CN115572993A - Method for preparing perfluoroacyl fluoride by electrochemical method - Google Patents
Method for preparing perfluoroacyl fluoride by electrochemical method Download PDFInfo
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- CN115572993A CN115572993A CN202211162052.XA CN202211162052A CN115572993A CN 115572993 A CN115572993 A CN 115572993A CN 202211162052 A CN202211162052 A CN 202211162052A CN 115572993 A CN115572993 A CN 115572993A
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- fluoride
- perfluoroacyl
- fatty acid
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000002848 electrochemical method Methods 0.000 title claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims description 20
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 29
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 21
- -1 fatty acid ester Chemical class 0.000 claims abstract description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 12
- 229930195729 fatty acid Natural products 0.000 claims abstract description 12
- 239000000194 fatty acid Substances 0.000 claims abstract description 12
- 150000001265 acyl fluorides Chemical class 0.000 claims abstract description 11
- YLCLKCNTDGWDMD-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)F YLCLKCNTDGWDMD-UHFFFAOYSA-N 0.000 claims abstract description 10
- DCEPGADSNJKOJK-UHFFFAOYSA-N 2,2,2-trifluoroacetyl fluoride Chemical compound FC(=O)C(F)(F)F DCEPGADSNJKOJK-UHFFFAOYSA-N 0.000 claims abstract description 7
- YYXWJNBPHDUWJP-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)C(F)(F)F YYXWJNBPHDUWJP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005257 alkyl acyl group Chemical group 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 9
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 8
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 238000003682 fluorination reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 229910052731 fluorine Inorganic materials 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 8
- 150000002148 esters Chemical class 0.000 abstract description 3
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 150000002222 fluorine compounds Chemical class 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- 238000006467 substitution reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 17
- 238000001816 cooling Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- JUCMRTZQCZRJDC-UHFFFAOYSA-N acetyl fluoride Chemical class CC(F)=O JUCMRTZQCZRJDC-UHFFFAOYSA-N 0.000 description 4
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 4
- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 description 4
- LMFJKKGDLAICPF-UHFFFAOYSA-N phenanthrene-9-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC3=CC=CC=C3C2=C1 LMFJKKGDLAICPF-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006735 epoxidation reaction Methods 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 1
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000007098 aminolysis reaction Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AOMUALOCHQKUCD-UHFFFAOYSA-N dodecyl 4-chloro-3-[[3-(4-methoxyphenyl)-3-oxopropanoyl]amino]benzoate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=C(Cl)C(NC(=O)CC(=O)C=2C=CC(OC)=CC=2)=C1 AOMUALOCHQKUCD-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YPJUNDFVDDCYIH-UHFFFAOYSA-N perfluorobutyric acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)F YPJUNDFVDDCYIH-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- WMFABESKCHGSRC-UHFFFAOYSA-N propanoyl fluoride Chemical compound CCC(F)=O WMFABESKCHGSRC-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
Abstract
The invention relates to a method for preparing perfluorinated acyl fluoride by an electrochemical method, which comprises the steps of adding alkyl acyl chloride into fatty acid ester, putting the fatty acid ester into an electrolytic bath containing anhydrous hydrogen fluoride, and electrolyzing at 4-20 ℃ to prepare perfluorinated acyl fluoride; perfluorinated acid fluorides include perfluoroacetyl fluoride, perfluoropropionyl fluoride or perfluorobutyryl fluoride; the products are collected by electrolysis and rectified to obtain high-purity perfluorinated acyl fluoride products. The invention adopts a mode of adding the initiator to initiate the electrolytic process, and the electrolytic process is milder; along with the proceeding of the electrolytic process, the insoluble ester product can generate fluorine substitution reaction or dissociation to form a substance soluble in hydrogen fluoride, so that the material between the polar plates can be maintained to have a certain concentration, the occurrence of the transitional electrolytic process is avoided, the yield of the target product obtained by the electrolytic method is over 80 percent and is far higher than the existing 65 to 70 percent of literature value, and the cost of the product is greatly reduced.
Description
Technical Field
The invention relates to a method for preparing perfluoroacyl fluoride by an electrochemical method, belonging to the field of fluorine-containing fine chemical engineering.
Background
Perfluoroacyl fluorides are important chemical synthesis intermediates. The compound can be subjected to different reactions such as addition, decomposition, hydrolysis, aminolysis, alcoholysis and the like to obtain very wide derivative compounds, such as high-value-added fluorine-containing fine chemicals such as perfluorooctanoic acid, perfluorobutyric acid, perfluoropropionic acid, perfluoroalkoxy acyl fluoride and the like, and is widely applied to the fields of fluorine-containing medicines, fluorine-containing pesticides, electronics, precise instruments and the like.
According to the literature reports, the prior preparation methods of the propionyl fluoride mainly comprise an electrolysis method, a perfluoromethyl vinyl ether isomerization method, a tetrafluoroethylene and fluorophosphorus telomerization method and the like. Wherein the electrolysis method and the propylene oxide isomerization method are the main synthetic routes for preparing the perfluoroacyl fluoride on an industrial scale at present. Patents US4729856, US5684193, CN103145544, CN105541606 and CN105315150 all report the preparation of pentafluoropropionyl fluoride from hexafluoropropylene oxide by isomerization reaction, and the yield can reach more than 90%. Although there are some of these processes described above which can produce pentafluoropropionyl fluoride, these processes require hexafluoropropylene oxide as a raw material to undergo an isomerization reaction, and hexafluoropropylene oxide is produced by epoxidation from hexafluoropropylene. The yield of hexafluoropropylene oxide prepared by the epoxidation reaction of hexafluoropropylene is low at present, and the price of hexafluoropropylene is high, so that the cost for preparing pentafluoropropionyl fluoride is high.
Many organic compound products can be produced by electrolysis, but the yield is very low. When acyl fluoride or ester raw materials are adopted for electrolysis, a sodium fluoride additive is required to be added to improve the conductivity of the electrolyte to increase the electrolysis efficiency.
Patents US2717871 and GB735730 mention that when preparing perfluorocarboxylic acid products by electrolysis, the yield of perfluoroacetic acid produced by electrolysis of acetyl fluoride can reach 70%, and the yield is greatly reduced when preparing perfluoroacyl fluoride having a higher carbon number. The above studies also caused the problem of salt contamination due to the addition of a third substance such as sodium fluoride.
Compared with a propylene oxide isomerization method, the electrolytic method uses industrial bulk products as raw materials, the source of the raw materials is wide, compared with hexafluoropropylene as the raw material, the raw material of the non-fluorine-containing organic compound is cheaper, and if the yield of the electrolytic process can be better improved, the process route for preparing pentafluoropropionyl fluoride by electrolytic fluorination is more suitable for large-scale industrial production.
Disclosure of Invention
The invention aims to provide a new electrolysis process route aiming at the current situation that the yield is lower (65-70%) in the process of preparing the perfluoroacyl fluoride by an electrolysis method, and the electrolysis is carried out under a milder electrolysis condition, so that the yield in the electrolysis process can be obviously improved, the production cost of the perfluoroacyl fluoride is reduced, and the environmental protection pressure in the production process is reduced. In the process of preparing perfluoroacyl fluoride by adopting acyl fluoride or ester compounds, a certain amount of acyl halide is added into the electrolyte, so that the conductivity of the electrolyte can be greatly improved, and the yield of the electrolytic product of fatty acid ester is improved.
The invention provides a method for preparing perfluoroacyl fluoride by an electrochemical method, which mainly comprises the following steps:
(1) Adding fatty acid ester and alkyl acyl chloride into an electrolytic bath containing anhydrous hydrogen fluoride, and electrolyzing at 4-20 ℃ to prepare perfluorinated acyl fluoride;
(2) The electrolysis collected product is rectified to obtain the perfluorinated acyl fluoride product with high purity
Further, the perfluorinated acid fluoride described in the above (1) has the following structural formula:
wherein R is a perfluorinated aliphatic group containing 1 to 3 carbon atoms
Such as perfluoroacetyl fluoride CF3-COF
Perfluorpropionyl fluoride CF3CF2-COF
Perfluorobutanoyl fluoride CF3CF2CF2-COF
Further, the electrolysis raw material fatty acid ester described in the above (1) has the following structure:
wherein R is a C1-3 aliphatic hydrogen-containing alkyl group, and R1 is a hydrogen containing group in which the number of carbon atoms corresponding to R is increased by one carbon
Aliphatic radicals, such as ethyl acetate, propyl propionate and butyl butyrate.
Further, the additive alkyl acyl halide described in the above (1) has the following structural formula:
wherein R is an aliphatic group containing 1 to 3C atoms, and Z is a halogen element
Further, the fatty acid ester described in the above (1) accounts for 1 to 15% by mass, preferably 4 to 10% by mass of HF.
Further, the content of the alkyl acid chloride in the above (1) is 0.1 to 15% by mass, preferably 1 to 3% by mass, based on the HF content
Further, the voltage for the electrolytic fluorination described in the above (1) is 5.0V to 7.0V.
Further, the electrolytic fluorination described in the above (1) has a current density of 1.2 to 1.5A/dm 2 。
Further, the electrolytic temperature in the electrolytic fluorination process described in the above (1) is 4 to 20 ℃.
Further, the distillation column for separating the product described in the above (2) may be a packed column or a plate column
Further, the distillation column used in the above (2) is operated at a reflux ratio of 10
Further, the number of theoretical plates of the rectifying column used in the above (2) is: 20 to 50 percent of the total weight of the composition,
further, the operating pressure of the rectifying column used in the above (2): normal pressure-positive pressure 8kg/cm 2 Preferably from atmospheric pressure to 2kg/cm 2
The raw materials are mainly dissolved in anhydrous hydrogen fluoride for conducting electricity in the electrolysis process, and the reason that the yield of the electrolysis method is low is that the solubility of the raw materials in the anhydrous hydrogen fluoride is low, so that current is unevenly distributed on a polar plate in the electrolysis process, local current is overlarge, and excessive electrolysis is carried out. On the other hand, when the first hydrogen atom in the molecule is replaced by a fluorine atom, the electron cloud of the whole molecule is polarized largely, and when the local current is too large, the C — C bond is broken, thereby generating a small molecule product.
In the traditional electrolysis process, for raw materials which are insoluble in hydrogen fluoride, a large amount of sodium fluoride conductive agent is added into the hydrogen fluoride to promote electrolysis, so that although the electrolysis process can be carried out, the concentration of materials between polar plates is low, and simultaneously, due to the existence of the conductive agent, the current is large, so that the local content of fluorine ions between the polar plates is too high, the material transition electrolysis process is caused, and the yield of electrolysis products is low. The invention adopts a mode of adding the initiator to initiate the electrolytic process, and the electrolytic process is milder; along with the proceeding of the electrolytic process, the insoluble ester product can generate fluorine substitution reaction or dissociation to form a substance soluble in hydrogen fluoride, thus the material between the polar plates can be maintained to have a certain concentration, the occurrence of the transition electrolytic process is avoided, and the yield of the electrolytic product is higher.
Detailed Description
The present invention will be described in further detail with reference to specific examples below:
EXAMPLE 1 preparation of Perfluoroacetyl fluoride
7500kg of anhydrous hydrogen fluoride was charged into an electrolytic cell equipped with a thermometer, a tubular condenser, four nickel anode plates and four stainless steel cathode plates, the total area of the plates being 20.8dm2, and 75g of acetyl chloride and 370g of ethyl acetate were mixed and charged into the electrolytic cell. Electrolyzing at 4-6 deg.c and average voltage of 4-6.0V and average current of 32A for 72 hr, cooling the electrolytic gas in a low temperature condenser, returning the hydrogen fluoride liquid to the electrolytic bath, further cooling the gas containing perfluoro acetyl fluoride (CF 3-COF) and collecting in a low temperature cold trap receiving tank.
The material of the low-temperature cold trap receiving tank is put into a packed tower (the number of theoretical plates is about 22) containing a stainless steel wire mesh, and the pressure of the packed tower is 2kg/cm under the conditions that the reflux ratio is 5 2 Collecting fractions at-32 to-34 ℃ to obtain a perfluorinated acetyl fluoride product with the purity of more than 99 percent, wherein the yield of the perfluorinated acetyl fluoride based on the fed ethyl acetate is as follows: 86.1% ethyl acetate and anhydrous HF were continuously replenished during this electrolysis to maintain the initial feed concentration.
EXAMPLE 2 Perfluoroacetyl fluoride preparation
Using the same electrolytic cell as in example 1, 8000g of anhydrous hydrogen fluoride was charged into the electrolytic cell, and then 80g of acetyl chloride and 800g of ethyl acetate were mixed and charged into the electrolytic cell. Electrolyzing for 72 hours continuously at the temperature of 6-8 ℃ and the average voltage of 5-6.0V under the condition of average current of 32A, cooling the electrolytic gas by a low-temperature condenser, returning the hydrogen fluoride liquid into the electrolytic cell, further cooling the gas containing the perfluoroacetyl fluoride, and collecting the gas into a low-temperature cold trap receiving tank.
The material of the low-temperature cold trap receiving tank is put into a packed tower (the number of theoretical plates is about 30) containing a stainless steel wire mesh, and the pressure of the packed tower is 2kg/cm under the conditions that the reflux ratio is 5 2 Collecting fractions at-32 to-34 ℃ to obtain a perfluorinated acetyl fluoride product with the purity of more than 99.5 percent, wherein the yield of the perfluorinated acetyl fluoride based on the fed ethyl acetate is as follows: 85.3 percent
EXAMPLE 3 preparation of perfluoropropionyl fluoride
Using the same electrolytic cell as in example 1, 8000g of anhydrous hydrogen fluoride was charged into the electrolytic cell, and then 220g of propionyl chloride and 320g of propyl propionate were mixed and charged into the electrolytic cell. Electrolyzing for 72 hours continuously under the conditions that the temperature of an electrolytic bath is 4-6 ℃, the average voltage is 6.0-7.0V and the average current is 32A, cooling the electrolytic gas by a low-temperature condenser, returning the hydrogen fluoride liquid into the electrolytic bath, further cooling the gas containing the perfluoropropionyl fluoride (CF 3CF 2-COF) and collecting the gas into a low-temperature cold trap receiving tank.
Putting the material of the low-temperature cold trap receiving tank into a packed tower containing a stainless steel wire mesh (the number of theoretical plates is about 20), collecting fractions at-29.5 to-30.5 ℃ under normal pressure at a reflux ratio of 3 to 1 to obtain a perfluoropropionyl fluoride product with the purity of more than 99.1%, wherein the yield of the perfluoropropionyl fluoride based on the feeding propyl propionate is as follows: 85.9 percent
EXAMPLE 4 perfluoropropionyl fluoride preparation
Using the same electrolytic cell as in example 1, 8000g of anhydrous hydrogen fluoride was charged into the electrolytic cell, and then 80g of propionyl chloride and 650g of propyl propionate were mixed and charged into the electrolytic cell. Electrolyzing for 72 hours continuously at the temperature of 4-6 ℃ under the average voltage of 5-6.0V and the average current of 28A, cooling the electrolytic gas by a low-temperature condenser, returning the hydrogen fluoride liquid into the electrolytic cell, further cooling the gas containing the perfluoropropionyl fluoride, and collecting the gas into a low-temperature cold trap receiving tank.
Putting the material of the low-temperature cold trap receiving tank into a packed tower containing a stainless steel wire mesh (the number of theoretical plates is about 35), collecting fractions at-29.5 to-30.5 ℃ under normal pressure at a reflux ratio of 4 to 1 to obtain a perfluoropropionyl fluoride product with the purity of more than 99%, wherein the yield of the perfluoropropionyl fluoride based on the fed propyl propionate is as follows: 87.2 percent
EXAMPLE 5 preparation of perfluorobutyryl fluoride
7600g of anhydrous hydrogen fluoride was charged into the electrolytic cell using the same electrolytic cell as in example 1, and then 80g of butyryl chloride and 380g of butyl butyrate were mixed and charged into the electrolytic cell. Electrolyzing at the temperature of 18-20 ℃ under the average voltage of 6.0-7V and the average current of 25A for 72 hours continuously, cooling the electrolytic gas by a low-temperature condenser, returning the hydrogen fluoride liquid into the electrolytic cell, further cooling the gas containing the perfluorobutyryl fluoride (CF 3CF2CF 2-COF) and collecting the gas in a low-temperature cold trap receiving tank.
Putting the material of the low-temperature cold trap receiving tank into a stainless steel wire mesh-containing packed tower (the number of theoretical plates is about 40), collecting fractions at 7-9 ℃ under the normal pressure with a reflux ratio of 3: 82.6 percent
EXAMPLE 6 Perfluorobutyryl fluoride preparation
Using the same electrolytic cell as in example 1, 8000g of anhydrous hydrogen fluoride was charged into the electrolytic cell, and then 100g of butyryl chloride and 480g of butyl butyrate were mixed and charged into the electrolytic cell. Electrolyzing at the temperature of 20 ℃ in an electrolytic bath at the average voltage of 6.0-7V and at the average current of 32A for 72 hours continuously, cooling the electrolytic gas by a low-temperature condenser, returning the hydrogen fluoride liquid into the electrolytic bath, further cooling the gas containing the perfluorobutyryl fluoride, and collecting the gas into a low-temperature cold trap receiving tank.
Putting the material of the low-temperature cold trap receiving tank into a stainless steel wire mesh-containing packed tower (the number of theoretical plates is about 45), collecting fractions at 8-9 ℃ under normal pressure at a reflux ratio of 10: 83.6 percent
The yield of the target product obtained by the electrolysis method of the patent is over 80 percent and is far higher than the existing literature value of 65 to 70 percent, and the cost of the product is greatly reduced.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A method for preparing perfluoroacyl fluoride by an electrochemical method is characterized by comprising the following steps:
(1) Adding alkyl acyl chloride into fatty acid ester, putting the fatty acid ester into an electrolytic bath containing anhydrous hydrogen fluoride, and electrolyzing at 4-20 ℃ to prepare perfluorinated acyl fluoride;
(2) The products are collected by electrolysis and rectified to obtain high-purity perfluorinated acyl fluoride products.
2. The method for electrochemically preparing a perfluoroacyl fluoride according to claim 1, wherein the perfluorinated acyl fluoride comprises perfluoroacetyl fluoride, perfluoropropionyl fluoride or perfluorobutyryl fluoride.
3. The method for electrochemically producing a perfluoroacyl fluoride according to claim 1, wherein said fatty acid ester as a raw material for electrolysis has the following structure:
wherein R is a C1-3 hydrogen-containing alkyl fatty acid, R1 is a C one-carbon-increased hydrogen-containing aliphatic group corresponding to R, and comprises ethyl acetate, propyl propionate and butyl butyrate.
4. The method of claim 1, wherein the alkyl acid halide is of the formula:
wherein R is an aliphatic group containing 1 to 3C, and Z is a halogen element.
5. The method for electrochemically producing a perfluoroacyl fluoride according to claim 1, wherein the fatty acid ester in the step (1) accounts for 1 to 15% by mass of the HF; the mass percentage of the alkyl acyl chloride in the HF is 0.1-15%.
6. The method for electrochemically producing perfluoroacyl fluoride according to claim 1, wherein the fatty acid ester in the step (1) accounts for 4 to 10% by mass of HF; the mass percentage of the alkyl acyl chloride in the HF is 1-3%.
7. The method for electrochemically producing perfluoroacyl fluoride according to claim 1, wherein said electrolytic fluorination in step (1) is carried out at a voltage of 5.0V to 7.0V; the current density is 1.2-1.5A/dm2; the electrolysis temperature is 4-20 ℃.
8. The method for electrochemically producing perfluoroacyl fluoride according to claim 1, wherein the rectification column for product separation in the step (2) is a packed column or a plate column.
9. The method for electrochemically producing a perfluoroacyl fluoride according to claim 1, wherein the rectifying column used in the step (2) is operated at a reflux ratio of 10; the theoretical plate number of the rectifying tower is as follows: 10 to 50; operating pressure of the rectifying column: normal pressure-positive pressure 8kg/cm 2 。
10. The method for electrochemically producing a perfluoroacyl fluoride according to claim 1, wherein the rectifying column used in the step (2) is operated at a reflux ratio of 10; the theoretical plate number of the rectifying tower is as follows: 20 to 50 percent; operating pressure of the rectifying column: normal pressure-positive pressure 2kg/cm 2 。
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