CN103739450A - Preparation method of hydrofluoroether - Google Patents
Preparation method of hydrofluoroether Download PDFInfo
- Publication number
- CN103739450A CN103739450A CN201310744750.5A CN201310744750A CN103739450A CN 103739450 A CN103739450 A CN 103739450A CN 201310744750 A CN201310744750 A CN 201310744750A CN 103739450 A CN103739450 A CN 103739450A
- Authority
- CN
- China
- Prior art keywords
- preparation
- fluorine ether
- hydrogen fluorine
- solvent
- fluoroalkanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
Abstract
The invention relates to a preparation method of hydrofluoroether. The preparation method comprises the following steps: (1), dissolving an alkali compound in fluorine-containing alkanol, adding a solvent, adding fluorinated olefin, and heating and stirring for reaction to obtain a mixed solution; (2), washing the mixed solution obtained in the step (1) by using water, standing for demixing, collecting an organic phase solution of a lower layer, and rectifying to obtain a hydrofluoroether product. According to the preparation method, the generation of double-bond impurities can be inhibited, and a reaction product from which a target product is easily purified can be obtained; the reaction temperature and the reaction pressure are relatively mild, the safety coefficient is high, and more satisfactory reaction speed can be obtained; the solvent is easily recycled, the cost is lowered, and a plurality of wastes are prevented from polluting the environment.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogen fluorine ether.
Background technology
In recent years, hydrogen fluorine ether more and more receives people's concern as the surrogate of Chlorofluorocarbons (CFCs), and it is short that it has atmospheric lifetime, and the advantage such as do not damage the ozone layer and Greenhouse effect are low.
The method of preparing hydrogen fluorine ether has a lot, wherein also comprises the preparation technology who much has solvent to participate in, and under solvent and basic cpd exist as alkali metal hydroxide, containing fluoroalkanol and fluorinated olefin reaction, prepares hydrogen fluorine ether.But in these preparation methods, de-hydrogen halide can occur target product hydrogen fluorine ether, thereby generate two key by products, account for greatly 0.1% to 10% of gross product.Problem is that such by product and target product boiling point approach, and therefore by a step rectifying is difficult, separates.
If the purity of hydrogen fluorine ether is wanted to reach more than 99%, must be first except two key impurity before the thick product rectifying that above-mentioned reaction obtains, general method is to add chlorine or bromine in the compound that contains two key impurity, thereby generate easily separation with target product containing chlorine or bromine by product, after rectifying, can improve the purity of target product, so just increased treatment process, and chlorine used or bromine toxicity large, to operation steps, require strict.
Some researchs have also been done in the generation that people control two key by products for control reaction, but respectively have deficiency, such as shortcomings such as the raw material of severe reaction conditions, use are not easy to obtain.
Summary of the invention
The object of this invention is to provide under mild conditions speed of response fast, target product yield is high, the hydrogen fluorine ether preparation method who easily purifies.
The preparation method of hydrogen fluorine ether of the present invention, under basic cpd effect, adopts solvent method, by reacting and make with fluorinated olefin containing fluoroalkanol; Comprise the following steps:
(1) basic cpd is dissolved in containing in fluoroalkanol, adds solvent, add fluorinated olefin, heated and stirred reaction, obtains mixing solutions;
(2) mixing solutions that water-washing step (1) obtains, stratification, takes off a layer organic phase solution, and rectifying obtains hydrogen fluorine ether product.
Mol ratio containing fluoroalkanol, fluorinated olefin, basic cpd and solvent is: 1: 1: 5～15: 9～11, preferably 1: 1: 6～10: 9.5～10.5, more preferably 1: 1: 7～10: 9.7～10.2.
Described basic cpd is NaOH, KOH, CsOH, LiOH, Ca (OH)
2, Ba (OH)
2, KF, CsF or LiF one.
Described is R containing fluoroalkanol general formula
fcH
2oH; R
fthe fluorine-containing alkyl group of representative, is linear or side chain containing fluoroalkyl, contains 1～8 carbon atom.
Described is R containing fluoroalkanol general formula
fcH
2oH;
Rf is CF
3-, CF
3cF
2-, CF
3(CF
2)
2-, CF
3(CF
2)
3-, CF
3(CF
2)
4-, CF
3(CF
2)
5-, CHF
2cF
2-, CHF
2(CF
2)
3-, CHF
2(CF
2)
5-, (CF
3)
2cF-or (CF
3)
2the one of CH-, preferably CF
3-, CF
3cF
2-or CHF
2cF
2-one.
Described solvent is the one of methylene dichloride, chloroform, DMF, dimethyl sulfoxide (DMSO), acetonitrile or propionitrile.
Described fluorinated olefin is the one of R 1216, tetrafluoroethylene, trifluoro-ethylene, vinylidene or trifluorochloroethylene.
Described heated and stirred temperature of reaction is-15～15 ℃, and preferably-35～35 ℃, pressure be-0.09MPa～0.10MPa, preferred-0.07～0.05MPa.
According to the present invention, although with add other starting material and basic cpd amount relevant, when solvent is when being no more than 11 containing the mol ratio of fluoroalkanol, be especially no more than at 10.5 o'clock, the weight ratio that unsaturated double-bond by product accounts for gross product is no more than 0.5%.Reaction after washing is divided into two-layer, and basic cpd, unreacted alcohol and solvent are present in upper water, the hydrogen fluorine ether in lower floor's organic liquid phase, and after simple rectifying, purity to 99.5%.
In reaction system of the present invention, the add-on of solvent and speed of response are parabolical relation, if reaction system of the present invention adopts solvent-free reaction, the time is more than 10 hours, but the solvent adding is too much, fluorinated olefin and the contact area that contains fluoroalkanol have been reduced, increase on the contrary the reaction times, be unfavorable for the raising of production capacity.Solvent is the shortest at 11 the reaction times with the mol ratio containing fluoroalkanol, but dehydrogenation reaction can occur the target product hydrogen fluorine ether generating, thereby the ratio of the two key impurity difficult separation with target product that generate in thick product increases.So from the viewpoint of these, solvent is no more than 11 with the mol ratio containing fluoroalkanol, is better no more than 10.5, is better no more than 10.2, is not less than 9.5, is better not less than 9.7, is better not less than 9.9.
In the present invention, solvent for use can be methylene dichloride, chloroform, N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), acetonitrile and propionitrile, from follow-up rectification and purification difficulty or ease, consider, with solvent boiling point and the larger solvent of product boiling point difference for well, select in addition the solvent that boiling point is lower as far as possible, be conducive to the easy recovery of solvent, recycling, thereby reduce costs, avoid discarding in a large number welding.
Compared with prior art, the present invention has following beneficial effect:
(1) the method reaction process can suppress the generation of two key impurity, the reaction product of the target product that can obtain easily purifying;
(2) temperature of reaction and reaction pressure are relatively gentle, and safety coefficient is high, but still can obtain more satisfied speed of response;
(3) the easy recycling of solvent, has reduced cost, avoids discarding in a large number welding.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1
Steps A
10L autoclave is found time, nitrogen replacement 3 times, potassium hydroxide is dissolved in trifluoroethanol, join until completely dissolved in reactor, after add methylene dichloride, stir, remain on certain temperature, vacuum introduce R 1216, still internal pressure is remained unchanged.
Step B
When the add-on of R 1216 is 1 times of mole number of the trifluoroethanol that adds, stop dropping into R 1216.When question response still internal pressure is down to negative pressure, add pure water, continue to stir 0.5 hour, stop stirring emptying, blowing.
Step C
Be divided into two-layerly, upper strata is water, has dissolved the complete trifluoroethanol of methylene dichloride, potassium hydroxide and unreacted in water, separates lower floor's organic layer.Through makings, analyzing target product hydrogen fluorine ether purity in organic layer is 86%, and two key impurity ratios are 0.3%.
Step D
After simple rectifying, through makings analysis, target product purity is 99.7%, the results are shown in Table 1.
Embodiment 2
Press embodiment 1 implementation step A to D, except methylene dichloride in steps A changes DMF into, the results are shown in table 1.
Embodiment 3
Press embodiment 1 implementation step A to D, except methylene dichloride in steps A changes DMSO into, the results are shown in table 1.
Embodiment 4
Press embodiment 1 implementation step A to D, except methylene dichloride in steps A changes acetonitrile into, R 1216 changes tetrafluoeopropene into, constant with the mol ratio of trifluoroethanol, the results are shown in table 1.
Embodiment 5
Press embodiment 1 implementation step A to D, except R 1216 in steps A changes tetrafluoeopropene into, trifluoroethanol changes C3-Fluoroalcohol into, and fluorinated olefin, with constant with the mol ratio of fluorine alcohol, the results are shown in table 1.
Embodiment 6
Press embodiment 1 implementation step A to D, except R 1216 in steps A changes tetrafluoeopropene into, trifluoroethanol changes five fluorine propyl alcohol into, and fluorinated olefin, with constant with the mol ratio of fluorine alcohol, the results are shown in table 1.
Comparative example 1
Press embodiment 1 implementation step A to F, except change solvent-free reaction in steps A, the results are shown in table 1.
Comparative example 2
Press embodiment 1 implementation step A to F, except solvent in steps A and the proportioning containing fluoroalkanol are increased to 12:1, the mol ratio of fluorinated olefin and fluorine alcohol is constant, the results are shown in table 1.
Table 1 embodiment and comparative example experimental result
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Claims (10)
1. a preparation method for hydrogen fluorine ether, is characterized in that, under basic cpd effect, adopts solvent method, by reacting and make with fluorinated olefin containing fluoroalkanol; Comprise the following steps:
(1) basic cpd is dissolved in containing in fluoroalkanol, adds solvent, add fluorinated olefin, heated and stirred reaction, obtains mixing solutions;
(2) mixing solutions that water-washing step (1) obtains, stratification, takes off a layer organic phase solution, and rectifying obtains hydrogen fluorine ether product.
2. the preparation method of hydrogen fluorine ether according to claim 1, is characterized in that, is: 1: 1: 5～15: 9～11 containing the mol ratio of fluoroalkanol, fluorinated olefin, basic cpd and solvent.
3. the preparation method of hydrogen fluorine ether according to claim 2, is characterized in that, is: 1: 1: 7～10: 9.7～10.2 containing the mol ratio of fluoroalkanol, fluorinated olefin, basic cpd and solvent.
4. the preparation method of hydrogen fluorine ether according to claim 1, is characterized in that, described basic cpd is NaOH, KOH, CsOH, LiOH, Ca (OH)
2, Ba (OH)
2, KF, CsF or LiF one.
5. the preparation method of hydrogen fluorine ether according to claim 1, is characterized in that, described is R containing fluoroalkanol general formula
fcH
2oH; The fluorine-containing alkyl group of Rf representative, is linear or side chain containing fluoroalkyl, contains 1～8 carbon atom.
6. the preparation method of hydrogen fluorine ether according to claim 5, is characterized in that, described is R containing fluoroalkanol general formula
fcH
2oH;
Rf is CF
3-, CF
3cF
2-, CF
3(CF
2)
2-, CF
3(CF
2)
3-, CF
3(CF
2)
4-, CF
3(CF
2)
5-, CHF
2cF
2-, CHF
2(CF
2)
3-, CHF
2(CF
2)
5-, (CF
3)
2cF-or (CF
3)
2the one of CH-.
7. the preparation method of hydrogen fluorine ether according to claim 1, is characterized in that, described solvent is the one of methylene dichloride, chloroform, DMF, dimethyl sulfoxide (DMSO), acetonitrile or propionitrile.
8. the preparation method of hydrogen fluorine ether according to claim 1, is characterized in that, described fluorinated olefin is the one of R 1216, tetrafluoroethylene, trifluoro-ethylene, vinylidene or trifluorochloroethylene.
9. the preparation method of hydrogen fluorine ether according to claim 1, is characterized in that, described heated and stirred temperature of reaction is-15～15 ℃, and pressure is-0.09MPa～0.10MPa.
10. the preparation method of hydrogen fluorine ether according to claim 9, is characterized in that, described heated and stirred temperature of reaction is-35～35 ℃, and pressure is-0.07～0.05MPa.
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|---|---|---|---|
| CN201310744750.5A CN103739450A (en) | 2013-12-30 | 2013-12-30 | Preparation method of hydrofluoroether |
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|---|---|---|---|
| CN201310744750.5A CN103739450A (en) | 2013-12-30 | 2013-12-30 | Preparation method of hydrofluoroether |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107761130A (en) * | 2017-10-10 | 2018-03-06 | 山东华夏神舟新材料有限公司 | The electrochemical fluorination preparation method of hydrofluoroether |
| CN109529906A (en) * | 2018-12-25 | 2019-03-29 | 西安近代化学研究所 | A kind of catalyst and preparation method thereof synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether |
| CN110407673A (en) * | 2019-05-28 | 2019-11-05 | 浙江巨化技术中心有限公司 | A kind of preparation method of tetra- fluoro ethyl -2,2,2- trifluoroethyl ether of 1,1,2,2- |
| CN110922304A (en) * | 2019-10-22 | 2020-03-27 | 浙江巨化技术中心有限公司 | Production method of fluoroether |
| CN111601873A (en) * | 2018-01-19 | 2020-08-28 | 3M创新有限公司 | Fluorinated liquid regeneration method and regeneration apparatus using such method |
| CN111732500A (en) * | 2020-05-29 | 2020-10-02 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of hydrofluoroether |
| CN112250551A (en) * | 2020-10-30 | 2021-01-22 | 浙江诺亚氟化工有限公司 | Method for synthesizing hydrofluoroether by gas phase method |
| CN113929562A (en) * | 2021-10-28 | 2022-01-14 | 衢州氟硅技术研究院 | Preparation method of fluoroether |
| CN114456046A (en) * | 2021-12-31 | 2022-05-10 | 山东华夏神舟新材料有限公司 | High purity hydrofluoroethers and methods of purifying same |
| CN114907192A (en) * | 2022-04-20 | 2022-08-16 | 中国科学院上海有机化学研究所 | Preparation method of hydrofluoroether compound |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107761130B (en) * | 2017-10-10 | 2019-10-22 | 山东华夏神舟新材料有限公司 | The electrochemical fluorination preparation method of hydrofluoroether |
| CN107761130A (en) * | 2017-10-10 | 2018-03-06 | 山东华夏神舟新材料有限公司 | The electrochemical fluorination preparation method of hydrofluoroether |
| CN111601873A (en) * | 2018-01-19 | 2020-08-28 | 3M创新有限公司 | Fluorinated liquid regeneration method and regeneration apparatus using such method |
| CN111601873B (en) * | 2018-01-19 | 2022-04-12 | 3M创新有限公司 | Fluorinated liquid regeneration method and regeneration apparatus using such method |
| CN109529906B (en) * | 2018-12-25 | 2021-06-15 | 西安近代化学研究所 | Catalyst for synthesizing 1,1,2,3,3, 3-hexafluoropropyl methyl ether and preparation method thereof |
| CN109529906A (en) * | 2018-12-25 | 2019-03-29 | 西安近代化学研究所 | A kind of catalyst and preparation method thereof synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether |
| CN110407673A (en) * | 2019-05-28 | 2019-11-05 | 浙江巨化技术中心有限公司 | A kind of preparation method of tetra- fluoro ethyl -2,2,2- trifluoroethyl ether of 1,1,2,2- |
| CN110922304A (en) * | 2019-10-22 | 2020-03-27 | 浙江巨化技术中心有限公司 | Production method of fluoroether |
| CN110922304B (en) * | 2019-10-22 | 2022-06-03 | 浙江巨化技术中心有限公司 | Production method of fluoroether |
| CN111732500A (en) * | 2020-05-29 | 2020-10-02 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of hydrofluoroether |
| CN112250551A (en) * | 2020-10-30 | 2021-01-22 | 浙江诺亚氟化工有限公司 | Method for synthesizing hydrofluoroether by gas phase method |
| CN113929562A (en) * | 2021-10-28 | 2022-01-14 | 衢州氟硅技术研究院 | Preparation method of fluoroether |
| CN114456046A (en) * | 2021-12-31 | 2022-05-10 | 山东华夏神舟新材料有限公司 | High purity hydrofluoroethers and methods of purifying same |
| CN114456046B (en) * | 2021-12-31 | 2023-10-27 | 山东华夏神舟新材料有限公司 | High-purity hydrofluoroether and process for purifying same |
| CN114907192A (en) * | 2022-04-20 | 2022-08-16 | 中国科学院上海有机化学研究所 | Preparation method of hydrofluoroether compound |
| CN114907192B (en) * | 2022-04-20 | 2023-11-14 | 浙江永太氟乐科技有限公司 | Preparation method of hydrofluoroether compound |
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Application publication date: 20140423 |