CN111995502A - Method for synthesizing perfluorobutyl methyl ether - Google Patents
Method for synthesizing perfluorobutyl methyl ether Download PDFInfo
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- CN111995502A CN111995502A CN202010672282.5A CN202010672282A CN111995502A CN 111995502 A CN111995502 A CN 111995502A CN 202010672282 A CN202010672282 A CN 202010672282A CN 111995502 A CN111995502 A CN 111995502A
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- catalyst
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- methyl ether
- hydrogen fluoride
- nonachlorobutane
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- 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 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 27
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- 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 claims abstract description 25
- 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 claims abstract description 24
- 230000009471 action Effects 0.000 claims abstract description 22
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 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 claims abstract description 7
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 description 14
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000003213 activating effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000003682 fluorination reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910021583 Cobalt(III) fluoride Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- 229910021065 Pd—Fe Inorganic materials 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- -1 methoxyl compound Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Inorganic materials [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Inorganic materials [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- YGJMWVCEUNWDOU-UHFFFAOYSA-N methyl carbonofluoridate Chemical compound COC(F)=O YGJMWVCEUNWDOU-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- 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
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing perfluorobutyl methyl ether, belonging to the field of organic chemical synthesis. A method for synthesizing perfluorobutyl methyl ether is characterized in that: the first step is as follows: carbon tetrachloride (molecular formula CCl)4) With pentachloropropene (molecular formula CCl)3CH＝CCl2) Generating nonachlorobutane (molecular formula CCl) under the action of telomerization catalyst3CH(CCl3)CCl3). The second step is that: the nonachlorobutane is dehydrochlorinated in a gas phase catalysis way under the action of a catalyst to generate perchlorobutene (CCl)3C＝(CCl2)CCl3). The third step: the perchloro-butene and Anhydrous Hydrogen Fluoride (AHF) generate hexafluoro-dichlorobutene (CF) under the action of a catalyst3C＝(CCl2)CF3). The fourth step: hexafluorodichlorobutene with methanol (CH)3OH) and potassium hydroxide to generate hexafluoro-chloro-isopropenyl methyl ether (CH)3O(Cl)C＝C(CF3)2). The fifth step: hexafluoro-1Synthesis of perfluorobutyl methyl ether (CH) by gas phase catalysis of chlorine isopropenyl methyl ether, chlorine and anhydrous hydrogen fluoride under the action of catalyst3O(F2)C‑C(CF3)2)。
The raw materials are cheap and convenient to obtain; the catalyst has good stability and long service life; the product is simple to separate and purify; is easy for industrialized production.
Description
Technical Field
The invention discloses a method for synthesizing perfluorobutyl methyl ether, and relates to a method for synthesizing perfluorobutyl methyl ether by an easily industrialized method.
Background
Perfluorobutyl methyl ether (CAS: 163702-08-7, 1,1,2,3,3, 3-hexafluoro-1-methoxy-2- (trifluoromethyl) propane or HFE7100) is a general-purpose nonflammable liquid, and has the characteristics of excellent dielectric property, wide boiling point range, superior material compatibility and thermal stability, low Global Warming Potential (GWP) and zero Ozone Depletion Potential (ODP), and excellent environmental performance. The perfluorobutyl methyl ether has high industrial value, is an industrial raw material with wide application, and downstream products of the perfluorobutyl methyl ether can be used for cleaning agents of precision electronic circuit boards and pesticides, and simultaneously has high application value in the synthesis of fluorine-containing fine chemicals such as fluorine-containing medical intermediates and the like. Perfluorobutyl methyl ether is an excellent cleaning agent and has the potential of replacing Trichloroethylene (TCE), n-bromopropane (nPB) or other common cleaning agents. In addition, perfluorobutyl methyl ether can achieve cooling purposes in semiconductor, aerospace, electronics and other heat transfer applications in a safe, efficient and sustainable manner, particularly immersion cooling technology, and by directly immersing the server in the fluorinated liquid, accelerated heat dissipation can be facilitated, and the utilization efficiency of refrigeration energy of the data center is greatly improved. Therefore, the market demand for perfluorobutyl methyl ether is large.
At present, few reports about perfluorobutyl methyl ether synthesis methods exist, and the method almost belongs to the blank field in China. The literature (Synlett,2000,3, p.343-344) reports that perfluorobutyl methyl ether with a content of 69% is produced by a fluorination reaction of heptafluoroisopropenyl methyl ether with cobalt fluoride (trivalent) at-196 ℃ to 20 ℃ for 0.5 h. The reaction requires cobalt fluoride (trivalent) as a starting material. The cobalt fluoride (divalent) after the reaction is finished needs to be fluorinated by fluorine gas to synthesize cobalt fluoride (trivalent). The use of fluorine increases industrial safety risks and limits industrial popularization. The literature (Journal of Fluorine Chemistry,2005,126,11-12, p.1578-1586) reports that perfluorobutyl methyl ether is synthesized by reacting methoxy formyl fluoride with heptafluoroisopropenyl methyl ether under the action of tetraglyme at 100 ℃ for 48 h. The raw materials of the reaction are not easy to prepare, and the industrial cost is greatly improved. The patent (US2004192974) reports that 71% of perfluorobutyl methyl ether is synthesized by perfluoroalkane and a methoxyl compound under the action of CsF and KF. The method adopts a liquid phase method, and generates more industrial waste liquid. In addition, the reaction uses industrial raw materials which are difficult to prepare, and the possibility of industrial popularization is greatly limited.
From the above, in the existing route of perfluorobutyl methyl ether, the characteristics of long route, harsh conditions, very expensive raw materials, toxic fluorine gas, high equipment requirements and more three wastes limit the industrial production of perfluorobutyl methyl ether.
Disclosure of Invention
The invention aims to prepare high-yield perfluorobutyl methyl ether by using a simple reaction system and suitable reaction conditions, and the raw materials are cheap and convenient to obtain; the catalyst has good stability and long service life; the product is simple to separate and purify; the synthesis process is safe and suitable for industrial production.
The invention relates to a method for synthesizing perfluorobutyl methyl ether, belonging to the field of organic chemical synthesis. A method for synthesizing perfluorobutyl methyl ether is characterized in that: the first step is as follows: carbon tetrachloride (molecular formula CCl)4) With pentachloropropene (molecular formula CCl)3CH＝CCl2) Generating nonachlorobutane (molecular formula CCl) under the action of telomerization catalyst3CH(CCl3)CCl3). The second step is that: the nonachlorobutane is dehydrochlorinated in a gas phase catalysis way under the action of a catalyst to generate perchlorobutene (CCl)3C＝(CCl2)CCl3). The third step: the perchloro-butene and Anhydrous Hydrogen Fluoride (AHF) generate hexafluoro-dichlorobutene (CF) under the action of a catalyst3C＝(CCl2)CF3). The fourth step: hexafluorodichlorobutene with methanol (CH)3OH) and potassium hydroxide to generate hexafluoro-chloro-isopropenyl methyl ether (CH)3O(Cl)C＝C(CF3)2). The fifth step:hexafluoromonochloroisopropenyl methyl ether, chlorine and anhydrous hydrogen fluoride are subjected to gas phase catalysis to synthesize perfluorobutyl methyl ether (CH) under the action of catalyst3O(F2)C-C(CF3)2)。
The nonachlorobutane is generated by the carbon tetrachloride and the pentachloropropene under the action of a telomerization catalyst, wherein the telomerization catalyst is at least one of Fe, Ni, Cu and Ca.
The method comprises the following steps of carrying out gas-phase catalytic dehydrochlorination on nonachlorobutane to generate perchlorobutene under the action of a catalyst, wherein the catalyst is one or more of Pd, Ni, Fe, Al and Mn.
The method comprises the following steps of (1) dehydrochlorinating nonachlorobutane in a gas phase catalysis manner under the action of a catalyst to generate perchlorobutene, wherein the mol ratio of the nonachlorobutane to nitrogen is 1: 0.1-20.
The perchlorobutene and Anhydrous Hydrogen Fluoride (AHF) generate hexafluorodichlorobutene under the action of a catalyst, wherein the catalyst is a compound formed by at least one of Mg, Cr, Fe, Zn and Al or at least one of Mg, Cr, Fe, Zn and Al and one of metals such as Bi, Ti, Ni and the like.
Perchloro butene and Anhydrous Hydrogen Fluoride (AHF) generate hexafluoro dichlorobutene under the action of a catalyst, and the contact time is 0.1-20 s.
Perchloro-butene and Anhydrous Hydrogen Fluoride (AHF) generate hexafluoro-dichlorobutene under the action of a catalyst, and the reaction temperature is 200-600 ℃.
The perchlorobutene and Anhydrous Hydrogen Fluoride (AHF) generate hexafluorodichlorobutene under the action of a catalyst, wherein the molar ratio of the nonachlorobutane to the anhydrous hydrogen fluoride is 1: 6-30.
Carrying out telomerization on hexafluoro dichlorobutene, methanol and potassium hydroxide to generate hexafluoro monochloro isopropenyl methyl ether, wherein the molar ratio of the hexafluoro dichlorobutene to the methanol to the potassium hydroxide is 1: 1-4: 0.1 to 1.
And (2) carrying out gas-phase catalysis on the hexafluoro-chloro-isopropenyl methyl ether, chlorine and anhydrous hydrogen fluoride under the action of a catalyst to synthesize the perfluorobutyl methyl ether, wherein the contact time is 0.5-20 s.
The invention has the following beneficial effects:
1. the invention has cheap raw materials and convenient sources.
2. The catalyst has good stability and can be repeatedly recycled.
3. The solvent can be recycled.
4. The product is simple to separate and purify.
5. Safe synthesis process and suitability for industrial production
Drawings
Figure 1 is a synthetic scheme.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
Example 1
(1) The first step of reaction:
5.6g of iron powder and 49.0g of dimethylacetamide are added into a 150ml three-neck flask, the reaction temperature is controlled to be about-20 ℃ by adopting an ethanol and liquid nitrogen mixture, and the rotating speed of a magnetic stirrer is 200 r/min. After stirring for 2 hours, 15.4g of carbon tetrachloride and 21.5g of pentachloropropene were introduced therein. After stirring for 2 hours, the mixture was rectified under reduced pressure to collect 42.3g of organic matter. The GC analysis showed that 87.0% of the total was nonachlorobutane.
(2) The second step of reaction:
5.5g of PdCl2And 2.1g of NiCl3Dissolved in 200ml of deionized water and poured rapidly into a dried 200g solution having a specific surface area of 1000m2In the active carbon per gram, slow drying by a rotary evaporator is adopted. Thus, the Pd-Ni/C catalyst was prepared.
10ml of Pd-Ni/C catalyst was charged into a fixed bed reactor, which was heated with an open tube furnace. The catalyst is dried for 10 hours under the protection of nitrogen gas of 300ml/min and the temperature is increased to 300 ℃ at the speed of 10 ℃/min, and then the temperature is reduced to 100 ℃. This completes the drying process of the catalyst. Determination of the specific surface by the BET methodThe product is 750.0m2/g。
The reactor was heated to 130 ℃ and mixed well in a mixing chamber using a peristaltic pump with 0.1g/min nonachlorobutane (83% purity) along with 50ml/min nitrogen. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis, and the GC result showed that the collected product contained 80% of perchlorobutene and 5% of nonachlorobutane.
(3) The third step of reaction:
CrCl with the molar ratio of 85:5:103，Mg(NO3)2，Zn(NO3)2The solutions were mixed, and 30 wt.% aqueous ammonia was added dropwise to the mixed solution to adjust the pH to 10.0. Precipitating and filtering, washing with deionized water, drying, and pressing to obtain a fluorination catalyst precursor Cr-Mg-Zn;
50ml of fluorination catalyst Cr-Mg-Zn precursor was fed into a fixed bed reactor, which was heated with an open tube furnace. The catalyst is dried for 10 hours under the protection of 100ml/min nitrogen and at the temperature of 1 ℃/min rising to 400 ℃, and then the temperature is reduced to 200 ℃. This completes the drying process of the fluorination catalyst.
Heating the reactor to 200 ℃, activating the catalyst by 100ml/min nitrogen and 20ml/min hydrogen fluoride for 10 hours; activating the catalyst for 10 hours by 100ml/min nitrogen and 50ml/min hydrogen fluoride; activating the catalyst for 10 hours by 50ml/min nitrogen and 100ml/min hydrogen fluoride; activating the catalyst by pure hydrogen fluoride for 10 hours at a rate of 100 ml/min; the temperature was raised to 400 ℃ and the catalyst was activated with 100ml/min of pure hydrogen fluoride for 10 hours. This completes the activation process of the Cr-Mg-Zn catalyst.
The reactor was heated to 260 ℃ and mixed uniformly in a mixing chamber using a peristaltic pump with 0.1g/min perchlorobutene (95% purity) along with 78.4ml/min hydrogen fluoride. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed 78% hexafluorodichlorobutene in the collected product.
(4) And a fourth step of reaction:
5.6g of potassium hydroxide and 3.4g of anhydrous methanol are added into a 150ml three-neck flask, the reaction temperature is controlled to be about 0 ℃ by adopting an ethanol and liquid nitrogen mixture, and the rotating speed of a magnetic stirrer is 300 r/min. After stirring for 2 hours, 23.8g of hexafluorodichlorobutene (purity 96%) was introduced thereinto. After stirring for 2 hours, the mixture was rectified under reduced pressure to collect a total of 26.8g of organic matter. GC analysis showed 84% of these to be hexafluoroisopropenylmethyl ether.
(5) The fifth step of reaction:
the reactor containing 20ml of Cr-Mg-Zn catalyst was heated to 230 ℃ and mixed uniformly in a mixing chamber with 0.1g/min hexafluoroisopropenyl methyl ether (91% purity) and 62ml/min hydrogen fluoride and 22.4ml/min chlorine using a peristaltic pump. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC result showed that the product collected contained 67% perfluorobutyl methyl ether.
Example 2
(1) The first step of reaction:
6.5g of copper powder and 53g of dimethylacetamide are added into a 150ml three-neck flask, the reaction temperature is controlled to be about-20 ℃ by adopting an ethanol and liquid nitrogen mixture, and the rotating speed of a magnetic stirrer is 200 r/min. After stirring for 2 hours, 15.4g of carbon tetrachloride and 21.5g of pentachloropropene were introduced therein. After stirring for 6 hours, the mixture was rectified under reduced pressure to collect 37.8g of organic matter. GC analysis showed 91% of these to be nonachlorobutanes.
(2) The second step of reaction:
6.5g of PdCl2And 3.5g FeCl3Dissolved in 200ml of deionized water and poured rapidly into a dried 200g solution having a specific surface area of 1000m2In the active carbon per gram, slow drying by a rotary evaporator is adopted. Thus, the Pd-Fe/C catalyst was prepared.
10ml of Pd-Fe/C catalyst was charged into a fixed bed reactor, which was heated with an open tube furnace. Under the protection of nitrogen gas of 300ml/min, the catalyst is firstly preparedDrying at a temperature of 10 deg.C/min up to 300 deg.C for 10 hr, and then reducing the temperature to 100 deg.C. This completes the drying process of the catalyst. The specific surface area of the powder was 612.0m as determined by the BET method2/g。
The reactor was heated to 230 ℃ and mixed well with 0.1g/min nonachlorobutane (88% purity) and 62ml/min nitrogen using a peristaltic pump. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis, and the GC result showed that the collected product contained 87% of perchlorobutene and 2% of nonachlorobutane.
(3) The third step of reaction:
CrCl with the molar ratio of 75:15:103，Fe(NO3)3，Zn(NO3)2The solutions were mixed, and 30 wt.% aqueous ammonia was added dropwise to the mixed solution to adjust the pH to 10.0. Precipitating and filtering, washing with deionized water, drying, and pressing to obtain a fluorination catalyst precursor Cr-Fe-Zn;
50ml of fluorination catalyst Cr-Fe-Zn precursor was fed into a fixed bed reactor, which was heated with an open tube furnace. The catalyst is dried for 10 hours under the protection of 100ml/min nitrogen and at the temperature of 1 ℃/min rising to 400 ℃, and then the temperature is reduced to 200 ℃. This completes the drying process of the fluorination catalyst.
Heating the reactor to 200 ℃, activating the catalyst by 100ml/min nitrogen and 20ml/min hydrogen fluoride for 10 hours; activating the catalyst for 10 hours by 100ml/min nitrogen and 50ml/min hydrogen fluoride; activating the catalyst for 10 hours by 50ml/min nitrogen and 100ml/min hydrogen fluoride; activating the catalyst by pure hydrogen fluoride for 10 hours at a rate of 100 ml/min; the temperature was raised to 400 ℃ and the catalyst was activated with 100ml/min of pure hydrogen fluoride for 10 hours. This completes the activation process of the Cr-Fe-Zn catalyst.
The reactor was heated to 210 ℃ and mixed uniformly in a mixing chamber using a peristaltic pump with 0.1g/min perchlorobutene (91% purity) along with 78.4ml/min hydrogen fluoride. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed 84% hexafluorodichlorobutene in the collected product.
(4) And a fourth step of reaction:
5.6g of potassium hydroxide and 3.4g of anhydrous methanol are added into a 150ml three-neck flask, the reaction temperature is controlled to be about-30 ℃ by adopting an ethanol and liquid nitrogen mixture, and the rotating speed of a magnetic stirrer is 100 r/min. After stirring for 2 hours, 23.8g of hexafluorodichlorobutene (purity 91%) was introduced thereinto. After stirring for 2 hours, the mixture was rectified under reduced pressure to collect 22.8g of organic matter. GC analysis showed that 67% of the total was hexafluoroisopropenylmethyl ether.
(5) The fifth step of reaction:
the reactor containing 20ml of Cr-Fe-Zn catalyst was heated to 300 ℃ and mixed uniformly in a mixing chamber with 0.1g/min hexafluoroisopropenyl methyl ether (purity: 88%) by a peristaltic pump together with 100.8ml/min hydrogen fluoride and 36.6ml/min chlorine. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC result showed that the product collected contained 83% perfluorobutyl methyl ether.
Claims (10)
1. A method for synthesizing perfluorobutyl methyl ether is characterized in that: the first step is as follows: carbon tetrachloride (molecular formula CCl)4) With pentachloropropene (molecular formula CCl)3CH＝CCl2) Generating nonachlorobutane (molecular formula CCl) under the action of telomerization catalyst3CH(CCl3)CCl3). The second step is that: the nonachlorobutane is dehydrochlorinated in a gas phase catalysis way under the action of a catalyst to generate perchlorobutene (CCl)3C＝(CCl2)CCl3). The third step: the perchloro-butene and Anhydrous Hydrogen Fluoride (AHF) generate hexafluoro-dichlorobutene (CF) under the action of a catalyst3C＝(CCl2)CF3). The fourth step: hexafluorodichlorobutene with methanol (CH)3OH) and potassium hydroxide to generate hexafluoro-chloro-isopropenyl methyl ether (CH)3O(Cl)C＝C(CF3)2). The fifth step: hexafluoromonochloroSynthesis of perfluorobutyl methyl ether (CH) by gas phase catalysis of isopropenyl methyl ether, chlorine and anhydrous hydrogen fluoride under the action of catalyst3O(F2)C-C(CF3)2)。
2. The process of claim 1, wherein the nonachlorobutane is formed from carbon tetrachloride and pentachloropropene in the presence of a telomerization catalyst, wherein the telomerization catalyst is at least one of Fe, Ni, Cu, and Ca.
3. The process of claim 1, wherein the dehydrochlorination of nonachlorobutane to perchlorobutene is carried out in the presence of a catalyst comprising one or more of Pd, Ni, Fe, Al and Mn.
4. The process of claim 1, wherein the catalyst is used to perform gas-phase catalytic dehydrochlorination of nonachlorobutane to perchlorobutene, wherein the molar ratio of nonachlorobutane to nitrogen is 1: 0.1-20.
5. The method of claim 1, wherein the perchlorobutene and Anhydrous Hydrogen Fluoride (AHF) are reacted in the presence of a catalyst to form hexafluorodichlorobutene, wherein the catalyst is at least one of Mg, Cr, Fe, Zn and Al, or a composite of at least one of Mg, Cr, Fe, Zn and Al and one of Bi, Ti, Ni and other metals.
6. The process of claim 1 wherein perchlorobutene is reacted with Anhydrous Hydrogen Fluoride (AHF) in the presence of a catalyst to form hexafluorodichlorobutene, said contact time being in the range of 0.1 to 20 seconds.
7. The process of claim 1 wherein perchlorobutene is reacted with Anhydrous Hydrogen Fluoride (AHF) in the presence of a catalyst to produce hexafluorodichlorobutene, said reaction temperature being in the range of 200 to 600 ℃.
8. The process of claim 1 wherein perchlorobutene is reacted with Anhydrous Hydrogen Fluoride (AHF) in a molar ratio of 1: 6-30.
9. The process of claim 1, wherein the telomerization of hexafluorodichlorobutene with methanol and potassium hydroxide is carried out to produce hexafluoromonochloroisopropenyl methyl ether, wherein the molar ratio of hexafluorodichlorobutene to methanol to potassium hydroxide is 1: 1-4: 0.1 to 1.
10. The process of claim 1, wherein the hexafluoro-monochloro-isopropenyl methyl ether is synthesized into perfluorobutyl methyl ether by gas-phase catalysis with chlorine and anhydrous hydrogen fluoride in the presence of a catalyst, wherein the contact time is 0.5-20 s.
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| CN114591154A (en) * | 2022-03-17 | 2022-06-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of tetrafluorocyclobutenyl dimethyl ether |
| CN115490571A (en) * | 2022-10-13 | 2022-12-20 | 中国矿业大学(北京) | Method for synthesizing monobromo trifluoro chlorobutene |
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| CN114478207A (en) * | 2022-03-17 | 2022-05-13 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Hexafluorobutenyl dimethyl ether and preparation method and application thereof |
| CN114591154A (en) * | 2022-03-17 | 2022-06-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of tetrafluorocyclobutenyl dimethyl ether |
| CN114478207B (en) * | 2022-03-17 | 2024-05-24 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Hexafluorobutenyl dimethyl ether and preparation method and application thereof |
| CN115490571A (en) * | 2022-10-13 | 2022-12-20 | 中国矿业大学(北京) | Method for synthesizing monobromo trifluoro chlorobutene |
| CN115490571B (en) * | 2022-10-13 | 2024-09-20 | 中国矿业大学(北京) | Synthesis of monobromo-tribromo method for preparing fluorine chlorine butene |
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