CN107867978B - Synthesis method of heptafluoropropyl trifluoromethyl ether - Google Patents
Synthesis method of heptafluoropropyl trifluoromethyl ether Download PDFInfo
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- CN107867978B CN107867978B CN201610854808.5A CN201610854808A CN107867978B CN 107867978 B CN107867978 B CN 107867978B CN 201610854808 A CN201610854808 A CN 201610854808A CN 107867978 B CN107867978 B CN 107867978B
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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
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Abstract
The invention relates to a synthesis method of heptafluoropropyl trifluoromethyl ether, which takes trifluoromethyl hypofluorite and perfluoropropene as raw materials, and the gaseous trifluoromethyl hypofluorite and the liquid perfluoropropene generate free radical addition reaction at low temperature to generate the heptafluoropropyl trifluoromethyl ether. The invention provides a method for synthesizing perfluoroalkyl ether by a chemical method, which does not need fluorine gas with extremely high activity or expensive catalyst, can utilize the mixture of trifluoromethyl hypofluorite and fluorophosphoric acid produced in the previous step for polar synthesis, and simplifies the production steps; the perfluoroalkyl ether has high yield, simple synthesis method and certain industrial popularization value.
Description
Technical Field
The invention relates to the field of fluorine-containing organic compounds, in particular to a preparation method of perfluoroalkyl ether.
Background
The perfluoroalkyl ether is an ether generated by replacing all hydrogen atoms on carbon atoms in alkyl ether molecules by fluorine atoms, has the special properties of strong acid and strong base resistance, high chemical stability and the like, is non-conductive, colorless, tasteless and nontoxic, is not ignited, is basically nontoxic, is not easily decomposed when being heated, and can be used in the fields of biology, medicine, chemical industry, electronics, military industry and the like. The synthesis of perfluoroalkyl ethers is more difficult than the synthesis of fluoroalkyl ethers having hydrogen groups, for example, the synthesis reaction of fluoromethyl hexafluoroisopropyl ether can be carried out by using a halogenated aliphatic hydrocarbon or a halogenated aromatic hydrocarbon as a solvent in the presence of sulfuric acid or other strong acids at room temperature in the presence of difluoromethyl ether and hexafluoroisopropanol (patent CN 102414157 a).
The synthesis of perfluoroalkyl ethers currently uses electrochemical fluorination (i.e., Simons). The electrochemical fluorination method was invented by j.h. simons and co-workers in 1941, and then developed by 3M company in the united states for an industrial production method, and it is reported that 3M company can provide more than 250 fluorine-containing compounds by the method, but when synthesizing fluorine-containing organic compounds by the electrochemical fluorination method, organic compounds must have a certain solubility in anhydrous hydrogen fluoride, and thus some poorly soluble organic substrates are difficult to synthesize by the electrochemical fluorination method.
Another method for synthesizing perfluorinated organic compounds by using cobalt trifluoride or boron trifluoride as catalyst is disclosed in, for example, patent CN 102093550A in which boron trifluoride BF is used as catalyst3Under the existing condition, perfluoroalkyl alcohol is used for synthesizing perfluoroalkyl ethyl polyoxyethylene ether, and the technology needs to carry out reaction at higher temperature and pressure. The implementation difficulty of synthesizing the perfluoroalkyl ether by using cobalt trifluoride or boron trifluoride catalysis is higher.
Disclosure of Invention
Aiming at the defects in the field, the invention aims to provide a method for synthesizing heptafluoropropyl trifluoromethyl ether.
The technical scheme for realizing the purpose of the invention is as follows:
a process for synthesizing heptafluoropropyl trifluoromethyl ether from trifluoromethyl hypofluorite and perfluoropropene (CF)3CF＝CF2) Starting from gaseous trifluoromethyl hypofluorite (CF)3OF) at low temperatures with liquid perfluoropropene (CF)3CF＝CF2) Free radical addition reaction to produce heptafluoropropyl trifluoromethyl ether (CF)3-CF2-CF2-O-CF3)。
Further, said trifluoromethyl hypofluorite (CF)3OF) is diluted by inert gas and then added into a reaction container, wherein the inert gas is nitrogen, helium, argon, and fluorophosphoric acid (COF)2) And the volume concentration of the trifluoromethyl hypofluorite after being diluted by inert gas is 20-99%.
The inert gas fluorophosphorus (COF)2) The catalyst can be carried by the raw material trifluoromethyl hypofluorite, and the volume content can be 1-20%. For example, patent CN1018823B discloses a method for preparing fluoroxytrifluoromethane (i.e., trifluoromethyl hypofluorite) by catalytic fluorination, which comprises two steps, the first step is CO and F2Direct reaction to COF2The second step is COF2And F2Catalytic fluorination to CF3OF, the reaction synthesis condition OF the step is harsh, a solid catalyst is required to be used, the reaction yield is not too high generally, and the product generally contains COF within 20 percent2，COF2(boiling point-84 ℃ C.) and CF3OF (boiling point-95 ℃ C.) is very difficult to separate in the near boiling point phase, while COF is present in the system for synthesizing heptafluoropropyltrifluoromethyl ether2Substantially does not participate in the reaction, can be regarded as inert gas, and a mixed gas of the fluorophosphone gas and the trifluoromethyl hypofluorite and the CF are directly used3-CF＝CF2The reaction can reduce the cost and save the working procedure.
Wherein the free radical addition reaction is carried out at a low temperature ranging from-90 ℃ to-30 ℃,
preferably, the free radical addition reaction is carried out at a temperature of-70 to-40 ℃, and the temperature control is realized by placing the reaction vessel in a cold trap.
Wherein, the reaction vessel is filled with a filler, and the main body of the reaction vessel and the filler are made of one or more materials of 304 stainless steel, 316L stainless steel, nickel and nickel alloy; the filler is one of pall ring, raschig ring, arc saddle-shaped filler and rectangular saddle-shaped filler.
Or, a solvent is filled in the reaction container, and the solvent is perfluoro-n-pentane (C)5F12) Dichloromethane (CH)2Cl2) Perfluoro-n-hexane (C)6F14) One kind of (1). In the reaction with stirring, only the solvent may be used.
Wherein the free radical addition reaction is carried out for 5-12 hours, and the reaction product is separated by distillation. Gaseous trifluoromethyl hypofluorite is continuously added in the reaction, and the molar ratio of the added trifluoromethyl hypofluorite to the perfluoropropylene is (1-1.2): 1.
wherein, the reaction product is subjected to distillation separation, and a fraction with the boiling point of 6-7 ℃ is taken.
The invention has the beneficial effects that:
the invention provides a method for synthesizing perfluoroalkyl ether by a chemical method, which does not need fluorine gas with extremely high activity or expensive catalyst, can utilize the mixture of trifluoromethyl hypofluorite and fluorophosphoric acid produced in the previous step for polar synthesis, and simplifies the production steps; the perfluoroalkyl ether has high yield, simple synthesis method and certain industrial popularization value.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. Unless otherwise specified, the reagents used in the examples are all conventional commercially available reagents, and the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
A304 stainless steel vertical tubular reactor (50 mm in inside diameter, 600mm in length, about 1.2L in volume) was placed in a cold trap at-50 ℃ and filled with a 16 mm stainless steel pall ring packing. When the temperature of the inner wall of the reactor is consistent with the temperature of the refrigerant, 300g (2mol) of liquid hexafluoropropylene (CF) is slowly injected into the reactor3CF＝CF2) After the temperature of the inner wall of the reaction is stabilized at-50 ℃, introducing CF diluted by nitrogen in a ratio of 1:1 (volume ratio) at a flow rate of 20L/h3OF gas, reaction tail gas is washed by 20% potassium hydroxide lye and then is discharged, the reaction is continued for 5 hours, reaction products are distilled by a distillation column, 320g OF products with the purity OF 99% (boiling point is 6.8 ℃, and products are heptafluoropropyl trifluoromethyl ether products detected by a nuclear magnetic resonance spectrometer), and the product yield is 62.4%.
Example 2
The reactor set-up was as in example 1. CF is prepared by3OF and N2The dilution ratio of (1: 1.5) (i.e. the volume ratio of trifluoromethyl hypofluorite is 40%), and then the reaction is continued for 8h, and the reaction product is distilled to obtain 355g of product with the purity of 99% (boiling point is 6.8 ℃), and the yield of the product is 69.2%.
Example 3
The reactor in example 1 was placed in a cold trap at-60 ℃ and 450g (3mol) of hexafluoropropene liquid was slowly injected into the reactor after the temperature of the inner wall of the reactor was in agreement with that of the refrigerant, and after the temperature in the reactor was stabilized at-60 ℃, fluorophosphoric acid gas was injected into the reactor at a flow rate of 15L/h to dilute the reactorCF of3OF gas (crude trifluoromethyl hypofluorite prepared according to the method OF patent CN1018823B, wherein CF3OF volume content 80% COF2Content 20%), and reaction is continued for 6 h. The reaction product was distilled through a distillation column to obtain 562g (73% yield) of heptafluoropropyltrifluoromethyl ether having a purity of 99%.
Example 4
The reactor of example 1 was placed in a cold trap at-80 ℃ and then 450g (3mol) of hexafluoropropylene liquid was injected into the reactor, and CF diluted with nitrogen at 1.5:1 was introduced into the reactor at a flow rate of 15L/h3OF gas, continuously reacted for 6 hours. The reaction product was distilled through a distillation column to obtain 392g of heptafluoropropyltrifluoromethyl ether (yield: 50.9%) having a purity of 99% and 252g of an oily mixture having a boiling point higher than 6.8g and containing-CF-by GC-MS detection3、CF3O-、-CF2Oligomeric mixtures of-CF-initially analyzed as hexafluoropropylene oligomers and CF3OF.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (3)
1. A synthetic method of heptafluoropropyl trifluoromethyl ether is characterized in that trifluoromethyl hypofluorite and perfluoropropene are used as raw materials, and gaseous trifluoromethyl hypofluorite and liquid perfluoropropene undergo free radical addition reaction at low temperature to generate heptafluoropropyl trifluoromethyl ether;
diluting the trifluoromethyl hypofluorite with inert gas, and adding the diluted trifluoromethyl hypofluorite into a reaction container, wherein the inert gas is fluorophosphates, and the volume concentration of the fluorophosphates is 20%;
the low temperature is-70 to-40 ℃, and the temperature is controlled by placing the reaction container in a cold trap;
the reaction container is filled with filler or solvent, and the main body of the reaction container and the filler are made of one or more materials of 304 stainless steel, 316L stainless steel, nickel and nickel alloy; the filler is one of pall ring, raschig ring, arc saddle-shaped filler and rectangular saddle-shaped filler; the solvent is one of perfluoro-n-pentane, dichloromethane and perfluoro-n-hexane.
2. The synthesis method according to claim 1, wherein the free radical addition reaction is carried out for 5-12 hours, gaseous trifluoromethyl hypofluorite is continuously added in the reaction, and the molar ratio of the added trifluoromethyl hypofluorite to the perfluoropropene is 1-1.2: 1.
3. the synthesis method according to claim 2, wherein the reaction product is separated by distillation, and a fraction with a boiling point of 6-7 ℃ is taken.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5877357A (en) * | 1989-06-20 | 1999-03-02 | Ausimont S.P.A. | Process for preparing perhaloethers from perhaloolefins and new perhaloethers thereby obtained |
| ITMI20071481A1 (en) * | 2007-07-23 | 2009-01-24 | Milano Politecnico | PROCESS FOR THE SYNTHESIS OF PERFLUOROALCHILETERI |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5877357A (en) * | 1989-06-20 | 1999-03-02 | Ausimont S.P.A. | Process for preparing perhaloethers from perhaloolefins and new perhaloethers thereby obtained |
| ITMI20071481A1 (en) * | 2007-07-23 | 2009-01-24 | Milano Politecnico | PROCESS FOR THE SYNTHESIS OF PERFLUOROALCHILETERI |
Non-Patent Citations (2)
| Title |
|---|
| Comparison of the reactivity of CF3OX(X=Cl,F) with some simple alkenes;Johri, Kamalesh K.等;《Journal of Organic Chemistry》;19831231;第48卷(第2期);第242-250页 * |
| The use of perfluoroalkyl hypofluorites for an efficient synthesis of perfluorinated ethers characterized by low Ostwald coefficient;Walter Navarrini等;《Journal of Fluorine Chemistry》;20081231;第129卷;第680-685页 * |
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