](C)(OC)OCS RPCGDCYHXWVDNM-UHFFFAOYSA-N 0.000 claims description 2
- OSLCCLSWGZXIPF-UHFFFAOYSA-N [dimethoxy(propyl)silyl]methanethiol Chemical compound CCC[Si](CS)(OC)OC OSLCCLSWGZXIPF-UHFFFAOYSA-N 0.000 claims description 2
- FMJPIPZUGDGFNS-UHFFFAOYSA-N [ethyl(dimethoxy)silyl]methanethiol Chemical compound CC[Si](CS)(OC)OC FMJPIPZUGDGFNS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 5
- DFEYYRMXOJXZRJ-UHFFFAOYSA-N sevoflurane Chemical compound FCOC(C(F)(F)F)C(F)(F)F DFEYYRMXOJXZRJ-UHFFFAOYSA-N 0.000 abstract 1
- 229960002078 sevoflurane Drugs 0.000 abstract 1
- PGISRKZDCUNMRX-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-(trifluoromethoxy)butane Chemical compound FC(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PGISRKZDCUNMRX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XDIDQEGAKCWQQP-OWOJBTEDSA-N (e)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C(\Cl)=C(/Cl)C(F)(F)F XDIDQEGAKCWQQP-OWOJBTEDSA-N 0.000 description 2
- CAEGINLAOUNGOL-UHFFFAOYSA-N 1,1,2,3,3,4,4,4-octachlorobut-1-ene Chemical compound ClC(Cl)=C(Cl)C(Cl)(Cl)C(Cl)(Cl)Cl CAEGINLAOUNGOL-UHFFFAOYSA-N 0.000 description 2
- DJXNLVJQMJNEMN-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F DJXNLVJQMJNEMN-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- KUGBQWBWWNPMIT-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluoropentan-1-ol Chemical compound CC(F)(F)C(F)(F)C(F)(F)C(O)(F)F KUGBQWBWWNPMIT-UHFFFAOYSA-N 0.000 description 1
- CSUFEOXMCRPQBB-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropan-1-ol Chemical compound CC(F)(F)C(O)(F)F CSUFEOXMCRPQBB-UHFFFAOYSA-N 0.000 description 1
- MAXQCYDCBHPIAB-UHFFFAOYSA-N 1,1,2,3,3-pentachloroprop-1-ene Chemical compound ClC(Cl)C(Cl)=C(Cl)Cl MAXQCYDCBHPIAB-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical group CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K antimony trifluoride Chemical compound F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- KTJUNCYQALUJRL-UHFFFAOYSA-N dimethoxymethylsilylmethanethiol Chemical group COC(OC)[SiH2]CS KTJUNCYQALUJRL-UHFFFAOYSA-N 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229940104872 methyl perfluoroisobutyl ether Drugs 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000006336 tetrafluoro alkyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- WZCZNEGTXVXAAS-UHFFFAOYSA-N trifluoromethanol Chemical compound OC(F)(F)F WZCZNEGTXVXAAS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/22—Preparation of ethers by reactions not forming ether-oxygen bonds by introduction of halogens; by substitution of halogen atoms by other halogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
- B01J31/1633—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups covalent linkages via silicon containing groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer, and belongs to the technical field of preparation of hydrofluoroether. Putting sevoflurane, perfluorocarbon and immobilized catalyst into a fluorination reaction kettle, and introducing fluorine-nitrogen mixed gas to carry out fluorination reaction; when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine reaches a set proportion, terminating the reaction, removing tail gas, filtering and rectifying to obtain the methyl perfluorobutyl ether. The method adopts hexafluoropropylene trimer as solvent, can be recycled, is environment-friendly, has high product purity, and has the reaction yield of more than 75 percent.
Description
Technical Field
The invention relates to the technical field of preparation of hydrofluoroether, in particular to a catalytic method for preparing methyl perfluorobutyl ether by hexafluoropropylene trimerization.
Background
Methyl perfluorobutyl ether, english name METHYL PERFLUOROBUTYL ETHER, alias: methyl nonafluorobutyl ether and methyl perfluoro isobutyl ether are colorless, odorless, nontoxic, noncorrosive and nonflammable liquid substances. It is a fluoroether solvent, which is soluble in many components, is considered to have good lubricity, and is suitable for use as a solvent for oily formulations. The perfluoro isobutyl methyl ether is used as a precise cleaning agent in the fields of printed circuit board cleaning, metal and parts cleaning, liquid crystal display cleaning, precise cleaning (including electronic devices, optical parts, aerospace equipment devices, medical instrument parts, plastic parts and the like) and the like, and is used for removing grease, wax, rosin soldering flux, fingerprint sweat stains, particles and the like. The perfluor isobutyl methyl ether has the performance closest to CFCs, the ODP value of zero and the GWP value of 320, and is an ideal substitute for solvents of ozone-layer-consuming substances such as CFC-113, trichloroethane, carbon tetrachloride and the like. Thus, the market demand for perfluorobutyl methyl ether is great.
Patent number: CN201010607067.3 is prepared from 20-100 parts of alcohol as raw material, wherein the alcohol is one of methanol, ethanol, propanol, trifluoromethanol, tetrafluoropropanol and octafluoropentanol, 34-108 parts of fluorine-containing olefin is continuously added in the presence of 1-6 parts of strong base catalyst, the reaction is carried out at 110-180 ℃, the reaction pressure is 0.6-1.2 MPa, the reaction time is 1-5 h, and the target product is obtained after rectification and separation.
Patent number: CN202010672282.5 relates to a method for synthesizing perfluorobutyl methyl ether, which belongs to the field of organic chemical synthesis. A method for synthesizing perfluorobutyl methyl ether is characterized in that: the first step: carbon tetrachloride (molecular formula CCl) 4 ) With pentachloropropene (formula CCl) 3 CH＝CCl 2 ) To produce the nonachlorobutane (molecular formula CCl) under the action of a telomerization catalyst 3 CH(CCl 3 )CCl 3 ). And a second step of: production of perchlorobutene (CCl) by gas-phase catalytic dehydrochlorination of nonachlorobutane with catalyst 3 C＝(CCl 2 )CCl 3 ). And a third step of: the perchlorobutene and Anhydrous Hydrogen Fluoride (AHF) react with a catalyst to generate hexafluoro-dichloro butene (CF3C= (CCl) 2 )CF 3 ). Fourth step: telogenating hexafluoro-dichloro-butene with methanol (CH 3 OH) and triethylamine to obtain hexafluoro-chloro-isopropenyl methyl ether (CH) 3 O(Cl)C＝C(CF 3 ) 2 ). Fifth step: gas phase catalytic synthesis of perfluorobutyl methyl ether (CH) by hexafluoro-chloro isopropenyl methyl ether, chlorine and anhydrous hydrogen fluoride under the action of catalyst 3 O(F 2 )C-C(CF 3 ) 2 )。
However, in the prior disclosed scheme, the preparation of the hydrofluoroether has the disadvantages of long reaction time, high temperature, high production cost, and insufficient product yield and purity.
In view of this, the present invention proposes a catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer.
Disclosure of Invention
The invention provides a catalytic method for preparing methyl perfluorobutyl ether by hexafluoropropylene trimerization, which aims to solve at least one technical problem in the background art, and belongs to the technical field of preparation of hydrofluoroether.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: according to the weight portions, 100 to 300 portions of heptafluoroisobutylene methyl ether and 300 to 500 portions of perfluorocarbon are put into a fluorination reaction kettle, 30 to 50 portions of supported catalyst are started to be stirred, the reaction kettle is cooled, and fluorine-nitrogen mixed gas is slowly introduced for carrying out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
In the above technical solution, further perfluorocarbon is hexafluoropropylene trimer.
In the technical scheme, the temperature of the reaction kettle is further between-45 and 5 ℃.
In the technical scheme, the concentration of fluorine gas in the fluorine-nitrogen mixed gas is 5-15wt%.
In the technical scheme, the further set molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas is 1:0.6-0.9.
In the technical scheme, the further reaction is continued for 10-30 minutes after the introduction of the fluorine-nitrogen mixed gas is stopped.
In the above technical scheme, the further supported catalyst is a tourmaline ceramic ball supported organic metal antimony fluorination catalyst, and the preparation method thereof is as follows:
s1: according to the mass parts, 5-12 parts of antimony pentachloride is dissolved in 100-150 parts of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;
s2: 13-26 parts of 3-vinyl-2-methylpyridine, 120-200 parts of N-methyl-2-pyrrolidone and 3-6 parts of hydrochloric acid with the mass percent content of 20-30% are added into a stirring kettle, the stirring is carried out for 50-100min at 70-80 ℃, then the metal ion solution prepared by S1 is poured into the ligand solution for mixing, and then the mixture is added into a hydrothermal reaction kettle for reacting for 1-4 hours at 70-85 ℃ to obtain a vinyl fluorine-containing organic metal intermediate;
s3: adding 50-100 parts of tourmaline ceramic ball treated by mercaptosilane, 0.05-0.4 part of 1-vinyl-3-ethylimidazole hexafluorophosphate (1034364-43-6), 7-11 parts of triethylamine, 600-800 parts of N-methyl-2-pyrrolidone, stirring at 70-80 ℃ for 40-70 minutes, adding the vinyl fluorine-containing organic metal intermediate prepared by S2, stirring at 70-80 ℃ for 40-60 hours, filtering, and vacuum drying at 50-80 ℃ for 12-36 hours to obtain the fluoride catalyst of the tourmaline ceramic ball loaded with organic metal antimony.
In the above technical scheme, the preparation method of the tourmaline ceramic ball treated by the mercaptosilane further comprises the following steps:
according to the mass portion, 150-240 parts of tourmaline ceramic ball is taken and dissolved in 1000-1500 parts of water, 4-7 parts of mercaptosilane is added, the mixture reacts for 40-150 minutes at 30-45 ℃, and the mixture is filtered and dried to prepare the mercaptosilane treated tourmaline ceramic ball.
In the above technical scheme, the mercapto silane is further selected from one or more of mercapto propyl trimethoxy silane, mercapto propyl dimethoxy methyl silane, mercapto methyl trimethoxy silane, mercapto methyl dimethoxy methyl silane and mercapto ethyl dimethoxy methyl silane.
In the above technical scheme, the further supported catalyst can be reused.
The preparation reaction mechanism of the immobilized catalyst comprises the following steps:
the catalyst adopts: the sulfhydryl group of tourmaline ceramic ball treated by sulfhydryl silane firstly carries out addition reaction with 1-vinyl-3-ethylimidazole hexafluorophosphate, then carries out addition reaction of sulfhydryl-ethylene with vinyl fluorine-containing organic metal intermediate, and obtains the tourmaline ceramic ball supported organic metal antimony fluorination catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method has the advantages of simple process flow, avoiding tedious operation, shortening the reaction time and reducing the reaction temperature, thereby improving the production efficiency.
(2) According to the method, hexafluoropropylene trimer is used as a solvent, fluorine gas and heptafluoroisobutylene methyl ether are used for preparing methyl perfluorobutyl ether, and the hexafluoropropylene trimer can be recycled, so that the method is environment-friendly.
(3) The methyl perfluoro butyl ether product prepared by the method has high purity and the reaction yield can reach more than 75 percent.
(4) The tourmaline ceramic ball loaded organic metal antimony fluorination catalyst can be conveniently separated, and meanwhile, the tetrafluoroalkyl group and reactants of the tourmaline ceramic ball have good compatibility, the structure is beneficial to enriching the heptafluoroisobutylene methyl ether on the surface and micropores of the catalyst, the catalytic effect can be effectively improved, and the reaction time is shortened.
On the basis of conforming to the common knowledge in the art, the above preferred conditions can be mutually combined to obtain the preferred embodiments of the invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, without limiting the invention to these specific embodiments. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1 ]
A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: putting 100g of heptafluoroisobutylene methyl ether and 30g of perfluorocarbon into a fluorination reaction kettle, and 30g of immobilized catalyst, starting the reaction kettle to stir, cooling the reaction kettle, and slowly introducing fluorine-nitrogen mixed gas to carry out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
The perfluorocarbon in this embodiment is hexafluoropropylene trimer.
The reactor temperature in this particular example was-45 ℃.
The concentration of fluorine gas in the fluorine-nitrogen mixed gas in this embodiment is 5wt%.
The molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas in the specific example is set to be 1:0.6.
In this embodiment, the reaction is continued for 30 minutes after stopping the introduction of the fluorine-nitrogen mixed gas.
The supported catalyst in this embodiment is a tourmaline ceramic ball supported organic metal antimony fluorination catalyst, and the preparation method thereof is as follows:
s1: 5g of antimony pentachloride is dissolved in 100g N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;
s2: 13g of 3-vinyl-2-methylpyridine, 120g N-methyl-2-pyrrolidone and 3g of hydrochloric acid with the mass percent of 20% are added into a stirring kettle, the stirring is carried out for 50min at 70 ℃, then the metal ion solution prepared by S1 is poured into a ligand solution for mixing, and then the ligand solution is added into a hydrothermal reaction kettle for reacting for 1 hour at 70 ℃ to obtain a vinyl fluorine-containing organic metal intermediate;
s3: 50g of tourmaline ceramic ball treated by mercaptosilane, 0.1g of 1-vinyl-3-ethylimidazole hexafluorophosphate (1034364-43-6), 7g of triethylamine, 600g N-methyl-2-pyrrolidone and stirring for 40 minutes at 70 ℃ are added in a reaction kettle under the nitrogen atmosphere, then the vinyl fluorine-containing organic metal intermediate prepared by S2 is added, stirring is carried out for 40 hours at 70 ℃, filtering is carried out, and then vacuum drying is carried out for 12 hours at 50 ℃ to obtain the tourmaline ceramic ball supported organic metal antimony fluorination catalyst.
The preparation method of the tourmaline ceramic ball treated by the mercaptosilane in the specific embodiment comprises the following steps:
150g tourmaline ceramic ball is dissolved in 1000g water, 4g mercaptosilane is added, and the mixture is reacted for 40 minutes at 30 ℃, filtered and dried to prepare the tourmaline ceramic ball treated by mercaptosilane.
The mercaptosilane in this particular embodiment is selected from mercaptopropyl trimethoxysilane.
Through analytical calculation, the yield of the methyl perfluorobutyl ether prepared by the method is 83.8%, and the purity of the product is 99.94%.
Example 2 ]
A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: 200g of heptafluoroisobutylene methyl ether, 400g of perfluorocarbon and 40g of immobilized catalyst are put into a fluorination reaction kettle, the reaction kettle is started to be stirred, the temperature of the reaction kettle is reduced, and fluorine-nitrogen mixed gas is slowly introduced for carrying out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
The perfluorocarbon in this embodiment is hexafluoropropylene trimer.
The reactor temperature in this particular example was-15 ℃.
The concentration of fluorine gas in the fluorine-nitrogen mixed gas in this embodiment is 10wt%.
The molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas in the specific example is set to be 1:0.8.
In this embodiment, the reaction is continued for 20 minutes after stopping the introduction of the fluorine-nitrogen mixed gas.
The supported catalyst in this embodiment is a tourmaline ceramic ball supported organic metal antimony fluorination catalyst, and the preparation method thereof is as follows:
s1: 9g of antimony pentachloride was dissolved in 125g of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;
s2: 19g of 3-vinyl-2-methylpyridine, 160g N-methyl-2-pyrrolidone and 4.5g of hydrochloric acid with the mass percent content of 25% are added into a stirring kettle, the stirring is carried out for 75 minutes at the temperature of 75 ℃, then the metal ion solution prepared by S1 is poured into a ligand solution for mixing, and then the ligand solution is added into a hydrothermal reaction kettle for reaction for 3 hours at the temperature of 78 ℃ to obtain a vinyl fluorine-containing organic metal intermediate;
s3: under the nitrogen atmosphere, 75g of tourmaline ceramic ball treated by mercaptosilane, 0.2g of 1-vinyl-3-ethylimidazole hexafluorophosphate (1034364-43-6), 9g of triethylamine, 700g of N-methyl-2-pyrrolidone and 75g of stirring for 55 minutes, then adding the vinyl fluorine-containing organic metal intermediate prepared by S2, stirring for 50 hours at 75 ℃, filtering, and then drying in vacuum for 24 hours at 65 ℃ to obtain the tourmaline ceramic ball supported organic metal antimony fluorination catalyst.
The preparation method of the tourmaline ceramic ball treated by the mercaptosilane in the specific embodiment comprises the following steps:
dissolving 195g tourmaline ceramic ball in 1250g water, adding 6g mercaptosilane, reacting at 35 ℃ for 90 minutes, filtering, and drying to obtain mercaptosilane treated tourmaline ceramic ball.
The mercaptosilane in this particular embodiment is selected from mercaptopropyl dimethoxy methylsilane.
Through analytical calculation, the yield of the methyl perfluorobutyl ether prepared by the method is 87.5%, and the purity of the product is 99.97%.
Example 3 ]
A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: 300g of heptafluoroisobutylene methyl ether and 500g of perfluorocarbon are put into a fluorination reaction kettle, 50g of immobilized catalyst is put into the reaction kettle for stirring, the reaction kettle is cooled, and fluorine-nitrogen mixed gas is slowly introduced for carrying out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
The perfluorocarbon in this embodiment is hexafluoropropylene trimer.
The reactor temperature in this particular example was 5 ℃.
The fluorine gas concentration in the fluorine-nitrogen mixed gas in this embodiment is 15wt%.
The molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas in the specific example is set to be 1:0.9.
In this embodiment, the reaction was continued for 10 minutes after stopping the introduction of the fluorine-nitrogen mixed gas.
The supported catalyst in this embodiment is a tourmaline ceramic ball supported organic metal antimony fluorination catalyst, and the preparation method thereof is as follows:
s1: 12g of antimony pentachloride was dissolved in 150g of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;
s2: 26g of 3-vinyl-2-methylpyridine, 200g N-methyl-2-pyrrolidone and 6g of hydrochloric acid with the mass percent of 30% are added into a stirring kettle, stirring is carried out for 100min at 80 ℃, then the metal ion solution prepared by S1 is poured into a ligand solution for mixing, then the ligand solution is added into a hydrothermal reaction kettle, and the mixture is reacted for 4 hours at 85 ℃ to obtain a vinyl fluorine-containing organic metal intermediate;
s3: under nitrogen atmosphere, adding 100g of tourmaline ceramic ball treated by mercaptosilane, 0.4g of 1-vinyl-3-ethylimidazole hexafluorophosphate (1034364-43-6), 11g of triethylamine, 800g of N-methyl-2-pyrrolidone, stirring at 80 ℃ for 70 minutes, adding the vinyl fluorine-containing organic metal intermediate prepared by S2, stirring at 80 ℃ for 60 hours, filtering, and then vacuum drying at 80 ℃ for 36 hours to obtain the tourmaline ceramic ball supported organic metal antimony fluorination catalyst.
The preparation method of the tourmaline ceramic ball treated by the mercaptosilane in the specific embodiment comprises the following steps:
240g tourmaline ceramic ball is taken and dissolved in 1500g water, 7g mercaptosilane is added, and the mixture reacts for 150 minutes at 45 ℃, and then the mixture is filtered and dried to prepare the tourmaline ceramic ball treated by mercaptosilane.
The mercaptosilane in this particular embodiment is selected from mercaptomethyldimethoxymethylsilane.
Through analytical calculation, the yield of the methyl perfluorobutyl ether prepared by the method is 88.0%, and the purity of the product is 99.98%.
Comparative example 1 ]
A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
a catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: putting 100g of heptafluoroisobutylene methyl ether, 30g of perfluorocarbon and 30g of antimony fluoride into a fluorination reaction kettle, starting the reaction kettle for stirring, cooling the reaction kettle, and slowly introducing fluorine-nitrogen mixed gas for carrying out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
The perfluorocarbon in this embodiment is hexafluoropropylene trimer.
The reactor temperature in this particular example was-45 ℃.
The concentration of fluorine gas in the fluorine-nitrogen mixed gas in this embodiment is 5wt%.
The molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas in the specific example is set to be 1:0.6.
In this embodiment, the reaction is continued for 30 minutes after stopping the introduction of the fluorine-nitrogen mixed gas.
Through analytical calculation, the yield of the methyl perfluorobutyl ether prepared by the method is 69.1%, and the purity of the product is 99.88%.
Comparative example 2 ]
A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: putting 100g of heptafluoroisobutylene methyl ether and 30g of perfluorocarbon into a fluorination reaction kettle, and 30g of immobilized catalyst, starting the reaction kettle to stir, cooling the reaction kettle, and slowly introducing fluorine-nitrogen mixed gas to carry out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
The perfluorocarbon in this embodiment is hexafluoropropylene trimer.
The reactor temperature in this particular example was-45 ℃.
The concentration of fluorine gas in the fluorine-nitrogen mixed gas in this embodiment is 5wt%.
The molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas in the specific example is set to be 1:0.6.
In this embodiment, the reaction is continued for 30 minutes after stopping the introduction of the fluorine-nitrogen mixed gas.
The supported catalyst in this embodiment is a tourmaline ceramic ball supported organic metal antimony fluorination catalyst, and the preparation method thereof is as follows:
s1: 5g of antimony pentachloride is dissolved in 100g N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;
s2: 13g of 3-vinyl-2-methylpyridine, 120g N-methyl-2-pyrrolidone and 3g of hydrochloric acid with the mass percent of 20% are added into a stirring kettle, the stirring is carried out for 50min at 70 ℃, then the metal ion solution prepared by S1 is poured into a ligand solution for mixing, and then the ligand solution is added into a hydrothermal reaction kettle for reacting for 1 hour at 70 ℃ to obtain a vinyl fluorine-containing organic metal intermediate;
s3: 50g of tourmaline ceramic ball treated by mercaptosilane, 7g of triethylamine, 600g N-methyl-2-pyrrolidone and the like are added into a reaction kettle under the nitrogen atmosphere, stirred for 40 minutes at 70 ℃, then the vinyl fluorine-containing organic metal intermediate prepared by S2 is added, stirred for 40 hours at 70 ℃, filtered, and then vacuum dried for 12 hours at 50 ℃ to obtain the tourmaline ceramic ball supported organic metal antimony fluorination catalyst.
The preparation method of the tourmaline ceramic ball treated by the mercaptosilane in the specific embodiment comprises the following steps:
150g tourmaline ceramic ball is dissolved in 1000g water, 4g mercaptosilane is added, and the mixture is reacted for 40 minutes at 30 ℃, filtered and dried to prepare the tourmaline ceramic ball treated by mercaptosilane.
The mercaptosilane in this particular embodiment is selected from mercaptopropyl trimethoxysilane.
Through analysis and calculation, the yield of the methyl perfluorobutyl ether prepared by the method is 78.3%, and the purity of the product is 99.92%.
Comparative example 3 ]
A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: putting 100g of heptafluoroisobutylene methyl ether and 30g of perfluorocarbon into a fluorination reaction kettle, and 30g of immobilized catalyst, starting the reaction kettle to stir, cooling the reaction kettle, and slowly introducing fluorine-nitrogen mixed gas to carry out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
The perfluorocarbon in this embodiment is hexafluoropropylene trimer.
The reactor temperature in this particular example was-45 ℃.
The concentration of fluorine gas in the fluorine-nitrogen mixed gas in this embodiment is 5wt%.
The molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas in the specific example is set to be 1:0.6.
In this embodiment, the reaction is continued for 30 minutes after stopping the introduction of the fluorine-nitrogen mixed gas.
The supported catalyst in this embodiment is a tourmaline ceramic ball supported organic metal antimony fluorination catalyst, and the preparation method thereof is as follows:
s1: 5g of antimony pentachloride is dissolved in 100g N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;
s2: 13g of 3-vinyl-2-methylpyridine, 120g N-methyl-2-pyrrolidone and 3g of hydrochloric acid with the mass percent of 20% are added into a stirring kettle, the stirring is carried out for 50min at 70 ℃, then the metal ion solution prepared by S1 is poured into a ligand solution for mixing, and then the ligand solution is added into a hydrothermal reaction kettle for reacting for 1 hour at 70 ℃ to obtain a vinyl fluorine-containing organic metal intermediate;
s3: 50g of tourmaline ceramic ball treated by mercaptosilane, 0.1g of 1-vinyl-3-ethylimidazole hexafluorophosphate (1034364-43-6), 7g of triethylamine, 600g N-methyl-2-pyrrolidone and stirring for 40 minutes at 70 ℃ are added in a reaction kettle under the nitrogen atmosphere, then the vinyl fluorine-containing organic metal intermediate prepared by S2 is added, stirring is carried out for 40 hours at 70 ℃, filtering is carried out, and then vacuum drying is carried out for 12 hours at 50 ℃ to obtain the tourmaline ceramic ball supported organic metal antimony fluorination catalyst.
The preparation method of the tourmaline ceramic ball treated by the mercaptosilane in the specific embodiment comprises the following steps:
150g tourmaline ceramic ball is dissolved in 1000g water, 4g mercaptosilane is added, and the mixture is reacted for 40 minutes at 30 ℃, filtered and dried to prepare the tourmaline ceramic ball treated by mercaptosilane.
The mercaptosilane in this particular embodiment is selected from mercaptopropyl trimethoxysilane.
Through analytical calculation, the yield of the methyl perfluorobutyl ether prepared by the method is 77.9%, and the purity of the product is 99.91%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer is characterized in that: the method comprises the following operation steps:
s1: according to the weight portions, 100 to 300 portions of heptafluoroisobutylene methyl ether and 300 to 500 portions of perfluorocarbon are put into a fluorination reaction kettle, 30 to 50 portions of supported catalyst are started to be stirred, the reaction kettle is cooled, and fluorine-nitrogen mixed gas is slowly introduced for carrying out fluorination reaction;
s2: when the mole ratio of the heptafluoroisobutylene methyl ether to the introduced fluorine gas reaches a set proportion, stopping introducing the fluorine-nitrogen mixed gas, keeping the temperature for continuous reaction for a period of time, heating the reaction kettle to room temperature, removing tail gas, filtering the reaction liquid, and rectifying to obtain the methyl perfluorobutyl ether.
2. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as defined in claim 1, wherein: the perfluorocarbon is hexafluoropropylene trimer.
3. The catalytic method for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer according to claim 1, wherein the temperature of the reaction kettle is-45-5 ℃.
4. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as defined in claim 1, wherein: the concentration of fluorine gas in the fluorine-nitrogen mixed gas is 5-15wt%.
5. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as defined in claim 1, wherein: the set molar ratio of the heptafluoroisobutenyl methyl ether to the fluorine gas is 1:0.6-0.9.
6. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as defined in claim 1, wherein: and stopping introducing the fluorine-nitrogen mixed gas, and continuing the reaction for 10-30 minutes.
7. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as defined in claim 1, wherein: the immobilized catalyst is a tourmaline ceramic ball supported organic metal antimony fluorination catalyst, and the preparation method comprises the following steps:
s1: according to the mass parts, 5-12 parts of antimony pentachloride is dissolved in 100-150 parts of N-methyl-2-pyrrolidone (DMF) to prepare a metal ion solution;
s2: 13-26 parts of 3-vinyl-2-methylpyridine, 120-200 parts of N-methyl-2-pyrrolidone and 3-6 parts of hydrochloric acid with the mass percent content of 20-30% are added into a stirring kettle, the stirring is carried out for 50-100min at 70-80 ℃, then the metal ion solution prepared by S1 is poured into the ligand solution for mixing, and then the mixture is added into a hydrothermal reaction kettle for reacting for 1-4 hours at 70-85 ℃ to obtain a vinyl fluorine-containing organic metal intermediate;
s3: adding 50-100 parts of tourmaline ceramic ball treated by mercaptosilane, 0.05-0.4 part of 1-vinyl-3-ethylimidazole hexafluorophosphate (1034364-43-6), 7-11 parts of triethylamine, 600-800 parts of N-methyl-2-pyrrolidone, stirring at 70-80 ℃ for 40-70 minutes, adding the vinyl fluorine-containing organic metal intermediate prepared by S2, stirring at 70-80 ℃ for 40-60 hours, filtering, and vacuum drying at 50-80 ℃ for 12-36 hours to obtain the fluoride catalyst of the tourmaline ceramic ball loaded with organic metal antimony.
8. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as defined in claim 7, wherein: the preparation method of the tourmaline ceramic ball treated by the mercaptosilane comprises the following steps:
according to the mass portion, 150-240 parts of tourmaline ceramic ball is taken and dissolved in 1000-1500 parts of water, 4-7 parts of mercaptosilane is added, the mixture reacts for 40-150 minutes at 30-45 ℃, and the mixture is filtered and dried to prepare the mercaptosilane treated tourmaline ceramic ball.
9. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as claimed in claim 8, wherein: the mercapto silane is one or more selected from mercapto propyl trimethoxy silane, mercapto propyl dimethoxy methyl silane, mercapto methyl trimethoxy silane, mercapto methyl dimethoxy methyl silane and mercapto ethyl dimethoxy methyl silane.
10. A catalytic process for preparing methyl perfluorobutyl ether from hexafluoropropylene trimer as defined in claim 7, wherein: the supported catalyst is reusable.
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