CN101774902A - Preparation method of polyfluoro aliphatic carboxylic acid - Google Patents
Preparation method of polyfluoro aliphatic carboxylic acid Download PDFInfo
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- CN101774902A CN101774902A CN201010022742A CN201010022742A CN101774902A CN 101774902 A CN101774902 A CN 101774902A CN 201010022742 A CN201010022742 A CN 201010022742A CN 201010022742 A CN201010022742 A CN 201010022742A CN 101774902 A CN101774902 A CN 101774902A
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Abstract
The invention discloses a preparation method of polyfluoro aliphatic carboxylic acid, which comprises the following concrete steps: oxidizing polyfluoro aliphatic alcohol by potassium permanganate to obtain polyfluoro carboxylic acid potassium salt, purifying intermediate products of fluorine-containing potassium carboxylate, namely washing for removing unreacted raw materials, and then, acidizing for releasing polyfluoro carboxylic acid. By utilizing the characteristic that the polyfluoro aliphatic alcohol is oxidized by the potassium permanganate to obtain the polyfluoro carboxylic acid, but the acidity of the polyfluoro carboxylic acid is further stronger than the acidity of acetic acid, so that the generated polyfluoro carboxylic acid is neutralized with potassium hydroxide released by the potassium permanganate in the reaction process to obtain the fluorine-containing carboxylic acid potassium salt, the invention adopts the method of firstly washing the fluorine-containing potassium carboxylate and then acidizing for releasing the polyfluoro carboxylic acid, thereby solving the problem that the polyfluoro aliphatic alcohol and the polyfluoro aliphatic carboxylic acid can not be rectified and separated easily. The polyfluoro aliphatic alcohol which is used as a raw material in the invention is prepared by telomerization of tetrafluoroethylene and belongs to an industrialized raw material. The process for preparing the polyfluoro aliphatic carboxylic acid by oxidizing the polyfluoro aliphatic alcohol has mild conditions and is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of polyfluoro aliphatic carboxylic acid class surface active cpd, being specifically related to a kind of is raw material with the polyfluoro Fatty Alcohol(C12-C14 and C12-C18), through technologies such as oxidation, washing purification, acidifying, extractions, prepare a kind of method of polyfluoro aliphatic carboxylic acid, belong to the synthetic field of fine chemicals.
Background technology
Fluorocarbon is the fluorinated organic compound that a class has significant application value, before its production and use can be traced back to 50 years.Because performances such as its remarkable chemical stability, weathering resistance, erosion resistance, thermotolerance, pollution-free, oxidation-resistance are widely used in industry and civil areas such as weaving, papermaking, packing, agricultural chemicals, carpet, leather, floor polishing, shampoo and fire foam.
Polyfluoro aliphatic carboxylic acid is a kind of very important fluorocarbon.Useful as surfactants, hydrophobic and oleophobic agent, and the intermediate of synthetic fluoropolymer.Can utilize the carboxyl-reactive in its molecular structure, by making polyfluoro aliphatic carboxylic acid salt with mineral alkali reactions such as sodium hydroxide, potassium hydroxide.Obtaining having simultaneously in the molecular structure polyfluoro aliphatic carboxylic acid salt of wetting ability carboxylate salt functional group and water and oil repellant Polyfluoroalkyl, is the surfactant of a class uniqueness.
The major industry synthetic method of perfluorocarboxylic acid is the electrochemical fluorination method, and promptly electrochemical fluorinated alkyl acyl chlorides makes polyfluoro or perfluoroalkyl acyl fluorides, and latter's hydrolysis again can prepare polyfluoro or perfluorocarboxylic acid.Chinese invention patent " method for preparing fluorocarboxylic acid " (publication number CN1684937A), a kind of method is disclosed, this method is included under the existence of aqueous sulfuric acid the hydrolysis of fluorocarboxylic acid acyl fluorides, generates the reaction product that contains fluoro carboxylic acid and hydrogen fluoride (form with hydrofluoric acid exists); And from reaction product, remove at least some hydrofluoric acid with aqueous sulfuric acid washing reaction product.Hydrolysis and washing are to carry out under fluorocarboxylic acid is the condition of liquid.But this method by product is many, and productive rate is low, and especially along with carbochain increases, productive rate reduces.Therefore, people more and more become the higher perfluorocarboxylic acid of synthetic yield under mild conditions and press for.
Different with hydrocarbon chain is, polyfluoro Fatty Alcohol(C12-C14 and C12-C18) that is derived by fluorocarbon chain and polyfluoro aliphatic carboxylic acid are because a little less than the intermolecular interaction, the boiling point difference is very little.Usually, the polyfluoro Fatty Alcohol(C12-C14 and C12-C18) is difficult to separate by the method for rectifying with polyfluoro aliphatic carboxylic acid.
Summary of the invention
The objective of the invention is the deficiency at the prior art existence, provide a kind of synthetic method simple, the reaction conditions gentleness is easy to purify the preparation method of the polyfluoro aliphatic carboxylic acid that product purity is high.
For achieving the above object, technical scheme of the present invention is: a kind of preparation method of polyfluoro aliphatic carboxylic acid comprises the steps:
(1) by weight, 100 parts of fluorine-containing alcohols, 100～300 parts of acetic acid and 100～200 parts of potassium permanganate joined successively in 300～800 parts the water, stir, under 60～90 ℃ temperature condition, carried out oxidizing reaction 2～8 hours;
(2) mixture that oxidizing reaction is obtained is cooled to room temperature, obtains water white transparency filtrate after the filtration; As washing composition, it is washed purification processes with organic solvent, obtain containing the carboxylic acid fluoride sylvite aqueous solution; By weight, washing composition: fluorine-containing alcohol is 1: 1～6;
(3) carrying out acidification with hydrochloric acid to containing the carboxylic acid fluoride sylvite aqueous solution, obtain the acidizing fluid of pH=2, is extraction agent with the organic solvent again, and acidizing fluid is extracted; By weight, extraction agent: fluorine-containing alcohol is 1: 1～10;
(4) in extraction liquid, add siccative and carry out drying treatment; By weight, siccative: fluorine-containing alcohol is 0.05～0.5: 1; The drying treatment time is 0.5～10 hour;
(5) remove by filter siccative after, be 20～80 ℃ in temperature, vacuum tightness is under the condition of 0.5～20mmHg, filtrate is carried out underpressure distillation handle, and removes extraction agent, obtains a kind of polyfluoro aliphatic carboxylic acid.
Described fluorine-containing alcohol is: 2,2,3, and 3-C3-Fluoroalcohol, 2,2,3,4,4,4-hexafluoro butanols, 2,2,3,3,4,4,5,5-octafluoropentanol, 2,2,3,3,4,4,5,5,6,6,7,7-ten difluoro enanthol or 2,2,3,3,4,4,5,5,6,6,7,7, a kind of in the 7-ten trifluoro enanthol.
Described washing composition is a kind of in ethyl acetate, chloroform, methylene dichloride, ethylene dichloride, sherwood oil, Skellysolve A, normal hexane or the normal heptane, or any two kinds mixture in them.
Described extraction agent is a kind of in ethyl acetate, chloroform, methylene dichloride, ethylene dichloride, sherwood oil, Skellysolve A, normal hexane or the normal heptane, or any two kinds mixture in them.
Described siccative is anhydrous sodium sulphate or anhydrous magnesium sulfate.
Compare with conventional art, the invention has the advantages that: prepare polyfluoro aliphatic carboxylic acid with the potassium permanganate oxidation fluorine-containing alcohol, the technology environmental protection, byproduct of reaction is few, the productive rate height, and the carbon chain lengths of reaction yield and fluorine-containing alcohol is irrelevant.Technical solution of the present invention adopts in oxidizing reaction and finishes the back by removing unreacted raw material to containing the washing of carboxylic acid fluoride potassium intermediate product earlier, carry out acidification again, since the acidity that contains carboxylic acid fluoride than hydrochloric acid a little less than, therefore contain carboxylic acid fluoride sylvite and hydrochloric acid reaction and generate Repone K, containing carboxylic acid fluoride simultaneously discharges and dissociates out, discharge multi-fluoro carboxy acid's method by acidifying, can solve the problem that polyfluoro Fatty Alcohol(C12-C14 and C12-C18) and polyfluoro aliphatic carboxylic acid are difficult to rectifying separation.The last polyfluoro aliphatic carboxylic acid that goes out to obtain through rectifying again is easy to purify the polyfluoro aliphatic carboxylic acid product purity height that obtains.Synthetic method of the present invention is simple, and the reaction conditions gentleness is easy to implement.
Embodiment
Below in conjunction with embodiment the present invention is further described:
Embodiment 1
Synthetic 2,2,3,3,4,4,5,5-octafluoro valeric acid:
There-necked flask at 2L adds 2,2,3,3,4,4,5 successively, 5-octafluoropentanol 116.0g, 700g water, 200g acetic acid.Stirring is warming up to 80 ℃, divides three times and adds potassium permanganate 126.4g, insulation reaction 4 hours.Be cooled to room temperature, filter water white transparency filtrate.Filtrate is divided three washings with the 300g ethyl acetate, is acidified to pH=2 with concentrated hydrochloric acid again, divides three extractions with the 750g ethyl acetate, extraction liquid washing, add the 12g anhydrous sodium sulfate drying 1 hour, cross the filtering siccative, concentrate crude product, rectifying gets 96.0g product 2,2,3,3,4,4,5,5-octafluoro valeric acid, recording its purity by gas-chromatography is 98.5%.Yield 78.0%.Product IR v:3219.8 (COOH), 2997.4 (H-CF
2), 1776.1 (C=O), 1181.8,1078.3 (C-F).
Embodiment 2
There-necked flask at 2L adds 2,2,3,3,4,4,5 successively, 5-octafluoropentanol 116.0g, 700g water, 200g acetic acid.Stirring is warming up to 80 ℃, divides three times and adds potassium permanganate 142.2g, insulation reaction 4 hours.Cold filtration gets water white transparency filtrate.Filtrate is divided three washings with the 300g methylene dichloride, is acidified to pH=2 with concentrated hydrochloric acid again, divides three extractions with the 750g methylene dichloride, extraction liquid washing adds the 10g anhydrous magnesium sulfate drying, crosses filtering siccative 30 minutes, filtrate concentrate crude product, rectifying gets 104.6g product 2,2,3,3,4,4,5,5-octafluoro valeric acid, recording its purity by gas-chromatography is 98.0%.Yield 85.1%.
Embodiment 3
There-necked flask at 2L adds 2,2,3,3,4,4,5 successively, 5-octafluoropentanol 116.0g, 700g water, 200g acetic acid.Stirring is warming up to 90 ℃, divides three times and adds potassium permanganate 158.0g, insulation reaction 5 hours.Cold filtration gets water white transparency filtrate.Filtrate is divided three washings with the 300g ethylene dichloride, is acidified to pH=2 with concentrated hydrochloric acid again, divides three extractions with the 750g ethylene dichloride, extraction liquid washing, add the 12g anhydrous sodium sulfate drying 2 hours, cross the filtering siccative, filtrate concentrate crude product, rectifying gets 111.4g product 2,2,3,3,4,4,5,5-octafluoro valeric acid, recording its purity by gas-chromatography is 98.7%.Yield 90.6%.
Embodiment 4
Synthetic 2,2,3,3-tetrafluoro propionic acid:
There-necked flask at 2L adds 2,2,3 successively, 3-C3-Fluoroalcohol 66.0g, 700g water, 120g acetic acid.Stirring is warming up to 90 ℃, divides three times and adds potassium permanganate 158.0g, insulation reaction 5 hours.Cold filtration gets water white transparency filtrate.Filtrate is divided three washings with the 240g methylene dichloride, be acidified to pH=2 with concentrated hydrochloric acid again, divide three extractions, the extraction liquid washing with the 450g methylene dichloride, added the 10g anhydrous sodium sulfate drying 1 hour, filtering siccative, filtrate concentrate crude product, rectifying gets 65.3g product 2,2,3,3-tetrafluoro propionic acid, recording its purity by gas-chromatography is 96.6%.Yield 89.5%.Product IR v:3226.0 (COOH), 2996.1 (H-CF
2), 1773.2 (C=O), 1182.9,1080.6 (C-F).
Embodiment 5
Synthetic 2,2,3,4,4,4-hexafluoro butyric acid:
There-necked flask at 2L adds 2,2,3,4,4 successively, 4-hexafluoro butanols 73.0g, 700g water, 200g acetic acid.Stirring is warming up to 85 ℃, divides three times and adds potassium permanganate 153.1g, insulation reaction 5 hours.Cold filtration gets water white transparency filtrate.Filtrate is divided three washings with the 300g normal hexane, is acidified to pH=2 with concentrated hydrochloric acid again, divides three extractions with the 450g normal hexane, the extraction liquid washing, add the 20g anhydrous magnesium sulfate drying 1 hour, cross the filtering siccative, filtrate concentrate crude product, rectifying gets 69.2g product 2,2,3,4,4,4-hexafluoro butyric acid, recording its purity by gas-chromatography is 96.6%.Yield 86.5%.Product IR v:3225.3 (COOH), 2993.1 (H-CF), 1770.6 (C=O), 1176.8,1082.6 (C-F).
Claims (5)
1. the preparation method of a polyfluoro aliphatic carboxylic acid is characterized in that comprising the steps:
(1) by weight, 100 parts of fluorine-containing alcohols, 100～300 parts of acetic acid and 100～200 parts of potassium permanganate joined successively in 300～800 parts the water, stir, under 60～90 ℃ temperature condition, carried out oxidizing reaction 2～8 hours;
(2) mixture that oxidizing reaction is obtained is cooled to room temperature, obtains water white transparency filtrate after the filtration; As washing composition, it is washed purification processes with organic solvent, obtain containing the carboxylic acid fluoride sylvite aqueous solution; By weight, washing composition: fluorine-containing alcohol is 1: 1～6;
(3) carrying out acidification with hydrochloric acid to containing the carboxylic acid fluoride sylvite aqueous solution, obtain the acidizing fluid of pH=2, is extraction agent with the organic solvent again, and acidizing fluid is extracted; By weight, extraction agent: fluorine-containing alcohol is 1: 1～10;
(4) in extraction liquid, add siccative and carry out drying treatment; By weight, siccative: fluorine-containing alcohol is 0.05～0.5: 1; The drying treatment time is 0.5～10 hour;
(5) remove by filter siccative after, be 20～80 ℃ in temperature, vacuum tightness is under the condition of 0.5～20mmHg, filtrate is carried out underpressure distillation handle, and removes extraction agent, obtains polyfluoro aliphatic carboxylic acid.
2. the preparation method of a kind of polyfluoro aliphatic carboxylic acid according to claim 1, it is characterized in that: described fluorine-containing alcohol is: 2,2,3,3-C3-Fluoroalcohol, 2,2,3,4,4,4-hexafluoro butanols, 2,2,3,3,4,4,5,5-octafluoropentanol, 2,2,3,3,4,4,5,5,6,6,7,7-ten difluoro enanthol or 2,2,3,3,4,4,5,5,6,6,7,7, a kind of in the 7-ten trifluoro enanthol.
3. the preparation method of a kind of polyfluoro aliphatic carboxylic acid according to claim 1, it is characterized in that: described washing composition is a kind of in ethyl acetate, chloroform, methylene dichloride, ethylene dichloride, sherwood oil, Skellysolve A, normal hexane or the normal heptane, or any two kinds mixture in them.
4. the preparation method of a kind of polyfluoro aliphatic carboxylic acid according to claim 1, it is characterized in that: described extraction agent is a kind of in ethyl acetate, chloroform, methylene dichloride, ethylene dichloride, sherwood oil, Skellysolve A, normal hexane or the normal heptane, or any two kinds mixture in them.
5. the preparation method of a kind of polyfluoro aliphatic carboxylic acid according to claim 1, it is characterized in that: described siccative is anhydrous sodium sulphate or anhydrous magnesium sulfate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277163A (en) * | 2013-07-01 | 2015-01-14 | 山东东岳高分子材料有限公司 | Fluorine-containing carboxylic acid emulsifier and preparation method of fluorine-containing polymer |
| CN104355987A (en) * | 2014-11-17 | 2015-02-18 | 中昊晨光化工研究院有限公司 | Method for preparing octafluorovaleric acid under catalytic oxidation action of oxydol |
| CN108569962A (en) * | 2017-03-07 | 2018-09-25 | 中昊晨光化工研究院有限公司 | A kind of method of phase transfer catalysis (PTC) potassium permanganate oxidation synthesis dodecafluoroheptanoiacid acid |
| CN111333501A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Preparation method of fluorine-containing carboxylic acid |
| CN111333499A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Process for producing fluorine-containing carboxylic acid |
| CN113045380A (en) * | 2019-12-26 | 2021-06-29 | 中蓝晨光化工研究设计院有限公司 | Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin |
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| CN1405141A (en) * | 2002-11-04 | 2003-03-26 | 东华大学 | Fluoro polybasic carboxylic acid synthesis method and use thereof |
| US6891064B1 (en) * | 1998-06-03 | 2005-05-10 | Daikin Industries, Ltd. | Process for producing fluoroalkylcarboxylic acid |
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Patent Citations (3)
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| DD268685B1 (en) * | 1988-02-12 | 1990-10-24 | Nuenchritz Chemie | PROCESS FOR THE PREPARATION OF OMEGA-H-POLYFLUORCARBONSAEURES |
| US6891064B1 (en) * | 1998-06-03 | 2005-05-10 | Daikin Industries, Ltd. | Process for producing fluoroalkylcarboxylic acid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104277163A (en) * | 2013-07-01 | 2015-01-14 | 山东东岳高分子材料有限公司 | Fluorine-containing carboxylic acid emulsifier and preparation method of fluorine-containing polymer |
| CN104355987A (en) * | 2014-11-17 | 2015-02-18 | 中昊晨光化工研究院有限公司 | Method for preparing octafluorovaleric acid under catalytic oxidation action of oxydol |
| CN104355987B (en) * | 2014-11-17 | 2016-01-06 | 中昊晨光化工研究院有限公司 | A kind of hydrogen peroxide catalytic oxidation prepares the method for octafluoro valeric acid |
| CN108569962A (en) * | 2017-03-07 | 2018-09-25 | 中昊晨光化工研究院有限公司 | A kind of method of phase transfer catalysis (PTC) potassium permanganate oxidation synthesis dodecafluoroheptanoiacid acid |
| CN111333501A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Preparation method of fluorine-containing carboxylic acid |
| CN111333499A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Process for producing fluorine-containing carboxylic acid |
| CN111333501B (en) * | 2018-12-19 | 2022-11-04 | 中蓝晨光化工研究设计院有限公司 | Preparation method of fluorine-containing carboxylic acid |
| CN111333499B (en) * | 2018-12-19 | 2023-02-10 | 中蓝晨光化工研究设计院有限公司 | Process for producing fluorine-containing carboxylic acid |
| CN113045380A (en) * | 2019-12-26 | 2021-06-29 | 中蓝晨光化工研究设计院有限公司 | Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin |
| CN113045380B (en) * | 2019-12-26 | 2023-03-14 | 中蓝晨光化工研究设计院有限公司 | Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin |
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