CN109608311A - A kind of synthetic method of 1,1,2,3,3,3- hexafluoro propyl methyl ether - Google Patents
A kind of synthetic method of 1,1,2,3,3,3- hexafluoro propyl methyl ether Download PDFInfo
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- CN109608311A CN109608311A CN201811588777.9A CN201811588777A CN109608311A CN 109608311 A CN109608311 A CN 109608311A CN 201811588777 A CN201811588777 A CN 201811588777A CN 109608311 A CN109608311 A CN 109608311A
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- hexafluoropropene
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- 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
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Abstract
The invention discloses one kind 1, 1, 2, 3, 3, the synthetic method of 3- hexafluoro propyl methyl ether, the following steps are included: methanol is added in a kettle, solvent, catalyst and ligand, hexafluoropropene is passed through under stirring to start to react, the molar ratio of the methanol and hexafluoropropene is 1~10:1, the mass ratio of solvent and hexafluoropropene is 1~20:1, the molar ratio of catalyst and hexafluoropropene is 0.01~0.2:1, the molar ratio of catalyst and ligand is 1:1~6, controlling reaction temperature is 30~150 DEG C, reaction pressure is 0.1~2MPa, stopping is passed through after hexafluoropropene that the reaction was continued 2~for 24 hours, it cools down after reaction, discharging, distillation obtains 1, 1, 2, 3, 3, 3- hexafluoro propyl methyl ether.The method of 1,1,2,3,3,3- hexafluoro propyl methyl ether of synthesis of the invention does not use highly basic, and simple process, environmental protection, reaction condition is mild, at low cost, good product quality.
Description
Technical field
The present invention relates to a kind of synthetic methods of hydrofluoroether that can be used as delicate electronic device cleaning agent, and in particular to and 1,1,
The synthetic method of 2,3,3,3- hexafluoro propyl methyl ether.
Background technique
With the raising of global environmental requirement, various countries are also increasingly enhanced the protection of atmospheric ozone layer.Traditional is fluorine-containing clear
Lotion fluorochlorohydrocarbon is limited and is eliminated use, hydrogen fluorochlorohydrocarbon as fluorochlorohydrocarbon substitute also because of its higher consumption ozone
Latent energy value (ODP) and global warming potential (GWP) and longer atmosphere residence time and will be eliminated and limit use.
Hydrofluoroether is mainly used for the cleaning field of delicate electronic device as a kind of novel, efficient fluorine-containing cleaning agent, and ODP value is 0,
GWP value is relatively low, and atmospheric residence time is short, is the ideal substitute of the fluorine-containing cleaning agent of hydrogen fluorochlorohydrocarbon class.1,1,2,3,
As one of numerous hydrofluoroethers, recent domestic synthesizes it and has conducted extensive research 3,3- hexafluoro propyl methyl ethers, but
Document report is less.
United States Patent (USP) US 20030209685A1 discloses a kind of method for synthesizing 1,1,2,3,3,3- hexafluoro propyl methyl ether,
This method is catalyst using the KOH solution that mass fraction is 45% using hexafluoropropene and methanol as raw material, at -3~0 DEG C
At a temperature of react, after reaction, detect the yield of 1,1,2,3,3,3- hexafluoro propyl methyl ether (with hexafluoro in reaction solution crude product
Propylene meter) it is 85%, and there is 9% heavy constituent to generate.This method uses 45% KOH solution for catalyst, easily causes tight
The environmental pollution of weight has in reaction a large amount of heavy constituent to generate, and product quality is difficult to guarantee, and is not joined in reaction process in order to recycle
With the hexafluoropropene reacted, needs to be equipped with the condenser that temperature is -40~-30 DEG C, also increases 1,1,2,3 to a certain extent,
The production cost of 3,3- hexafluoro propyl methyl ether.
The Matsukawa seminar of Japan also reports one kind using hexafluoropropene and methanol as raw material, synthesizes 1,1,2,3,
The method (Angew.Chem.Int.Ed.2005,44,1128-1130) of 3,3- hexafluoro propyl methyl ethers, the difference is that they with
Pd(PPh3)4For catalyst, the experimental results showed that being ligand when bis- (diphenyl phosphine) butane of Isosorbide-5-Nitrae-are added, and 72h is reacted at room temperature
Afterwards, the yield of 1,1,2,3,3,3- hexafluoro propyl methyl ether is up to 83%.Although this method is catalyst without using highly basic, will not produce
Raw problem of environmental pollution, but using precious metals pd as catalyst, costly, and homogeneous Pd catalyst can not recycle circulation and make price
With this directly results in 1,1,2,3,3, the 3- higher preparation cost of hexafluoro propyl methyl ether.
Above-mentioned technique the problems such as there is environmental pollution is serious, preparation cost is high, product quality is difficult to guarantee.
Summary of the invention
The present invention in view of the deficiencies of the prior art, provides a kind of environment friendly and pollution-free, and reaction condition is mild, preparation cost
The synthetic method of the 1,1,2,3,3,3- hexafluoro propyl methyl ether low, product quality is high.
In order to achieve the above objectives, the present invention is achieved by the following technical solutions: of the invention 1, and 1,2,3,3,3- six
The synthetic method of fluoropropyl methyl ether, comprising the following steps: methanol, solvent, catalyst and Phosphine ligands are added in a kettle, it is described
Solvent be one of acetonitrile, Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide, the catalyst be Co-N/C or Fe-
N/C is passed through hexafluoropropene and starts to react under stirring, the molar ratio of the methanol and hexafluoropropene is 1~10:1, solvent and six
The mass ratio of fluoropropene is 1~20:1, and the molar ratio of catalyst and hexafluoropropene is 0.01~0.2:1, catalyst and ligand
Molar ratio is 1:1~6, and control reaction temperature is 30~150 DEG C, and reaction pressure is 0.1~2MPa, after stopping is passed through hexafluoropropene
The reaction was continued 2~for 24 hours, it is cooling after reaction, discharge, distillation obtains 1,1,2,3,3,3- hexafluoro propyl methyl ether.
Preferably, the Phosphine ligands are tricyclohexyl phosphine, bis- (diphenylphosphine) propane of 1,3-, the bis- (diphenyl of 1,1'-
One of phosphine) ferrocene.
Preferably, the molar ratio of the methanol and hexafluoropropene is 2~5:1, and the mass ratio of solvent and hexafluoropropene is 2
~10:1, the molar ratio of metal and hexafluoropropene is 0.02~0.1:1 in catalyst, and the molar ratio of catalyst and ligand is 1:1
~2.
Preferably, control reaction temperature is 40~100 DEG C, and reaction pressure is 0.2~1MPa, and it is subsequent to stop logical hexafluoropropene
6~20h of continuous reaction.
In further technical solution, it is highly preferred that a kind of synthetic method of 1,1,2,3,3,3- hexafluoro propyl methyl ether, packet
It includes following steps: methanol, acetonitrile, Co-N/C and 1 being added in a kettle, 3- bis- (diphenylphosphine) propane are passed through six under stirring
Fluoropropene starts to react, and the molar ratio of the methanol and hexafluoropropene is 2~4:1, and the mass ratio of acetonitrile and hexafluoropropene is 2
~8:1, the molar ratio of metal and hexafluoropropene is 0.04~0.06:1 in catalyst, and the molar ratio of catalyst and ligand is 1:1
~2, control reaction temperature is 40~80 DEG C, and reaction pressure is 0.2~0.8MPa, and stopping is passed through after hexafluoropropene that the reaction was continued 10
~20h, cooling after reaction, discharging, distillation obtain 1,1,2,3,3,3- hexafluoro propyl methyl ether.
The beneficial effects of the present invention are:
(1) transition metal (Co or Fe) is used directly to prepare 1,1,2,3 for catalyst hexafluoropropene and methanol addition,
The method of 3,3- hexafluoro propyl methyl ethers, catalyst is not only cheap and easy to get, can also recycle reuse, therefore, 1,1,2,3,3,
The lower production costs of 3- hexafluoro propyl methyl ether；
(2) the problem of this method does not use highly basic, not will cause environmental pollution is the process route an of green, environmental protection,
And 1,1,2,3,3,3- hexafluoro propyl methyl ether selectivity is higher, and purity is high, therefore, the quality of product is higher.
Specific embodiment
It is as described below to be merely preferred embodiments of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Catalyst preparation: the preparation of catalyst Co-N/C and Fe-N/C can refer to document
Angew.Chem.Int.Ed.2014,53,4359-4363 and J.Catal.2015,323,55-64.
Embodiment 1
It is sequentially added in the 5L stainless steel autoclave that one shows with mechanical stirring, electric heating, thermocouple and pressure
42.7g methanol, 800g acetonitrile, the tricyclohexyl phosphine of 15.7gCo-N/C catalyst and 7.5g, raw material add rear enclosed charging
Mouthful, stirring is opened, opening and heating and control reaction temperature is 150 DEG C, and hexafluoro third is passed through into kettle by gas mass flow meter
Alkene gas, starts to react, and hexafluoropropene is continually fed into reaction process and maintains in kettle pressure between 0.1~2MPa.It is passed through
Stop being passed through hexafluoropropene after 200g hexafluoropropene, the reaction was continued 10h.Cooling, discharging, rectifying obtain 182.5g1, and 1,2,3,3,3-
Hexafluoro propyl methyl ether, purity 99.3%, yield 75.2%.
Embodiment 2
It is sequentially added in the 5L stainless steel autoclave that one shows with mechanical stirring, electric heating, thermocouple and pressure
Bis- (diphenylphosphines) third of 1, the 3- of 427.1g methanol, 2400g1,4- dioxane, 59.7gFe-N/C catalyst and 88.1g
Alkane, raw material add rear enclosed feed opening, open stirring, and opening and heating and control reaction temperature is 30 DEG C, pass through gas mass flow
Meter is passed through hexafluoropropene gas into kettle, starts to react, and hexafluoropropene is continually fed into reaction process and maintains pressure in kettle
Between 0.1~1.5MPa.It is passed through and stops after 200g hexafluoropropene being passed through hexafluoropropene, the reaction was continued 2h.Cooling, discharging, essence
Evaporate to obtain 154.6g1,1,2,3,3,3- hexafluoro propyl methyl ether, purity 99.1%, yield 63.7%.
Embodiment 3
It is sequentially added in the 5L stainless steel autoclave that one shows with mechanical stirring, electric heating, thermocouple and pressure
Bis- (diphenylphosphine) propane of 1, the 3- of 128.1g methanol, 1000g acetonitrile, 78.6gCo-N/C catalyst and 55.1g, raw material add
Complete rear enclosed feed opening opens stirring, and opening and heating and control reaction temperature is 80 DEG C, through gas mass flow meter into kettle
Be passed through hexafluoropropene gas, start to react, hexafluoropropene is continually fed into reaction process and maintain in kettle pressure 0.2~
Between 0.8MPa.It is passed through and stops after 200g hexafluoropropene being passed through hexafluoropropene, the reaction was continued 20h.Cooling, discharging, rectifying obtain
237.1g1,1,2,3,3,3- hexafluoro propyl methyl ether, purity 99.9%, yield 97.7%.
Embodiment 4
It is sequentially added in the 5L stainless steel autoclave that one shows with mechanical stirring, electric heating, thermocouple and pressure
256.3g methanol, 200gN, dinethylformamide, the bis- (diphenyl of 1,1'- of 94.3gCo-N/C catalyst and 221.7g
Phosphine) ferrocene, raw material adds rear enclosed feed opening, opens stirring, and opening and heating and control reaction temperature is 50 DEG C, passes through gas
Mass flowmenter is passed through hexafluoropropene gas into kettle, starts to react, and hexafluoropropene is continually fed into reaction process and maintains kettle
Interior pressure is between 0.1~1MPa.Stop being passed through hexafluoropropene after being passed through 200g hexafluoropropene, the reaction was continued for 24 hours.Cooling goes out
Material, rectifying obtain 198.1g1,1,2,3,3,3- hexafluoro propyl methyl ether, purity 99.7%, yield 81.6%.
Embodiment 5
It is sequentially added in the 5L stainless steel autoclave that one shows with mechanical stirring, electric heating, thermocouple and pressure
341.6g methanol, 3600gN, dinethylformamide, the bis- (diphenyl of 1,3- of 179.2gFe-N/C catalyst and 66.1g
Phosphine) propane, raw material adds rear enclosed feed opening, opens stirring, and opening and heating and control reaction temperature is 120 DEG C, passes through gas
Mass flowmenter is passed through hexafluoropropene gas into kettle, starts to react, and hexafluoropropene is continually fed into reaction process and maintains kettle
Interior pressure is between 0.1~2MPa.It is passed through and stops after 200g hexafluoropropene being passed through hexafluoropropene, the reaction was continued 16h.Cooling goes out
Material, rectifying obtain 208.2g1,1,2,3,3,3- hexafluoro propyl methyl ether, purity 99.6%, yield 85.8%.
Embodiment 6
It is sequentially added in the 5L stainless steel autoclave that one shows with mechanical stirring, electric heating, thermocouple and pressure
170.8g methanol, 1400g acetonitrile, the tricyclohexyl phosphine of 314.3gCo-N/C catalyst and 101.1g, raw material add rear enclosed
Feed opening opens stirring, and opening and heating and control reaction temperature is 70 DEG C, and hexafluoro is passed through into kettle by gas mass flow meter
Propylene gas, starts to react, and hexafluoropropene is continually fed into reaction process and maintains in kettle pressure between 0.1~0.8MPa.
It is passed through and stops after 200g hexafluoropropene being passed through hexafluoropropene, the reaction was continued 12h.Cooling, discharging, rectifying obtain 213.3g1, and 1,2,3,
3,3- hexafluoro propyl methyl ethers, purity 99.8%, yield 87.9%.
Claims (4)
1. the synthetic method of 1,1,2,3,3,3- hexafluoro propyl methyl ether of one kind, it is characterised in that the following steps are included: in reaction kettle
Middle addition methanol, solvent, catalyst and Phosphine ligands, the solvent are acetonitrile, Isosorbide-5-Nitrae-dioxane, n,N-Dimethylformamide
One of, the catalyst be Co-N/C or Fe-N/C, hexafluoropropene is passed through under stirring and starts to react, the methanol with
The molar ratio of hexafluoropropene is 1~10:1, and the mass ratio of solvent and hexafluoropropene is 1~20:1, catalyst and hexafluoropropene
Molar ratio is 0.01~0.2:1, and the molar ratio of catalyst and ligand is 1:1~6, and control reaction temperature is 30~150 DEG C, reaction
Pressure is 0.1~2MPa, stopping is passed through after hexafluoropropene that the reaction was continued 2~for 24 hours, it cools down, discharge, distill after reaction to obtain the final product
To 1,1,2,3,3,3- hexafluoro propyl methyl ether.
2. the synthetic method of according to claim 11,1,2,3,3,3- hexafluoro propyl methyl ether, which is characterized in that described
Phosphine ligands are one of tricyclohexyl phosphine, bis- (diphenylphosphine) propane of 1,3-, bis- (diphenylphosphine) ferrocene of 1,1'-.
3. the synthetic method of according to claim 11,1,2,3,3,3- hexafluoro propyl methyl ether, which is characterized in that described
The molar ratio of methanol and hexafluoropropene is 2~5:1, and the mass ratio of solvent and hexafluoropropene is 2~10:1, catalyst and hexafluoro third
The molar ratio of alkene is 0.02~0.1:1, and the molar ratio of catalyst and ligand is 1:1~2.
4. the synthetic method of according to claim 11,1,2,3,3,3- hexafluoro propyl methyl ether, which is characterized in that control is anti-
Answering temperature is 40~100 DEG C, and reaction pressure is 0.2~1MPa, the 6~20h that stops after logical hexafluoropropene that the reaction was continued.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113929562A (en) * | 2021-10-28 | 2022-01-14 | 衢州氟硅技术研究院 | Preparation method of fluoroether |
| WO2023204189A1 (en) * | 2022-04-20 | 2023-10-26 | ダイキン工業株式会社 | Method for producing composition containing purified fluorine-containing ether compound |
| WO2023204066A1 (en) * | 2022-04-20 | 2023-10-26 | ダイキン工業株式会社 | Method for producing fluoroether |
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| CN105906489A (en) * | 2016-05-05 | 2016-08-31 | 巨化集团技术中心 | Method for synchronously preparing hydrofluoroether and fluorine-containing olefine ether |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929562A (en) * | 2021-10-28 | 2022-01-14 | 衢州氟硅技术研究院 | Preparation method of fluoroether |
| WO2023204189A1 (en) * | 2022-04-20 | 2023-10-26 | ダイキン工業株式会社 | Method for producing composition containing purified fluorine-containing ether compound |
| WO2023204066A1 (en) * | 2022-04-20 | 2023-10-26 | ダイキン工業株式会社 | Method for producing fluoroether |
| JP7473826B2 (en) | 2022-04-20 | 2024-04-24 | ダイキン工業株式会社 | Method for producing fluoroether |
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