CN112358395A - Preparation process of perfluoroheptanoic acid - Google Patents
Preparation process of perfluoroheptanoic acid Download PDFInfo
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- CN112358395A CN112358395A CN202011248265.5A CN202011248265A CN112358395A CN 112358395 A CN112358395 A CN 112358395A CN 202011248265 A CN202011248265 A CN 202011248265A CN 112358395 A CN112358395 A CN 112358395A
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- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- JZHDEEOTEUVLHR-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F JZHDEEOTEUVLHR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 21
- BYKNGMLDSIEFFG-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F BYKNGMLDSIEFFG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- 239000012074 organic phase Substances 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 10
- 150000002576 ketones Chemical class 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000003682 fluorination reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 9
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 6
- GBDGHHBEUZVCBC-UHFFFAOYSA-N [Br-].[NH4+].C(CCCCCCCCCCCCCCC)C1=NC=CC=C1 Chemical compound [Br-].[NH4+].C(CCCCCCCCCCCCCCC)C1=NC=CC=C1 GBDGHHBEUZVCBC-UHFFFAOYSA-N 0.000 claims description 5
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 5
- 229940005605 valeric acid Drugs 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- XLIFBQWTSCGUEB-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoyl fluoride Chemical compound FC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XLIFBQWTSCGUEB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-M 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoate Chemical compound [O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 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 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of preparation of fluorine-containing compounds, and discloses a preparation process of perfluoroheptanoic acid, which comprises the following steps: step one, oxidation: the method comprises the steps of adding potassium permanganate, an organic weak acid solution and a quaternary ammonium salt catalyst into a reaction container, slowly dripping dodecafluoroheptanol into the reaction container, controlling the reaction temperature to be 70-85 ℃ after dripping, carrying out suction filtration on reaction liquid after reacting for 0.5-1 hour, acidifying filtrate, extracting the acidified liquid with an extractant ketone, separating out an organic phase, distilling the organic phase, collecting 192 ℃ fraction, and obtaining dodecafluoroheptanoic acid, wherein the application field of dodecafluoroheptanol is limited, and the use of dodecafluoroheptanol is greatly limited.
Description
Technical Field
The invention relates to the technical field of preparation of fluorine-containing compounds, in particular to a preparation process of perfluoroheptanoic acid.
Background
Perfluoroheptanoic acid is a very important new fluorine-containing material, and is mainly applied to an emulsifier and a dispersant of a fluorine-containing polymer, and a leveling agent of printing ink, coating and the like. Currently, perfluorooctanoic acid (PFOA) is mainly used as a fluorine-containing emulsifier, but is being banned gradually in europe, the united states and the like because of its bioaggregability and difficult degradability. The perfluoroheptanoic acid has wide application prospect as a substitute thereof.
The existing preparation method of the perfluoroheptanoic acid adopts an electrolytic fluorination method, and a perfluoroheptanoic acid product or a perfluoroheptanoate product is prepared through conversion, and the method has the obvious defects that the product yield is too low and is only 10-20%, the energy consumption is high, the pollution is heavy, and the like.
Disclosure of Invention
Technical problem to be solved
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a preparation process of perfluoroheptanoic acid, which solves the problems that the conventional preparation method of perfluoroheptanoic acid adopts an electrolytic fluorination method and prepares a perfluoroheptanoic acid product or a perfluoroheptanoate product through conversion, and the method has obvious defects, is low in product yield which is only 10-20%, high in energy consumption, heavy in pollution and the like.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation process of perfluoroheptanoic acid comprises the following steps:
step one, oxidation: adding potassium permanganate, an organic weak acid solution and a quaternary ammonium salt catalyst into a reaction container, slowly dripping dodecafluoroheptanol into the reaction container, controlling the reaction temperature to be 70-85 ℃ after dripping, performing suction filtration on reaction liquid after reacting for 0.5-1 hour, extracting the acidified liquid with an extractant ketone after filtrate is acidified, separating an organic phase, distilling the organic phase and collecting 192 ℃ fraction to obtain dodecafluoroheptanoic acid;
step two, chlorination: adding the dodecafluoroheptanoic acid obtained in the first step into another reaction container, adding diethyl ether, keeping the temperature below 30 ℃, dropwise adding thionyl chloride under the stirring condition, after dropwise adding, heating to 55-65 ℃, reacting for 3-5 hours, and rectifying to remove diethyl ether and excessive thionyl chloride to obtain a product;
step three, fluorination: adding the product obtained in the step two into a fluorination reaction kettle, stirring and heating to 70 ℃, simultaneously introducing 25% fluorine gas from the bottom of the reaction kettle at the speed of 200-300 ml/min, and continuously introducing the fluorine gas for 15-18 hours to obtain a fluorinated product;
step four, hydrolysis: and (3) heating the fluorinated product obtained in the third step to 50 ℃, adding deionized water, continuously stirring for 3 hours, and carrying out negative pressure rectification to obtain the perfluoroheptanoic acid.
Preferably, the organic weak acid is selected from one or more of acetic acid, propionic acid, butyric acid and valeric acid, and the mass of the organic weak acid solution is 1-2 times that of potassium permanganate.
Preferably, the quaternary ammonium salt catalyst is selected from one of octadecyl trimethyl ammonium bromide, hexadecyl pyridine ammonium bromide, trioctyl methyl ammonium chloride and tetrabutyl ammonium bromide, and the mole number of the quaternary ammonium salt catalyst is 8-12% of that of the potassium permanganate.
Preferably, the molar ratio of the potassium permanganate to the dodecafluoroheptanol is 5: 3.
Preferably, the filtrate is acidified by sulfuric acid or hydrochloric acid, and the extractant ketone is acetone or butanone.
Preferably, the mass ratio of the dodecafluoroheptanoic acid to the diethyl ether to the thionyl chloride in the step II is 10:6: 5.
Preferably, the mass ratio of the fluorinated product to the deionized water is 10: 1.
(III) advantageous effects
Compared with the prior art, the invention provides a preparation process of perfluoroheptanoic acid, which has the following beneficial effects:
(1) the application field of dodecafluoroheptanol is limited, the use of dodecafluoroheptanol is greatly limited, and perfluoroheptanoic acid is prepared by taking dodecafluoroheptanol as a raw material through reactions such as oxidation, chlorination, fluorination, hydrolysis and the like, so that the method has wider application prospect.
(2) The technological process of preparing perfluoro heptanoic acid with dodecafluoro heptanol has low energy consumption, no pollution, easy operation, high yield, comprehensive yield up to over 75%, and higher competitive advantage than the existing production process of perfluoro heptanoic acid.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a preparation process of perfluoroheptanoic acid comprises the following steps:
step one, oxidation: adding potassium permanganate, an organic weak acid solution and a quaternary ammonium salt catalyst into a reaction container, wherein the mass of the organic weak acid solution is 1 time of that of the potassium permanganate, the molar number of the quaternary ammonium salt catalyst is 8 percent of that of the potassium permanganate, slowly dripping dodecafluoroheptanol into the reaction container, the molar ratio of the potassium permanganate to the dodecafluoroheptanol is 5:3, controlling the reaction temperature to be 70 ℃ after dripping, reacting for 1 hour, then carrying out suction filtration on reaction liquid, acidifying filtrate, extracting the acidified liquid with an extractant ketone, separating out an organic phase, distilling the organic phase, and collecting 192 ℃ fraction to obtain dodecafluoroheptanoic acid;
oxidation of dodecafluoroheptanol to give dodecafluoroheptanoic acid, the reaction is as follows:
H(CF2CF2)3CH2OH+[O]——H(CF2CF2)3COOH。
step two, chlorination: adding the dodecafluoroheptanoic acid obtained in the first step into another reaction container, adding ether, keeping the temperature below 30 ℃, dropwise adding thionyl chloride under the stirring condition, heating to 55 ℃ after dropwise adding, carrying out rectification to remove ether and excessive thionyl chloride after the reaction time is 5 hours, and obtaining a product, wherein the mass ratio of the dodecafluoroheptanoic acid to the ether to the thionyl chloride is 10:6: 5;
reacting dodecafluoroheptanoic acid with thionyl chloride to obtain dodecafluoroheptanoyl chloride, wherein the reaction is as follows:
H(CF2CF2)3COOH+SO2Cl2——H(CF2CF2)3COCl。
step three, fluorination: adding the product obtained in the step two into a fluorination reaction kettle, stirring and heating to 70 ℃, simultaneously introducing 25% fluorine gas from the bottom of the reaction kettle at the speed of 200ml/min, and continuously introducing the fluorine gas for 18 hours to obtain a fluorination product; fluorinating dodecafluoroheptanoyl chloride to obtainTo perfluoroheptanoyl fluoride, the reaction is as follows: h (CF)2CF2)3COCl+F2——H(CF2CF2)3COF。
Step four, hydrolysis: heating the fluorinated product obtained in the third step to 50 ℃, adding deionized water, continuously stirring for 3 hours with the mass ratio of the fluorinated product to the deionized water being 10:1, and carrying out negative pressure rectification to obtain perfluoroheptanoic acid, wherein the comprehensive yield of the perfluoroheptanoic acid is 75.6%;
hydrolysis of perfluoroheptanoyl fluoride gives perfluoroheptanoic acid, the reaction is as follows:
F(CF2CF2)3COF+H2O——F(CF2CF2)3COOH。
further, the organic weak acid is selected from one or more of acetic acid, propionic acid, butyric acid and valeric acid; the quaternary ammonium salt catalyst is one of octadecyl trimethyl ammonium bromide, hexadecyl pyridine ammonium bromide, trioctyl methyl ammonium chloride and tetrabutyl ammonium bromide; acidifying the filtrate with sulfuric acid or hydrochloric acid, and extracting with acetone or butanone.
Example two:
a preparation process of perfluoroheptanoic acid comprises the following steps:
step one, oxidation: adding potassium permanganate, an organic weak acid solution and a quaternary ammonium salt catalyst into a reaction container, wherein the mass of the organic weak acid solution is 1.5 times that of the potassium permanganate, the mole number of the quaternary ammonium salt catalyst is 10 percent of that of the potassium permanganate, slowly dripping dodecafluoroheptanol into the reaction container, the mole ratio of the potassium permanganate to the dodecafluoroheptanol is 5:3, controlling the reaction temperature to be 80 ℃ after dripping, reacting for 0.75 hour, then carrying out suction filtration on reaction liquid, acidifying filtrate, extracting the acidified liquid with an extractant ketone, separating out an organic phase, distilling the organic phase, and collecting 192 ℃ fraction to obtain dodecafluoroheptanoic acid;
oxidation of dodecafluoroheptanol to give dodecafluoroheptanoic acid, the reaction is as follows:
H(CF2CF2)3CH2OH+[O]——H(CF2CF2)3COOH。
step two, chlorination: adding the dodecafluoroheptanoic acid obtained in the first step into another reaction container, adding ether, keeping the temperature below 30 ℃, dropwise adding thionyl chloride under the stirring condition, heating to 60 ℃ after dropwise adding, carrying out rectification to remove ether and excessive thionyl chloride after the reaction time is 4 hours, and obtaining a product, wherein the mass ratio of the dodecafluoroheptanoic acid to the ether to the thionyl chloride is 10:6: 5;
reacting dodecafluoroheptanoic acid with thionyl chloride to obtain dodecafluoroheptanoyl chloride, wherein the reaction is as follows:
H(CF2CF2)3COOH+SO2Cl2——H(CF2CF2)3COCl。
step three, fluorination: adding the product obtained in the step two into a fluorination reaction kettle, stirring and heating to 70 ℃, simultaneously introducing 25% fluorine gas from the bottom of the reaction kettle at the speed of 250ml/min, and continuously introducing the fluorine gas for 16.5 hours to obtain a fluorinated product;
the dodecafluoroheptanoyl chloride is fluorinated to obtain perfluoroheptanoyl fluoride, and the reaction is as follows: h (CF)2CF2)3COCl+F2——H(CF2CF2)3COF；
Step four, hydrolysis: heating the fluorinated product obtained in the third step to 50 ℃, adding deionized water, continuously stirring for 3 hours with the mass ratio of the fluorinated product to the deionized water being 10:1, and carrying out negative pressure rectification to obtain perfluoroheptanoic acid, wherein the comprehensive yield of the perfluoroheptanoic acid is 75.4%;
hydrolysis of perfluoroheptanoyl fluoride gives perfluoroheptanoic acid, the reaction is as follows:
F(CF2CF2)3COF+H2O——F(CF2CF2)3COOH。
further, the organic weak acid is selected from one or more of acetic acid, propionic acid, butyric acid and valeric acid; the quaternary ammonium salt catalyst is one of octadecyl trimethyl ammonium bromide, hexadecyl pyridine ammonium bromide, trioctyl methyl ammonium chloride and tetrabutyl ammonium bromide; acidifying the filtrate with sulfuric acid or hydrochloric acid, and extracting with acetone or butanone.
Example three:
a preparation process of perfluoroheptanoic acid comprises the following steps:
step one, oxidation: adding potassium permanganate, an organic weak acid solution and a quaternary ammonium salt catalyst into a reaction vessel, wherein the mass of the organic weak acid solution is 2 times that of the potassium permanganate, the molar number of the quaternary ammonium salt catalyst is 12% of that of the potassium permanganate, slowly dripping dodecafluoroheptanol into the reaction vessel, the molar ratio of the potassium permanganate to the dodecafluoroheptanol is 5:3, controlling the reaction temperature to be 85 ℃ after dripping, reacting for 0.5 hour, then carrying out suction filtration on reaction liquid, acidifying filtrate, extracting the acidified liquid with an extractant ketone, separating out an organic phase, distilling the organic phase, and collecting 192 ℃ fractions to obtain dodecafluoroheptanoic acid;
oxidation of dodecafluoroheptanol to give dodecafluoroheptanoic acid, the reaction is as follows:
H(CF2CF2)3CH2OH+[O]——H(CF2CF2)3COOH
step two, chlorination: adding the dodecafluoroheptanoic acid obtained in the first step into another reaction container, adding ether, keeping the temperature below 30 ℃, dropwise adding thionyl chloride under the stirring condition, heating to 65 ℃ after dropwise adding, carrying out rectification to remove ether and excessive thionyl chloride after the reaction time is 3 hours, and obtaining a product, wherein the mass ratio of the dodecafluoroheptanoic acid to the ether to the thionyl chloride is 10:6: 5;
reacting dodecafluoroheptanoic acid with thionyl chloride to obtain dodecafluoroheptanoyl chloride, wherein the reaction is as follows:
H(CF2CF2)3COOH+SO2Cl2——H(CF2CF2)3COCl
step three, fluorination: adding the product obtained in the step two into a fluorination reaction kettle, stirring and heating to 70 ℃, simultaneously introducing 25% fluorine gas from the bottom of the reaction kettle at the speed of 300ml/min, and continuously introducing the fluorine gas for 15 hours to obtain a fluorination product;
the dodecafluoroheptanoyl chloride is fluorinated to obtain perfluoroheptanoyl fluoride, and the reaction is as follows: h (CF)2CF2)3COCl+F2——H(CF2CF2)3COF。
Step four, hydrolysis: heating the fluorinated product obtained in the third step to 50 ℃, adding deionized water, continuously stirring for 3 hours with the mass ratio of the fluorinated product to the deionized water being 10:1, and carrying out negative pressure rectification to obtain perfluoroheptanoic acid, wherein the comprehensive yield of the perfluoroheptanoic acid is 75.3%;
hydrolysis of perfluoroheptanoyl fluoride gives perfluoroheptanoic acid, the reaction is as follows:
F(CF2CF2)3COF+H2O——F(CF2CF2)3COOH。
further, the organic weak acid is selected from one or more of acetic acid, propionic acid, butyric acid and valeric acid; the quaternary ammonium salt catalyst is one of octadecyl trimethyl ammonium bromide, hexadecyl pyridine ammonium bromide, trioctyl methyl ammonium chloride and tetrabutyl ammonium bromide; acidifying the filtrate with sulfuric acid or hydrochloric acid, and extracting with acetone or butanone.
The foregoing is only a preferred embodiment of the present invention; the scope of the invention is not limited thereto. Any person skilled in the art should be able to cover the technical scope of the present invention by equivalent or modified solutions and modifications within the technical scope of the present invention.
Claims (7)
1. A preparation process of perfluoroheptanoic acid is characterized by comprising the following steps: the method comprises the following steps:
step one, oxidation: adding potassium permanganate, an organic weak acid solution and a quaternary ammonium salt catalyst into a reaction container, slowly dripping dodecafluoroheptanol into the reaction container, controlling the reaction temperature to be 70-85 ℃ after dripping, performing suction filtration on reaction liquid after reacting for 0.5-1 hour, extracting the acidified liquid with an extractant ketone after filtrate is acidified, separating an organic phase, distilling the organic phase and collecting 192 ℃ fraction to obtain dodecafluoroheptanoic acid;
step two, chlorination: adding the dodecafluoroheptanoic acid obtained in the first step into another reaction container, adding diethyl ether, keeping the temperature below 30 ℃, dropwise adding thionyl chloride under the stirring condition, after dropwise adding, heating to 55-65 ℃, reacting for 3-5 hours, and rectifying to remove diethyl ether and excessive thionyl chloride to obtain a product;
step three, fluorination: adding the product obtained in the step two into a fluorination reaction kettle, stirring and heating to 70 ℃, simultaneously introducing 25% fluorine gas from the bottom of the reaction kettle at the speed of 200-300 ml/min, and continuously introducing the fluorine gas for 15-18 hours to obtain a fluorinated product;
step four, hydrolysis: and (3) heating the fluorinated product obtained in the third step to 50 ℃, adding deionized water, continuously stirring for 3 hours, and carrying out negative pressure rectification to obtain the perfluoroheptanoic acid.
2. The process according to claim 1, wherein the process comprises the following steps: the organic weak acid is selected from one or more of acetic acid, propionic acid, butyric acid and valeric acid, and the mass of the organic weak acid solution is 1-2 times that of potassium permanganate.
3. The process according to claim 1, wherein the process comprises the following steps: the quaternary ammonium salt catalyst is selected from one of octadecyl trimethyl ammonium bromide, hexadecyl pyridine ammonium bromide, trioctyl methyl ammonium chloride and tetrabutyl ammonium bromide, and the mole number of the quaternary ammonium salt catalyst is 8-12% of that of the potassium permanganate.
4. The process according to claim 1, wherein the process comprises the following steps: the molar ratio of the potassium permanganate to the dodecafluoroheptanol is 5: 3.
5. The process according to claim 1, wherein the process comprises the following steps: and acidifying the filtrate by using sulfuric acid or hydrochloric acid, wherein the extracting agent ketone is acetone or butanone.
6. The process according to claim 1, wherein the process comprises the following steps: in the second step, the mass ratio of the dodecafluoroheptanoic acid to the diethyl ether to the thionyl chloride is 10:6: 5.
7. The process according to claim 1, wherein the process comprises the following steps: the mass ratio of the fluorinated product to the deionized water is 10: 1.
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| CN202011248265.5A CN112358395A (en) | 2020-11-10 | 2020-11-10 | Preparation process of perfluoroheptanoic acid |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3606174A1 (en) * | 1986-02-26 | 1987-08-27 | Hoechst Ag | METHOD FOR PRODUCING PERFLUORIC CARBONIC ACIDS |
| CN101759551A (en) * | 2009-12-30 | 2010-06-30 | 济南大学 | Method for preparation of dodecafluoroheptanoic acid |
| RU2489416C1 (en) * | 2012-04-27 | 2013-08-10 | Открытое акционерное общество "ГалоПолимер Пермь" | Method of producing perfluorocarboxylic acid |
| CN106831388A (en) * | 2017-01-18 | 2017-06-13 | 济南齐氟新材料技术有限公司 | A kind of preparation method of perfluoro-heptanoic acid |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3606174A1 (en) * | 1986-02-26 | 1987-08-27 | Hoechst Ag | METHOD FOR PRODUCING PERFLUORIC CARBONIC ACIDS |
| CN101759551A (en) * | 2009-12-30 | 2010-06-30 | 济南大学 | Method for preparation of dodecafluoroheptanoic acid |
| RU2489416C1 (en) * | 2012-04-27 | 2013-08-10 | Открытое акционерное общество "ГалоПолимер Пермь" | Method of producing perfluorocarboxylic acid |
| CN106831388A (en) * | 2017-01-18 | 2017-06-13 | 济南齐氟新材料技术有限公司 | A kind of preparation method of perfluoro-heptanoic acid |
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