CN107118074B - A method of purification perfluoromethylcyclohexane (PFMCH) - Google Patents
A method of purification perfluoromethylcyclohexane (PFMCH) Download PDFInfo
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Abstract
The invention discloses a kind of methods for purifying perfluoromethylcyclohexane (PFMCH), comprising the following steps: (1) the perfluoromethylcyclohexane (PFMCH) crude product for preparing electrofluorination method is added aqueous alkali and is neutralized to upper strata aqueous phase as neutrality；Liquid separation is stood, lower layer's organic phase is transferred to distillation still；(2) simple distillation；(3) it extracts；(4) depth is fluorinated: component is passed through fluorine gas nitrogen mixture after to above-mentioned extraction, in -20~10 DEG C of reaction 0.5-10h, then leads to nitrogen purging displacement gaseous mixture；(5) alkali soluble: being transferred to reaction kettle for the perfluoromethylcyclohexane (PFMCH) after above-mentioned fluorination, and alcohol-alkali-aqueous solution of mass ratio 1: 1: 1 is added into reaction kettle, flows back after 10h, takes lower layer's organic phase, dry；(6) rectifying；(7) multi-stage absorption-desorption.This method is suitable for the purification of the perfluoromethylcyclohexane (PFMCH) crude product of electrofluorination method preparation, and process is simple to operation, it is easy to accomplish industrial production, product purity obtained is up to 99.9% or more.
Description
Technical field
The present invention relates to the methods of purification of electrofluorination method preparation high-purity perfluoromethylcyclohexane (PFMCH) product.
Background technique
Perfluoromethylcyclohexane (PFMCH) is one kind of fluorine system cleaning agent, since the fluorine atom contained has strong electron-withdrawing ability,
So that fluorine system cleaning agent can not only clean nonpolar organic pollutant, but also polar inorganic pollution can be cleaned, while by
It is smaller in its surface tension and viscosity, compared with other solvents of identical boiling point, and have many advantages, such as to be easy evaporation, be answered extensively
Cleaning for manufacturing enterprises such as precision instrument, liquid crystal, medical instruments.Furthermore perfluoromethylcyclohexane (PFMCH) is a kind of perfluoro solvent,
It can be applied to fluorine two-phase reaction system.
The synthetic method of perfluoromethylcyclohexane (PFMCH) has metal pentafluoride method and electrofluorination method.US3871975, US3876515 are public
A kind of method that electrofluorination prepares perfluoromethylcyclohexane (PFMCH) is opened, using benzotrifluoride as raw material, NaF is as conductive agent, nitrogen
Bottom is bubbled, and obtains fluorinated product after collection.Wherein perfluor C7 cyclic compound (perfluoromethylcyclohexane (PFMCH) 33.0g and perfluor 1,3
Dimethyl cyclohexane 4.2g etc.) yield 53.5%.Because electrofluorination process is complicated, dopant species are more and feed stock conversion is low, with
Product is miscible, and the perfluoromethylcyclohexane (PFMCH) crude product purification difficulty for causing electrofluorination method to be collected is big, it is difficult to obtain high purity product.
Either metal pentafluoride method or electrofluorination method, perfluoromethylcyclohexane (PFMCH) can generate polyfluorinated organic during the preparation process
It closes object (such as hydrogeneous, unsaturated bond), perfluorinated decomposition product, resin-like product and contains hetero atom-fluorine chain compound.These are changed
The quality and performance of target product can be reduced by closing object, such as increased viscosity, corrosion activity, toxicity and reduced dielectric properties.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of methods for purifying perfluoromethylcyclohexane (PFMCH).This method is suitable for electricity
The purification of the perfluoromethylcyclohexane (PFMCH) crude product of fluoride process preparation is solved, product purity obtained is up to 99.9% or more.
In order to solve the above-mentioned technical problem, the technical scheme is that it is a kind of purify perfluoromethylcyclohexane (PFMCH) method,
The perfluoromethylcyclohexane (PFMCH) crude product that electrofluorination method is obtained, neutralized, distillation, extraction, depth fluorination, alkali soluble, rectifying, multistage
Adsorption-desorption obtains high-purity perfluoromethylcyclohexane (PFMCH) product.
The perfluoromethylcyclohexane (PFMCH) crude product refers to that the mixing using benzotrifluoride as raw material, prepared through electrofluorination method produces
Object, main component are as follows: the changed perfluorochemical of a, carbon skeleton, such as perflexane, perfluorocyclohexane, PF 5070, complete
Fluorine 1,3- dimethyl cyclohexane etc.；B, incomplete fluoro product, such as perfluoro-methyl cyclohexene, 3- fluoride trifluoro toluene, ten fluorine of 3- hydrogen
Hexamethylene etc., the mixture of c, perfluorinated polymers and polyfluorinated polymer；D, oxidative impurities；E: incomplete reaction raw materials three
Toluene fluoride.
The method of purification perfluoromethylcyclohexane (PFMCH) of the present invention, comprising the following steps:
1) neutralize: perfluoromethylcyclohexane (PFMCH) crude product prepared by electrofluorination method is passed through neutralization reaction kettle, and it is molten that buck is added
Liquid is neutralized to upper strata aqueous phase as neutrality；Liquid separation is stood, lower layer's organic phase is transferred to distillation still.Alkali suitable for neutralization is generally
Weak base, such as sodium carbonate, sodium bicarbonate, aqueous alkali mass concentration general 5%~20%.
2) it distills: carrying out simple distillation, collect 70~80 DEG C of fractions.
3) extract: Xiang Shangshu fraction is passed through extractant, sufficiently extracts.The extractant is to mix with perfluoromethylcyclohexane (PFMCH)
Property poor, boiling point and perfluoromethylcyclohexane (PFMCH) boiling point differ greatly and easily by rectifying remove solvent.Such as hydrogen chlorocarbon class: dichloro
Methane, chloroform, 1,2- dichloroethanes, tetrachloromethane, preferably methylene chloride；Alcohols: methanol, ethyl alcohol, isopropanol etc.；Nitrile
Class: acetonitrile, propionitrile etc., preferably acetonitrile.Extractant may be reused, and extractant and fraction volume ratio are generally 10: 1~1:
10。
4) depth is fluorinated: component is passed through fluorine gas nitrogen mixture after to above-mentioned extraction, in -20~10 DEG C of reaction 0.5-10h,
Then lead to nitrogen purging displacement fluorine gas nitrogen mixture.The fluorine nitrogen mixed gas volume concentration is generally 2%~10%, preferably
For the diluted fluorine gas of 2%~20% nitrogen, more preferably 2%~5%.
5) alkali soluble: being transferred to reaction kettle for the perfluoromethylcyclohexane (PFMCH) after above-mentioned fluorination, and mass ratio 1 is added into reaction kettle
: 1: 1 alcohol-alkali-aqueous solution flows back after 10h, takes lower layer's organic phase, and it is spare that desiccant dryness is added.The alkali be alkali metal or
The hydroxide of alkaline-earth metal, preferably sodium hydroxide, potassium hydroxide；Alcohol is preferably methanol or ethyl alcohol.Desiccant such as molecular sieve,
Anhydrous sodium sulfate etc..
6) rectifying: rectifying in rectifying tower reactor is added to by step 5) is organic.Rectifying tower packing is preferable with triangle helical packing.
The infinite reflux time is generally 1~10h, and reflux ratio is generally 100: 1~1: 100, preferably 20: 1~1: 20, more preferably 10:
1。
7) multi-stage absorption-desorption: the perfluoromethylcyclohexane (PFMCH) that step 6) rectifying is collected passes through the multistage equipped with adsorbent
Adsorbent bed is adsorbed to saturation, then adsorbent bed adsorbent is heated, nitrogen purging, the chilled collection of perfluoromethylcyclohexane (PFMCH) after desorption
Obtain the perfluoromethylcyclohexane (PFMCH) product of high-purity.The multi-stage absorption bed is three-level absorption, the absorption of first order adsorbent bed
Agent is diatomite, and the adsorbent of second and third grade of adsorbent bed is active carbon, preferably cocoanut active charcoal.Desorption temperature is 70~200
DEG C preferably, preferential 80~100 DEG C.
The method of purification perfluoromethylcyclohexane (PFMCH) of the present invention, the perfluoro-methyl hexamethylene suitable for the preparation of electrofluorination method
The purification of alkane crude product eliminates hydrogen fluoride, low volatility high-boiling-point impurity, benzotrifluoride, incomplete fluoric compound, polyfluoro and takes
The trace impurities such as the impurity such as the unsaturated product in generation and hydrogen atom, hetero atom and unsaturated bond, product purity obtained are reachable
99.9% or more, hydrogen atom, hetero atom and unsaturated bond content are not detected, and can meet high-precision industry cleaning link requirement, make
It is long with the service life.This method process is simple to operation, it is easy to accomplish industrial production.
Detailed description of the invention
Fig. 1 is present invention process general flow chart
Fig. 2 is 2 product gas chromatogram partial enlarged view of embodiment.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
The perfluoromethylcyclohexane (PFMCH) crude product collected using electrofluorination method.
(1) Na of configuration quality concentration 10%2CO3Aqueous solution is slowly added into the 1000mL collected equipped with electrofluorination method
In perfluoromethylcyclohexane (PFMCH) crude product perfluoroethylene-propylene (copolymer) beaker, stirring is leaked using pH test paper measurement upper strata aqueous phase to neutrality with liquid separation
Struggle against liquid separation, takes lower layer's rufous organic phase.200mL distilled water is used every time, is washed twice, liquid separation, bottom rufous organic phase
Middle addition 20g anhydrous sodium sulfate drying for standby.
(2) 2000mL glass normal pressure simple distillation device, the air-tightness of check device are built；It, will after nitrogen displacement three times
The bottom rufous that step (1) obtains is organic to be added in there-necked flask, opens heating distillation, it is total to collect 70~80 DEG C of fractions
700mL, perfluoromethylcyclohexane (PFMCH) content is 64.3% as the result is shown for gas chromatographic analysis, and benzotrifluoride content is 21.5%,
His perfluoro and hydrogeneous polyfluoro are 14.2% for impurity such as property.
(3) mechanical stirring device is built, the methylene chloride that volume ratio 1: 2 is added in fraction is collected in step (2), is acutely stirred
10min is mixed, liquid separation collects methylene chloride and mutually saves standby reuse, bottom organic phase, and decompression, which evacuates, removes methylene chloride, altogether
About 650mL is collected, through gas chromatographic analysis wherein perfluoromethylcyclohexane (PFMCH) content about 83.3%, methylene chloride content 1.0%, three
Toluene fluoride content about 2.3%, the impurity such as other perfluoros and hydrogeneous polyfluoro generation are 13.4%.
(4) it is added to bottom that step (3) obtains is organic in 1000mLPTFE there-necked flask, is cooled to -10 DEG C, under stirring
After being passed through 2% fluorine nitrogen mixed gas 8h with 300mL/min rate, nitrogen purges 30min.
(5) into step (4) PTFE container, the KOH: ethyl alcohol: aqueous solution, there-necked flask of 1: 1: 1 weight ratio of 650mL is added
It is connected into condensing reflux pipe, keeps slightly boiled reflux 10h.Liquid separation after cooling, organic phase are washed with distilled water three times, drying for standby.It receives
Collection obtains obtaining organic 550mL that makes an appointment, chromatography perfluoromethylcyclohexane (PFMCH) content 96.6% as the result is shown, benzotrifluoride content
1.2%, methylene chloride content 0.2%, the impurity such as perfluoro and hydrogeneous polyfluoro generation are 2.0%.
(6) it is added to organic in step 5) in rectifying tower reactor, the heating of unlatching tower reactor, overhead condensation, after infinite reflux 4h, adjusts
Saving reflux ratio is 10: 1, collects 75 DEG C~78 DEG C or more components, and through gas chromatographic analysis, wherein perfluoromethylcyclohexane (PFMCH) content is about
99.2%, benzotrifluoride content about 0.1%, the impurity such as perfluoro and hydrogeneous polyfluoro generation are 0.7%.The rectifying column, in tower
Diameter is 50mm, using high vacuum silvered glass column, built-in 2mm × 2mm stainless steel triangle helical packing, and packed height 1500mm,
Tower reactor volume is 1000mL.
(7) component of the collection in step 6) is passed sequentially through into three-level adsorbent bed to being saturated, is desorbed at 100 DEG C,
Obtained perfluoromethylcyclohexane (PFMCH) content about 99.92%, perfluor 1 are collected in freezing, and 3- dimethyl cyclohexane is 0.08% for content,
Product is obviously absorbed in the ultraviolet nothing of 200~320nm shows no unsaturated bond and hetero atom, and hydrogen spectrum analysis does not find hydrogeneous chemical combination
Object.
Embodiment 2
(1) NaHCO of configuration 5%3Solution is slowly added into the 2000mL perfluoro-methyl ring collected equipped with electrofluorination method
In hexane crude product FEP beaker, stirring, using pH test paper measurement upper strata aqueous phase to neutrality, separatory funnel liquid separation takes lower layer's rufous
Organic phase.It is washed twice using 500mL distilled water, liquid separation, it is standby that the drying of 20g anhydrous sodium sulfate is added in the rufous organic phase of bottom
With.
(2) 2000mL glass normal pressure simple distillation device, the air-tightness of check device are built；It, will after nitrogen displacement three times
The bottom rufous that step (1) obtains is organic to be added in there-necked flask, opens heating distillation, it is total to collect 70-80 DEG C of fraction
1500mL, perfluoromethylcyclohexane (PFMCH) content is 89.6% as the result is shown for gas chromatographic analysis, and benzotrifluoride content is 0.93%,
His perfluoro and oxidative impurities are 9.47%.
(3) 1: 4 acetonitrile is added, is vigorously stirred 10min, liquid separation collects acetonitrile and mutually saves standby reuse, and bottom is organic
About 1450mL is mutually collected altogether, through gas chromatographic analysis wherein perfluoromethylcyclohexane (PFMCH) content about 93.6%, ethane nitrile content 0.8%,
Benzotrifluoride content about 0.53%, the impurity such as other perfluoros and hydrogeneous polyfluoro generation are 5.07%.
(4) it is added to bottom that step (3) obtains is organic in 2000mLPTFE there-necked flask, is cooled to -10 DEG C, under stirring
After being passed through 5% fluorine nitrogen mixed gas 2h with 200mL/min rate, nitrogen purges 30min.
(5) into step (4) PTFE container, it is added the KOH: ethyl alcohol: aqueous solution of 1: 1: 1 weight ratio of 1450mL, three mouthfuls
Bottle is connected into condensing reflux pipe, opens cooling, keeps slightly boiled reflux 10h.Liquid separation after cooling, organic phase are washed with distilled water three times,
Drying for standby.Collection obtains obtaining organic 1400mL that makes an appointment, chromatography perfluoromethylcyclohexane (PFMCH) content 97.8% as the result is shown, and three
Toluene fluoride content 0.25%, the impurity such as other perfluoros and hydrogeneous polyfluoro generation are 3.95%.
(6) it is added to organic in step 5) in rectifying tower reactor, the heating of unlatching tower reactor, overhead condensation, after infinite reflux 2h, adjusts
Saving reflux ratio is 10: 1, collects 75 DEG C~78 DEG C or more components, and through gas chromatographic analysis, wherein perfluoromethylcyclohexane (PFMCH) content is about
99.6%, benzotrifluoride content about 0.20%, the impurity such as other perfluoros and hydrogeneous polyfluoro generation) it is 0.20%.
(7) component of the collection in step 6) is passed sequentially through into three-level adsorbent bed to being saturated, is desorbed at 80 DEG C, it is cold
Freeze the perfluoromethylcyclohexane (PFMCH) content about 99.983% collected and obtained, perfluor 1, the content of 3- dimethyl cyclohexane is 0.017%,
Product is obviously absorbed in the ultraviolet nothing of 200~320nm, and hydrogen spectrum analysis does not find hydrogen-containing compound.
Product analysis (attached drawing 2) the result is as follows:
| Peak number | Retention time | Area | Highly | Area % | Label | Compound name |
| 1 | 1.243 | 398699109 | 140572901 | 99.983 | SV | Perfluoromethylcyclohexane (PFMCH) |
| 2 | 1.517 | 68674 | 24759 | 0.017 | T | Perfluor 1,3- dimethyl cyclohexane |
| It amounts to | 398767783 | 140597660 | 100.000 |
Claims (10)
1. a kind of method for purifying perfluoromethylcyclohexane (PFMCH), comprising the following steps:
(1) neutralize: perfluoromethylcyclohexane (PFMCH) crude product prepared by electrofluorination method is passed through neutralization reaction kettle, and aqueous alkali is added
Upper strata aqueous phase is neutralized to as neutrality；Liquid separation is stood, lower layer's organic phase is transferred to distillation still；
(2) it distills: carrying out simple distillation, collect 70~80 DEG C of fractions；
(3) extract: Xiang Shangshu fraction is passed through extractant, sufficiently extracts；
(4) depth is fluorinated: component is passed through fluorine gas nitrogen mixture after to above-mentioned extraction, in -20~10 DEG C of reaction 0.5-10h, so
Lead to nitrogen purging displacement fluorine gas nitrogen mixture afterwards；
(5) alkali soluble: being transferred to reaction kettle for the perfluoromethylcyclohexane (PFMCH) after above-mentioned fluorination, and mass ratio 1: 1 is added into reaction kettle:
1 alcohol-alkali-aqueous solution flows back after 10h, takes lower layer's organic phase, and it is spare that desiccant dryness is added；
(6) rectifying: rectifying in rectifying tower reactor is added to by step (5) is organic；
(7) multi-stage absorption-desorption: the perfluoromethylcyclohexane (PFMCH) that step (6) rectifying is collected passes through the multistage suction equipped with adsorbent
Attached bed is adsorbed to saturation, then adsorbent bed adsorbent is heated, nitrogen purging, and perfluoromethylcyclohexane (PFMCH) is chilled after desorption collects
To the perfluoromethylcyclohexane (PFMCH) product of high-purity.
2. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 1, alkali used in step (1) aqueous alkali are carbon
Sour sodium or sodium bicarbonate, aqueous alkali mass concentration are 5%~20%.
3. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 1, the extractant are and perfluoro-methyl hexamethylene
The solvent that alkane intermiscibility is poor, boiling point and perfluoromethylcyclohexane (PFMCH) boiling point differ greatly and easily removed by rectifying.
4. it is according to claim 3 purification perfluoromethylcyclohexane (PFMCH) method, the extractant be hydrogen chlorocarbon class, alcohols or
Nitrile solvents；Extractant and fraction volume ratio are 10: 1~1: 10.
5. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 4, the extractant are methylene chloride, three chloromethanes
Alkane, 1,2- dichloroethanes, tetrachloromethane, methanol, ethyl alcohol, isopropanol, acetonitrile or propionitrile.
6. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 1, fluorine gas nitrogen mixture described in step (4)
Volumetric concentration is 2%~10%.
7. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 1, in step (5) alcohol-alkali-aqueous solution
Alkali is the hydroxide of alkali or alkaline earth metal.
8. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 1, in step (5) alcohol-alkali-aqueous solution
Alkali is sodium hydroxide or potassium hydroxide；Alcohol is methanol or ethyl alcohol；Desiccant is molecular sieve or anhydrous sodium sulfate.
9. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 1, step (6) rectifying tower packing are triangle spiral
Filler；The infinite reflux time is 1~10h, reflux ratio 100: 1~1: 100.
10. the method for purification perfluoromethylcyclohexane (PFMCH) according to claim 1, step (6) desorption temperature are 70~200
℃；The multi-stage absorption bed is three-level absorption, and the adsorbent of first order adsorbent bed is diatomite, second and third grade of adsorbent bed
Adsorbent is active carbon.
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| CN112064053B (en) * | 2020-09-17 | 2021-10-12 | 济源市恒顺新材料有限公司 | Stirring type fluorination electrolytic tank |
| CN112986436B (en) * | 2021-02-24 | 2023-03-10 | 核工业理化工程研究院 | Gas chromatography quantitative analysis method of perfluoromethylcyclohexane |
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| US3871975A (en) * | 1972-06-01 | 1975-03-18 | Shunji Nagase | Electrolytic process for production of perfluorocyclohexane derivatives |
| US3876515A (en) * | 1972-12-27 | 1975-04-08 | Agency Ind Science Techn | Method for manufacture of perfluorocyclohexane derivatives |
| WO2002026673A1 (en) * | 2000-09-26 | 2002-04-04 | 3M Innovative Properties Company | Method for purifying perfluorocarbons |
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| US3004908A (en) * | 1957-08-14 | 1961-10-17 | Haszeldine Robert Neville | Treatment of fluorinated hydrocarbons |
| US3871975A (en) * | 1972-06-01 | 1975-03-18 | Shunji Nagase | Electrolytic process for production of perfluorocyclohexane derivatives |
| US3876515A (en) * | 1972-12-27 | 1975-04-08 | Agency Ind Science Techn | Method for manufacture of perfluorocyclohexane derivatives |
| CN1455699A (en) * | 2000-09-14 | 2003-11-12 | 昭和电工株式会社 | Adsorbent for purifying perfluorocarbon, process for producing same, high purity octafluoropropane and octafluorocyclobutane and use thereof |
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