CN116120149B - Method for preparing fluorine-containing alkyne by dehydrohalogenating saturated halogenated hydrocarbon - Google Patents

Method for preparing fluorine-containing alkyne by dehydrohalogenating saturated halogenated hydrocarbon Download PDF

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CN116120149B
CN116120149B CN202310352159.9A CN202310352159A CN116120149B CN 116120149 B CN116120149 B CN 116120149B CN 202310352159 A CN202310352159 A CN 202310352159A CN 116120149 B CN116120149 B CN 116120149B
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fluoride
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CN116120149A (en
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郭勤
庆飞要
张呈平
权恒道
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Quanzhou Yuji New Material Technology Co ltd
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Quanzhou Yuji New Material Technology Co ltd
Beijing Yuji Science and Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

Abstract

The application discloses a method for preparing a fluorine-containing alkyne by dehydrohalogenating saturated halogenated hydrocarbon, which takes fluoroolefin and halogen as initial raw materials, and obtains the fluorine-containing alkyne through gas phase addition reaction and dehydrohalogenation reaction in two steps.

Description

Method for preparing fluorine-containing alkyne by dehydrohalogenating saturated halogenated hydrocarbon
Technical Field
The application relates to the field of organic synthesis, in particular to a method for preparing a fluorine-containing alkyne by gas phase reaction, and especially relates to a method for preparing the fluorine-containing alkyne by taking fluoroolefin and halogen as starting materials through gas phase addition reaction and dehydrohalogenation reaction and two steps of reaction.
Background
1, 3-tetrafluoro-1-propyne is a typical fluoroalkyne compound, has the characteristics of environmental friendliness and excellent application performance in the field of chlorofluorocarbon substitutes, and is considered to be one of ideal chlorofluorocarbon substitutes. At present, the published literature reports that the synthesis methods of 1, 3-tetrafluoro-1-propyne are few, and mainly comprise the following methods:
1. 1, 2-dibromo-1, 3-tetrafluoropropene is taken as raw material
Document "Science of Synthesis (2006), 24,905-932" reports the debromination of 1, 2-dibromo-1, 3-tetrafluoropropene in the presence of a reducing agent to give 1, 3-tetrafluoro-1-propyne.
Document "Journal of Fluorine Chemistry (1977), 10 (6), 487-93" reports that 1, 2-dibromo-1, 3-tetrafluoropropene is reacted at a temperature of 330℃in the presence of a copper catalyst, the contact time was 56.25 seconds, and the conversion of 1, 2-dibromo-1, 3-tetrafluoropropene was 68%, and the single pass yield of 1, 3-tetrafluoro-1-propyne was 11%.
U.S. Pat. No. 3,124A, document "Journal of the Chemical Society [ Section ] C Organic (1969), (7), 1104-7" and "Tetrahedron Letters (1968), (36), 3909-10" report that 1, 2-dibromo-1, 3-tetrafluoropropene was reacted with zinc powder under reflux conditions in dioxane solvent to give 1, 3-tetrafluoro-1-propyne in a yield of 43%.
2. Takes 3, 4-difluoro-3-cyclobutene-1, 2-diketone as raw material
Document "Journal of Fluorine Chemistry (1999), 99 (2), 99-104" reports that 3, 4-difluoro-3-cyclobutene-1, 2-dione is subjected to a pyrolysis reaction to give difluoropropenone, 1, 3-tetrafluoro-1-propyne, tetrafluoropropadiene and tetrafluorocyclopropene.
3. Takes tetrafluoropropadiene as raw material
Chinese patent document CN112811978A discloses that tetrafluoropropadiene undergoes an isomerization reaction at 20 ℃ in the presence of a catalyst to obtain 1, 3-tetrafluoro-1-propyne, wherein the conversion of tetrafluoropropadiene is 100% and the selectivity of 1, 3-tetrafluoro-1-propyne is 99.5%.
Disclosure of Invention
The above route for synthesizing 1, 3-tetrafluoro-1-propyne has the following problems: (1) The raw materials of the method 1 are difficult to obtain, and the product yield is very low; (2) the raw materials of method 2 are difficult to obtain and the by-products are too much; (3) raw materials of method 3 are difficult to obtain.
The technical problem to be solved by the application is to overcome the defects existing in the background technology, and the method for preparing the fluorine-containing alkyne is easy to obtain the initial raw material, high in conversion rate and high in selectivity. Specifically, the application adopts the following technical scheme,
1. a preparation method of fluorine-containing alkyne uses a compound of formula (I) or a compound of formula (II) as a raw material to carry out dehydrohalogenation reaction to obtain the fluorine-containing alkyne,
wherein the structure of the compound of formula (I) is shown below,
Figure GDA0004274131580000021
wherein R is 1 Is C m F 2m+1 ，R 2 H, cl or C n F 2n+1 M and n are non-negative integers, m+n is more than or equal to 0 and less than or equal to 12, the structural formula of the obtained fluorine-containing alkyne is shown as a formula (III),
Figure GDA0004274131580000022
the structure of the compound of formula (II) is shown below,
Figure GDA0004274131580000023
Wherein R is 3 Is C p F 2p+1 ，R 4 F, cl or Br, p is a non-negative integer, and p is more than or equal to 0 and less than or equal to 12; the structural formula of the obtained fluorine-containing alkyne is shown as a formula (IV),
Figure GDA0004274131580000024
x is Cl or Br.
2. The process of item 1, wherein the dehydrohalogenation reaction is a gas phase dehydrohalogenation reaction or a liquid phase dehydrohalogenation reaction.
3. The process according to item 2, wherein in the vapor phase dehydrohalogenation reaction, the starting material is reacted in the presence of a catalyst A consisting of an alkali metal halide and an alkaline earth metal oxide.
4. The method according to item 3, wherein the alkali metal halide and alkaline earth metal oxide are 1 to 70% and 30 to 99% by mass.
5. The method according to item 4, wherein the alkali metal halide is any one or two or more of lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, or
The alkaline earth metal oxide is any one or more than two of magnesium oxide, calcium oxide, strontium oxide and barium oxide.
6. The process according to any one of claim 35, wherein the catalyst a is prepared by mixing an alkali metal halide and an alkaline earth metal oxide powder, tabletting, drying at 100 to 200 ℃ under nitrogen atmosphere, and then calcining.
7. The method according to item 6, wherein the drying time is 5 to 10 hours, or the firing temperature is 400 ℃, or the firing time is 5 to 20 hours.
8. The process according to any one of the above 2 to 7, wherein the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 300 to 600℃and the contact time of the raw materials is 5 to 200s,
preferably, the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 400-550 ℃, and the contact time of raw materials is 30-100 s.
9. The process according to item 2, wherein in the liquid phase dehydrohalogenation reaction, the raw material is reacted with a base in the presence of a catalyst B, which is any one of tetrabutylammonium bromide, benzyltriethylammonium chloride, chain polyethylene glycol, 18-crown ether-6, 15-crown ether-5, and cyclodextrin.
10. The method according to item 9, wherein the base is any one or two or more of potassium hydroxide, sodium hydroxide, rubidium hydroxide, and cesium hydroxide.
11. The process according to item 9 or 10, wherein the ratio of the amounts of the materials of the raw material, the base and the catalyst B is 1: (2 to 10): (0.005 to 0.05).
12. The process according to any one of claims 9 to 11, wherein the reaction is carried out in an autoclave, preferably at a reaction pressure of 0.1 to 0.5MPa, a reaction temperature of 25 to 100 ℃, and a reaction time of 2 to 20 hours.
13. The process according to any one of items 1 to 12, wherein the starting material is composed of a compound of formula (V) or formula (VI) and X 2 Is obtained by gas phase addition reaction in the presence of a catalyst C,
wherein the structure of the compound of formula (V) is as follows,
Figure GDA0004274131580000041
wherein R is 1 Is C m F 2m+1 ，R 2 H, cl or C n F 2n+1 M and n are non-negative integers, and m+n is more than or equal to 0 and less than or equal to 12;
the structure of the compound of formula (VI) is shown below,
Figure GDA0004274131580000042
wherein R is 3 Is C p F 2p+1 ，R 4 F, cl or Br, p is a non-negative integer, and p is more than or equal to 0 and less than or equal to 12;
x is Cl or Br.
14. The process according to claim 13, wherein, in the reaction conditions of the gas phase addition reaction, the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 150 to 300 ℃, preferably the reaction pressure is 0.1 to 0.5MPa, and the reaction temperature is 200 to 250 ℃.
15. The method of item 13, wherein the compound of formula (V) or (VI) is mixed with X 2 The ratio of the amounts of the substances is 1: (1-5), preferably the ratio of the amounts of the substances is 1: (1-3).
16. The process according to item 13, wherein the residence time of the compound of formula (V) or (VI) in the reactor is from 5 to 100s, preferably from 10 to 60s.
17. The method according to claim 13, wherein the catalyst C is any one or two or more of chromium fluoride, magnesium fluoride, aluminum fluoride, iron fluoride, and calcium fluoride.
Effects of the invention
(1) The raw materials of the preparation method of the fluorine-containing alkyne are easy to obtain. Wherein the raw materials are 3, 3-trifluoropropene, E-1, 3-tetrafluoropropene Z-1, 3-tetrafluoropropene, 2, 3-tetrafluoropropene raw materials such as E-1-chloro-3, 3-trifluoropropene, Z-1-chloro-3, 3-trifluoropropene, 2-chloro-3, 3-trifluoropropene, and Cl 2 Or Br (Br) 2 Are available from direct commercial sources.
(2) The preparation method of the fluorine-containing alkyne adopts two-step reaction preparation, has the advantages of high conversion rate and high selectivity, and is easy to realize large-scale production of the fluorine-containing alkyne.
(3) The method for preparing the fluorine-containing alkyne by dehydrohalogenation not only realizes gas-phase continuous production, but also can realize high-efficiency liquid-phase preparation. In the gas phase continuous method, the reaction condition is mild, the operation is simple, and the byproduct olefin can be continuously participated in the reaction for generating the fluorine-containing alkyne as the reaction raw material, so that the raw material loss is almost avoided, and three wastes are hardly generated in the process.
(4) In the method for preparing the fluorine-containing alkyne by dehydrohalogenation, the reaction is rapid and efficient in liquid phase reaction, the reaction conversion rate and the selectivity are high, the difference of the boiling points of the target product and other substances in the reaction system is large after the reaction, and the product with high purity can be obtained by simple gas-liquid phase separation, so that the subsequent product separation difficulty is reduced.
Drawings
The drawings are included to provide a better understanding of the present application and are not to be construed as unduly limiting the present application. Wherein:
FIG. 1 shows a process flow diagram for preparing 1, 3-tetrafluoropropene and chlorine gas as starting materials by two-step reaction of gas phase addition and gas phase dehydrohalogenation to prepare 1, 3-tetrafluoro-1-propyne,
the reference numerals in fig. 1 are as follows. Pipeline: 1. 2, 4, 6, 7, 8, 10, 12, 13, 15, 16 and 17 are each part of a pipeline; 3-a first reactor; 9-a second reactor; 5-a first distillation column; 11-a second distillation column; 14-a third distillation column.
Detailed Description
Exemplary embodiments of the present application are described below, including various details of embodiments of the present application to facilitate understanding, which should be considered as merely exemplary. Accordingly, one of ordinary skill in the art will recognize that various changes and modifications of the embodiments described herein can be made without departing from the scope and spirit of the present application. Also, descriptions of well-known functions and constructions are omitted in the following description for clarity and conciseness.
The present application provides a method for preparing a fluorine-containing alkyne.
The preparation method comprises the steps of using a compound of the formula (I) as a raw material to carry out dehydrohalogenation reaction, wherein the structure of the compound of the formula (I) is shown as follows,
Figure GDA0004274131580000061
wherein R is 1 Is C m F 2m+1 ，R 2 H, cl or C n F 2n+1 M and n are non-negative integers, and m+n is more than or equal to 0 and less than or equal to 12, and the structural formula of the obtained fluorine-containing alkyne is shown as formula (III)
Figure GDA0004274131580000062
X is Cl or Br.
In the compound of the formula (I) as raw material, R 1 Can be F, CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 、C 5 F 11 、C 6 F 13 、C 7 F 15 、C 8 F 17 、C 9 F 19 、C 10 F 21 、C 11 F 23 、C 12 F 25 ；
In the compound of the formula (I) as raw material, R 1 Can be H, cl, F, CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 、C 5 F 11 、C 6 F 13 、C 7 F 15 、C 8 F 17 、C 9 F 19 、C 10 F 21 、C 11 F 23 、C 12 F 25 。
The preparation method comprises the steps of using a compound of a formula (II) as a raw material to carry out dehydrohalogenation reaction, wherein the structure of the compound of the formula (II) is shown as follows,
Figure GDA0004274131580000063
wherein R is 3 Is C p F 2p+1 ，R 4 F, cl or Br, p is a non-negative integer, and p is more than or equal to 0 and less than or equal to 12; the structural formula of the obtained fluorine-containing alkyne is shown as a formula (IV),
Figure GDA0004274131580000064
x is Cl or Br.
In the raw material compound of formula (II), R 3 Can be F, CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 、C 5 F 11 、C 6 F 13 、C 7 F 15 、C 8 F 17 、C 9 F 19 、C 10 F 21 、C 11 F 23 、C 12 F 25 。
In this application, the dehydrohalogenation reaction is in accordance with the general definition in the art, meaning a reaction that loses 1 hydrogen atom and 1 halogen atom from the reaction substrate with concomitant multiple bond or ring formation. In a preferred embodiment of the process of the present application, the dehydrohalogenation reaction is a gas phase dehydrohalogenation reaction or a liquid phase dehydrohalogenation reaction. In a further preferred mode, the gas phase dehydrohalogenation is carried out when the compound of formula (I) is used as a raw material for preparing the fluorine-containing alkyne, and in a further preferred mode, the liquid phase dehydrohalogenation is carried out when the compound of formula (II) is used as a raw material for preparing the fluorine-containing alkyne.
In the gas phase dehydrohalogenation reaction, a catalyst may be used to catalyze the reaction to accelerate the reaction, in a preferred embodiment catalyst a, which is a catalyst composed of an alkali metal halide and an alkaline earth metal oxide.
In a further preferred embodiment, the alkali metal halide and alkaline earth metal oxide are 1% -70% by mass and 30% -99% by mass, for example, 1% by mass of alkali metal halide, 99% by mass of alkaline earth metal oxide, 2% by mass of alkali metal halide, 98% by mass of alkaline earth metal oxide, 5% by mass of alkali metal halide, 95% by mass of alkaline earth metal oxide, 10% by mass of alkali metal halide, 90% by mass of alkaline earth metal oxide, 15% by mass of alkali metal halide, 85% by mass of alkaline earth metal oxide, 20% by mass of alkali metal halide, 80% by mass of alkaline earth metal oxide, 25% by mass of alkali metal halide, 75% by mass of alkaline earth metal oxide, 30% by mass of alkali metal halide, 70% by mass of alkaline earth metal oxide, 35% by mass of alkaline earth metal halide, 65% by mass of alkaline earth metal halide, 40% by mass of alkaline earth metal halide, 60% by mass of alkaline earth metal halide, 45% by mass of alkaline earth metal halide, 50% by mass of alkaline earth metal halide, and 55% by mass of alkaline earth metal halide, the mass percentage of the alkali metal halide is 70 percent, and the mass percentage of the alkaline earth metal oxide is 30 percent.
In a preferred embodiment, in the catalyst a, the alkali metal halide is any one or two or more of lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, for example, three or four kinds.
In a preferred embodiment, the alkaline earth metal oxide in the catalyst a is any one or two or more of magnesium oxide, calcium oxide, strontium oxide and barium oxide, for example, three or four.
The catalyst a may be prepared by any method known in the art, and in this application, a preferred preparation method is given, specifically, mixing alkali metal halide and alkaline earth metal oxide powder, tabletting, drying at 100-200 ℃ under nitrogen atmosphere, and then calcining, where the drying temperature may be, for example, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃.
In the method for preparing the catalyst a, the drying time is not limited, and preferably, the drying time may be set to 5 to 10 hours, for example, 6 hours, 7 hours, 8 hours, 9 hours.
The baking temperature is not limited, and preferably, the baking temperature is 400 ℃.
The firing time is not limited, and preferably the firing time is 5 to 20 hours, for example, 6 hours, 7 hours, 8 hours, 9 hours.
In a preferred embodiment of the method for preparing the catalyst A, the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 300-600 ℃, the contact time of the raw materials is 5-200 s,
in a further preferred embodiment, the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 400 to 550 ℃, and the contact time of the raw materials is 30 to 100s.
In the liquid phase dehydrohalogenation reaction process, in one embodiment, the raw materials are reacted in the presence of a base, and the base may be any one or more than two, such as three or four, of potassium hydroxide, sodium hydroxide, rubidium hydroxide and cesium hydroxide.
In a preferred embodiment, the starting materials and the base may be catalyzed using a catalyst to accelerate the reaction.
In a preferred embodiment, the catalyst is catalyst B, and the catalyst B is any one of tetrabutylammonium bromide, benzyl triethylammonium chloride, chain polyethylene glycol, 18-crown ether-6, 15-crown ether-5 and cyclodextrin.
In one embodiment, the amount of the materials of the starting material, base and catalyst B during the liquid phase dehydrohalogenation reaction is 1:2:0.005, 1:2:0.05, 1:3:0.005, 1:3:0.05, 1:4:0.005, 1:4:0.05, 1:5:0.005, 1:5:0.05, 1:6:0.005, 1:6:0.05, 1:7:0.005, 1:8:0.005, 1:8:0.05, 1:9:0.005, 1:9:0.05, 1:10:0.005, 1:10:0.05, 1:2:0.006, 1:2:0.007, 1:3:0.008, 1:3:0.009, 1:4:0.01:7:0.005, 1:7:7:0.005, 1:7:0.05, 1:8:0.005, 1:9:0.005, 1:10:0.005, 1:0.005, 1:0.008, 1:2:0.025, 1:1:0.02, 1:0.03.
In the liquid phase dehydrohalogenation reaction, the reaction may be carried out in any apparatus to effect a liquid phase reaction, and in a preferred embodiment, the reaction is carried out in an autoclave, preferably at a pressure of from 0.1 to 0.5MPa, for example, 0.2MPa, 0.25MPa, 0.3MPa, 0.35MPa, 0.4MPa, 0.45MPa;
the reaction temperature is 25 to 100℃and may be, for example, 30℃40℃50℃60℃70℃80℃90 ℃.
The reaction time is 2 to 20 hours, and may be, for example, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours.
Method for preparing fluorine-containing alkyne in the present applicationThe starting materials may be obtained in any way, e.g., commercially purchased, prepared by themselves, etc. In one embodiment of the present application, the starting materials are obtained by self-preparation, which may be any method known in the art capable of preparing such starting materials, and the present application further provides a preferred method of preparation comprising reacting a compound of formula (V) or (VI) with X 2 Is obtained by gas phase addition reaction in the presence of a catalyst C,
wherein the structure of the compound of formula (V) is as follows,
Figure GDA0004274131580000091
wherein R is 1 Is C m F 2m+1 ，R 2 H, cl or C n F 2n+1 M and n are non-negative integers, and m+n is more than or equal to 0 and less than or equal to 12;
x is Cl or Br.
In the compound of the formula (I) as raw material, R 1 Can be F, CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 、C 5 F 11 、C 6 F 13 、C 7 F 15 、C 8 F 17 、C 9 F 19 、C 10 F 21 、C 11 F 23 、C 12 F 25 ；
In the compound of the formula (I) as raw material, R 1 Can be H, cl, F, CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 、C 5 F 11 、C 6 F 13 、C 7 F 15 、C 8 F 17 、C 9 F 19 、C 10 F 21 、C 11 F 23 、C 12 F 25 。
The structure of the compound of formula (VI) is shown below,
Figure GDA0004274131580000092
wherein R is 3 Is C p F 2p+1 ，R 4 F, cl or Br, p is a non-negative integer, and p is more than or equal to 0 and less than or equal to 12;
x is Cl or Br.
In the raw material compound of formula (II), R 3 Can be F, CF 3 、C 2 F 5 、C 3 F 7 、C 4 F 9 、C 5 F 11 、C 6 F 13 、C 7 F 15 、C 8 F 17 、C 9 F 19 、C 10 F 21 、C 11 F 23 、C 12 F 25 。
The catalyst C is one or more than two of chromium fluoride, magnesium fluoride, aluminum fluoride, ferric fluoride and calcium fluoride.
In the reaction conditions of the gas phase addition reaction, the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 150-300 ℃, preferably, the reaction pressure is 0.1-0.5 MPa, and the reaction temperature is 200-250 ℃.
In the preparation of the compound of formula (I) or the compound of formula (II) as raw materials, the compound of formula (V) or the compound of formula (VI) and X are reacted in the course of reaction 2 In a preferred embodiment, the amount of the substance is 1:1.5, for example, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, preferably the amount of the substance is 1:1.about.3.
In a preferred embodiment, the residence time of the compounds of the formula (V) or (VI) in the reactor is from 5 to 100s, for example from 10s, 15s, 20s, 25s, 30s, 35s, 40s, 45s, 50s, 55s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, preferably from 10 to 60s.
The catalyst C can be purchased commercially or prepared by itself, and a preferred preparation method is further provided herein,
Dissolving soluble salt of metal in water, adding precipitator ammonia water at 60 ℃, controlling the pH value of the solution to be between 7.5 and 8.5, fully precipitating the solution under the stirring condition, filtering the formed slurry, washing the slurry to be neutral by deionized water, and then drying the slurry at 150 ℃ for 12 hours to obtain hydroxide. Pressing and forming the obtained hydroxide to obtain a catalyst precursor; the catalyst precursor is roasted for 6 to 15 hours at 300 to 500 ℃ in nitrogen atmosphere, and then the molar ratio is 1 at 60 to 450 ℃:10 and activating for 6-15 hours in the atmosphere of mixed gas composed of fluorine and nitrogen to prepare the fluorination catalyst. Any one or more of chromium fluoride, magnesium fluoride, aluminum fluoride, iron fluoride, and calcium fluoride can be obtained according to the above method.
The gas phase addition process and the gas phase dehydrohalogenation process can realize gas phase independent circulation continuous process methods. Because the boiling points of the raw materials and the reaction products are greatly different, the raw materials and the products can be effectively separated in a distillation way of a distillation tower, unreacted raw materials are continuously recycled to the reactor to continuously participate in the reaction, and the products of the perfluor alkyne and the byproduct of the hydrogen halide are extracted from the system. The process mainly involves the following five materials:
(1) Organic raw materials such as: the boiling point of the 3, 3-trifluoropropene is-18 to-16 ℃ (760 mmHg); e-1, 3-tetrafluoropropene has a boiling point of-19 ℃ (760 mmHg); the boiling point of Z-1, 3-tetrafluoropropene is 9 ℃ (760 mmHg); the boiling point of 2, 3-tetrafluoropropene is-28 ℃ (760 mmHg); the boiling point of E-1-chloro-3, 3-trifluoropropene is 19 ℃ (760 mmHg); the boiling point of Z-1-chloro-3, 3-trifluoropropene is 38 ℃ (760 mmHg); the boiling point of the 2-chloro-3, 3-trifluoropropene is 14-15 ℃ (760 mmHg); the boiling point of 3, 4-pentafluoro-1-butene is 5-6 ℃ (760 mmHg); 2,3, 4-hexafluoro-1-butene has a boiling point of 3-7deg.C (760 mmHg); etc.
(2) Inorganic raw materials such as: cl 2 Boiling point of-34 ℃ (760 mmHg); br (Br) 2 The boiling point of (2) was 58.5 ℃ (760 mmHg).
(3) Reaction intermediates such as: the boiling point of 1, 2-dichloro-1, 3-tetrafluoropropane was 73.6deg.C (760 mmHg); the boiling point of 1, 2-dichloro-2, 3-tetrafluoropropane is 64.0deg.C (760 mmHg); the boiling point of the 1, 2-trichloro-3, 3-trifluoropropane is 104-105 ℃ (760 mmHg); the boiling point of 1, 2-trichloro-3, 3-trifluoropropane was 106.8 ℃ (760 mmHg); the boiling point of 1, 2-dichloro-3, 3-trifluoropropane was 76.7deg.C (760 mmHg); the boiling point of 1, 2-dichloro-3, 4-pentafluorobutane is 94.9 ℃ (760 mmHg); the boiling point of 1, 2-dichloro-2, 3, 4-hexafluorobutane was 72.0deg.C (760 mmHg); etc.
(4) Organic products such as: the boiling point of 3, 3-trifluoro-1-propyne is-48 ℃ (760 mmHg); the boiling point of 1, 3-tetrafluoro-1-propyne is-50 ℃ (760 mmHg); 3, 4-pentafluoro-1-butyne has a boiling point of-12 ℃ (760 mmHg); 1, 4-hexafluoro-2-butyne has a boiling point of-25 ℃ (760 mmHg); the boiling point of the 3,4, 5-heptafluoro-1-pentyne is 13-15 ℃ (760 mmHg); the boiling point of 1,4, 5-octafluoro-2-pentyne is 3-4deg.C (760 mmHg); etc.
(5) Inorganic products such as: the boiling point of hydrogen chloride is-85 ℃ (760 mmHg); the boiling point of hydrogen bromide was-66.38 ℃ (760 mmHg).
The type of reactor used for the reaction is not critical, and a tubular reactor, a fluidized bed reactor, etc. may be used as the reactor for carrying out the vapor phase addition or vapor phase dehydrohalogenation reaction, and in addition, an adiabatic reactor or an isothermal reactor may be used; the reactor for carrying out the liquid phase dehydrohalogenation reaction may be a reactor operated by a batch process using an autoclave, a glass reactor, an enamel reactor, or the like.
In a specific embodiment, the present application is further described in detail with reference to fig. 1. But not limiting the application. Fresh E-1, 3-tetrafluoropropene is fed via line 1 together with chlorine via line 17 and with a mixture of E-1, 3-tetrafluoropropene and chlorine recycled via line 6 via line 2 into a first reactor 3 filled with catalyst C, the product stream mainly comprises 1, 2-dichloro-1, 3-tetrafluoropropane and unreacted complete E-1, 3-tetrafluoropropene and chlorine, and the product stream passes through a pipeline 4 and enters a first distillation column 5 for separation; the overhead components of the first distillation column 5 were E-1, 3-tetrafluoropropene (boiling point: -19 ℃/760 mmHg) and chlorine (boiling point: -34 ℃/760 mmHg), the bottoms fraction was 1, 2-dichloro-1, 3-tetrafluoropropane (boiling point: 73.6 ℃/760 mmHg), wherein the tower top component enters the first reactor 3 through a pipeline 6 and a pipeline 2 to continue the reaction, the tower bottom component enters the second reactor 9 filled with the catalyst B through a pipeline 8 together with 1, 2-dichloro-1, 3-tetrafluoropropane recycled through a pipeline 16 to carry out gas-phase dehydrohalogenation, the reaction product flows are 1, 2-dichloro-1, 3-tetrafluoropropane, 1, 3-tetrafluoro-1-propyne, 2-chloro-1, 3-tetrafluoropropene and HCl, and the reaction product flows through a pipeline 10 to enter a second distillation tower 11 to be separated; the tower top component of the second distillation tower 11 is HCl (boiling point: 85 ℃/760 mmHg), the tower bottom component is 1, 2-dichloro-1, 3-tetrafluoropropane, 1, 3-tetrafluoro-1-propyne and 2-chloro-1, 3-tetrafluoropropene, the tower top component is extracted from the system through a pipeline 12, and the system can be continuously rectified and dehydrated to obtain high-purity HCl for selling, and can be configured into HCl solutions with different concentrations for selling; the tower bottom component of the second distillation tower 11 enters a third distillation tower 14 through a pipeline 13 for continuous separation; the tower top component of the third distillation tower 14 is 1, 3-tetrafluoro-1-propyne (boiling point: 50 ℃/760 mmHg), and the 3, 4-pentafluorobutyyne with high purity can be obtained through subsequent acid removal, water removal and rectification; the bottoms of the third distillation column 14 were 1, 2-dichloro-1, 3-tetrafluoropropane (boiling point: 73.6 ℃ C./760 mmHg) and 2-chloro-1, 3-tetrafluoropropene (boiling point: 32.8 ℃ C./760 mmHg), and were recycled to the second reactor 9 via line 16 and line 8 to continue the reaction. By the above process, quantitative conversion of the organic starting material E-1, 3-tetrafluoropropene to the target product 1, 3-tetrafluoro-1-propyne can be realized, and the final total yield is close to 100%. With a similar process flow as described above, only the organic starting material E-1, 3-tetrafluoropropene is replaced by 3, 3-trifluoropropene, E-1, 3-tetrafluoropropene, Z-1, 3-tetrafluoropropene any one of olefins such as 2, 3-tetrafluoropropene, E-1-chloro-3, 3-trifluoropropene, Z-1-chloro-3, 3-trifluoropropene, 2-chloro-3, 3-trifluoropropene, the chlorine can be replaced by liquid bromine, so that the corresponding fluorine-containing alkyne can be quantitatively synthesized.
Examples
Preparation of the catalyst
The preparation method of the catalyst A comprises the following steps: mixing the alkali metal halide and alkaline earth metal oxide powder according to the mass percentage of 1-70% and 30-99%, tabletting and forming, drying at 100-200 ℃ for 5-10 hours under nitrogen atmosphere, and roasting at 400 ℃ for 5-20 hours to obtain the catalyst A.
The preparation method of the catalyst C comprises the following steps: dissolving soluble salt of metal in water, adding precipitator ammonia water at 60 ℃, controlling the pH value of the solution to be between 7.5 and 8.5, fully precipitating the solution under the stirring condition, filtering the formed slurry, washing the slurry to be neutral by deionized water, and then drying the slurry at 150 ℃ for 12 hours to obtain hydroxide. Pressing and forming the obtained hydroxide to obtain a catalyst precursor; the catalyst precursor is roasted for 6 to 15 hours at 300 to 500 ℃ in nitrogen atmosphere, and then the molar ratio is 1 at 60 to 450 ℃:10 and activating for 6-15 hours in the atmosphere of mixed gas composed of fluorine and nitrogen to prepare the fluorination catalyst. Any one or more of chromium fluoride, magnesium fluoride, aluminum fluoride, iron fluoride, and calcium fluoride can be obtained according to the above method.
Analytical instrument: the Shimadzu GC-2010 column model was InterCap1 (i.d. 0.25mm; length60m; J & W Scientific Inc.).
Gas chromatography method: high purity helium and hydrogen are used as carrier gases. The temperature of the detector is 240 ℃, the temperature of the vaporization chamber is 150 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is increased to 240 ℃ at 20 ℃/min, and the temperature is kept for 10 minutes.
EXAMPLE 1 preparation of saturated halocarbons
The preparation route is shown as follows,
Figure GDA0004274131580000131
specifically, a tube reactor made of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of chromium fluoride prepared according to the "catalyst C preparation method". Carrying out gas phase addition reaction, heating the reactor to 150 ℃, introducing E-1, 3-tetrafluoropropene and chlorine gas for reaction, wherein the mass ratio of the E-1, 3-tetrafluoropropene to the chlorine gas is 1:1.5, the residence time of the raw materials in the reactor is 20 seconds, the reaction pressure is normal pressure, after the reactor was continuously operated for 20 hours, the composition of the material flow at the outlet of the reactor was analyzed by gas chromatography after washing with water, washing with alkali, and drying, the conversion of E-1, 3-tetrafluoropropene was 44.8%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.8%.
Example 2
The same operation as in example 1 was conducted except that the reaction temperature was changed to 200 ℃. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 98.4%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.5%.
Example 3
The same operation as in example 1 was conducted except that the reaction temperature was changed to 250 ℃. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 99.6%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.2%.
Example 4
The same operation as in example 1 was conducted except that the reaction temperature was changed to 300 ℃. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 100%, the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 85.3%, other byproducts are mainly the products of the excessive chlorination of 1, 2-dichloro-1, 3-tetrafluoropropane.
Example 5
The same operation as in example 3 was conducted except that the ratio of the amounts of E-1, 3-tetrafluoropropene and chlorine gas matters was changed to 1:1. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 88.9%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.5%.
Example 6
The same operation as in example 3 was conducted except that the ratio of the amounts of E-1, 3-tetrafluoropropene and chlorine gas matters was changed to 1:3. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 98.1%.
Example 7
The same operation as in example 3 was conducted except that the ratio of the amounts of E-1, 3-tetrafluoropropene and chlorine gas matters was changed to 1:5. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 95.8%.
Example 8
The same operation as in example 3 was performed except that the contact time was changed to 5 seconds. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 76.5%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.8%.
Example 9
The same operation as in example 3 was performed except that the contact time was changed to 10 seconds. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 85.6%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.6%.
Example 10
The same operation as in example 3 was performed except that the contact time was changed to 60 seconds. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 98.3%.
Example 11
The same operation as in example 3 was performed except that the contact time was changed to 100 seconds. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 95.8%.
Example 12
The same operation as in example 3 was conducted except that the reaction pressure was changed to 0.3MPa. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 99.8%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 98.5%.
Example 13
The same operation as in example 3 was conducted except that the reaction pressure was changed to 0.5MPa. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 96.7%.
Example 14
The same operation as in example 3 was carried out except that the catalyst was changed to magnesium fluoride. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 98.5%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.0%.
Example 15
The same operation as in example 3 was carried out, except that the catalyst was changed to aluminum fluoride. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 98.3%.
Example 16
The same operation as in example 3 was carried out except that the catalyst was changed to ferric fluoride. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 97.1%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 98.6%.
Example 17
The same operation as in example 3 was carried out, except that the catalyst was changed to calcium fluoride. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 96.2%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 98.0%.
Example 18
The preparation route is shown as follows,
Figure GDA0004274131580000161
the same operation as in example 3 was conducted except that the starting material E-1, 3-tetrafluoropropene was replaced with Z-1, 3-tetrafluoropropene in the same amount. The reaction results were as follows: the conversion of Z-1, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-1, 3-tetrafluoropropane was 97.8%.
Example 19
The preparation route is shown as follows,
Figure GDA0004274131580000162
the same operation as in example 3 was conducted except that the starting material E-1, 3-tetrafluoropropene was replaced with 2, 3-tetrafluoropropene in the same amount. The reaction results were as follows: the conversion of 2, 3-tetrafluoropropene was 100%, and the selectivity of 1, 2-dichloro-2, 3-tetrafluoropropane was 96.9%.
Example 20
The preparation route is shown as follows,
Figure GDA0004274131580000171
the same operation as in example 3 was conducted except that the starting material E-1, 3-tetrafluoropropene was replaced with 3, 3-trifluoropropene in the same amount. The reaction results were as follows: the conversion of 3, 3-trifluoropropene was 100%, and the selectivity of 1, 2-dichloro-3, 3-trifluoropropane was 99.5%.
Example 21
The preparation route is shown as follows,
Figure GDA0004274131580000172
the same operation as in example 3 was conducted except that E-1-chloro-3, 3-trifluoropropene as a raw material was replaced with E-1-chloro-3, 3-trifluoropropene in an equal amount. The reaction results were as follows: the conversion of E-1-chloro-3, 3-trifluoropropene was 98.7%, and the selectivity of 1, 2-trichloro-3, 3-trifluoropropane was 99.4%.
Example 22
The preparation route is shown as follows,
Figure GDA0004274131580000173
the same operation as in example 3 was conducted except that Z-1-chloro-3, 3-trifluoropropene as a starting material E-1, 3-tetrafluoropropene was replaced with an equivalent amount of Z-1-chloro-3, 3-trifluoropropene. The reaction results were as follows: the conversion of Z-1-chloro-3, 3-trifluoropropene was 100%, and the selectivity of 1, 2-trichloro-3, 3-trifluoropropane was 97.8%.
Example 23
The preparation route is shown as follows,
Figure GDA0004274131580000181
the same operation as in example 3 was conducted except that the starting material E-1, 3-tetrafluoropropene was replaced with an equivalent amount of 2-chloro-3, 3-trifluoropropene. The reaction results were as follows: the conversion of 2-chloro-3, 3-trifluoropropene was 100%, and the selectivity of 1, 2-trichloro-3, 3-trifluoropropane was 96.1%.
Example 24
The preparation route is shown as follows,
Figure GDA0004274131580000182
the same operation as in example 3 was conducted except that the raw material chlorine gas was replaced with liquid bromine in the same amount as in example 3. The reaction results were as follows: the conversion of E-1, 3-tetrafluoropropene was 95.2%, and the selectivity of 1, 2-dibromo-1, 3-tetrafluoropropane was 98.9%.
EXAMPLE 25 preparation of Fluoroalkynes
The preparation route is shown as follows,
Figure GDA0004274131580000183
specifically, a tube reactor made of Inconel having an inner diameter of 1/2 inch and a length of 30cm was charged with 10 ml of 60% CsF/BaO prepared according to the "catalyst A preparation method". The temperature of the reactor is raised to 300 ℃,1, 2-dichloro-1, 3-tetrafluoropropane is introduced to react for 60 seconds, the reaction pressure is normal pressure, after continuous operation for 20 hours, the reaction product is washed with water, alkali washed, dried and dehydrated to obtain an organic phase, the composition of the organic matter was analyzed by gas chromatography, and the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 98.9%, the selectivity to 1, 3-tetrafluoro-1-propyne was 10.27% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 89.73%.
Example 26
The same operation as in example 25 was conducted except that the reaction temperature was changed to 350 ℃. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 15.65%, the selectivity to 2-chloro-1, 3-tetrafluoropropene was 84.35%.
Example 27
The same operation as in example 25 was conducted except that the reaction temperature was changed to 400 ℃. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 21.78%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 78.22%.
Example 28
The same operation as in example 25 was conducted except that the reaction temperature was changed to 450 ℃. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 25.48%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 74.52%.
Example 29
The same operation as in example 25 was conducted except that the reaction temperature was changed to 500 ℃. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 30.24%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 69.76%.
Example 30
The same operation as in example 25 was conducted except that the reaction temperature was changed to 550 ℃. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 25.72%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 67.28% and the sum of the selectivities of the other byproducts was 7.00%.
Example 31
The same operation as in example 25 was conducted except that the reaction temperature was changed to 600 ℃. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 20.56%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 63.15% and the sum of the selectivities of the other byproducts was 16.29%.
Example 32
The same operation as in example 29 was performed except that the contact time was changed to 5 seconds. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 36.70%, the selectivity to 1, 3-tetrafluoro-1-propyne was 15.72% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 84.28%.
Example 33
The same operation as in example 29 was performed except that the contact time was changed to 30 seconds. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 87.45%, the selectivity to 1, 3-tetrafluoro-1-propyne was 25.28% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 74.72%.
Example 34
The same operation as in example 29 was performed except that the contact time was changed to 100 seconds. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 27.35%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 72.05% and the sum of the selectivities of the other byproducts was 0.60%.
Example 35
The same operation as in example 29 was performed except that the contact time was changed to 200 seconds. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 24.67%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 70.46% and the sum of the selectivities of the other byproducts was 5.87%.
Example 36
The same operation as in example 29 was conducted except that the reaction pressure was changed to 0.3MPa. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 85.71%, the selectivity to 1, 3-tetrafluoro-1-propyne was 27.35% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 72.65%.
Example 37
The same operation as in example 29 was conducted except that the reaction pressure was changed to 0.5MPa. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 76.82%, the selectivity to 1, 3-tetrafluoro-1-propyne was 21.73% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 78.27%.
Example 38
The same operation as in example 29 was conducted except that the catalyst was changed to 60% CsF/BaO and 1% CsF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 65.85%, the selectivity to 1, 3-tetrafluoro-1-propyne was 25.72% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 74.28%.
Example 39
The same operation as in example 29 was conducted except that the catalyst was changed to 10% CsF/BaO at 60% CsF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 85.85%, the selectivity to 1, 3-tetrafluoro-1-propyne was 26.81% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 73.19%.
Example 40
The same operation as in example 29 was conducted except that the catalyst was changed to 60% CsF/BaO and 30% CsF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 91.12%, the selectivity to 1, 3-tetrafluoro-1-propyne was 27.26% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 72.74%.
Example 41
The same operation as in example 29 was conducted except that the catalyst was changed to 60% CsF/BaO and 70% CsF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 30.30%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 69.70%.
Example 42
The same operation as in example 29 was carried out, except that the catalyst was changed to 60% CsF/BaO and 60% LiF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 89.75%, the selectivity to 1, 3-tetrafluoro-1-propyne was 15.27% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 84.73%.
Example 43
The same operation as in example 29 was conducted except that the catalyst was changed to 60% CsF/BaO and 60% NaF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 93.56%, the selectivity of 1, 3-tetrafluoro-1-propyne was 18.75%, the selectivity of 2-chloro-1, 3-tetrafluoropropene was 81.25%.
Example 44
The same operation as in example 29 was conducted except that the catalyst was changed to 60% CsF/BaO and 60% KF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 97.74%, the selectivity to 1, 3-tetrafluoro-1-propyne was 22.76% and the selectivity to 2-chloro-1, 3-tetrafluoropropene was 77.24%.
Example 45
The same operation as in example 29 was conducted except that 60% CsF/BaO of the catalyst was changed to 60% RbF/BaO. The reaction results were as follows: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 100%, the selectivity of 1, 3-tetrafluoro-1-propyne was 25.89%, the selectivity to 2-chloro-1, 3-tetrafluoropropene was 74.11%.
Example 46
The same operation as in example 29 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 2-chloro-1, 3-tetrafluoropropene in the same amount. The reaction results were as follows: the conversion of 2-chloro-1, 3-tetrafluoropropene was 35.78%, and the selectivity of 1, 3-tetrafluoro-1-propyne was 100%.
The results of example 29 demonstrate that 2-chloro-1, 3-tetrafluoropropene in the reaction products of examples 25-43 can be recycled to the reactor, continuing the dehydrochlorination reaction to convert to the desired product 1, 3-tetrafluoro-1-propyne. After a plurality of times of circulation, the device, finally, the initial raw material 1, 2-dichloro-1, 3-tetrafluoropropane and the intermediate 2-chloro can be realized complete conversion of 1, 3-tetrafluoropropene to the target product 1, 3-tetrafluoro-1-propyne, in particular, according to the process conditions of example 29, quantitative conversion of 1, 2-dichloro-1, 3-tetrafluoropropane to 1, 3-tetrafluoro-1-propyne as the starting material can be achieved.
Example 47
The same operation as in example 29 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-dichloro-2, 3-tetrafluoropropane in the same amount. The reaction results were as follows: the conversion of 1, 2-dichloro-2, 3-tetrafluoropropane was 100%, the selectivity of 1-chloro-3, 3-trifluoro-1-propyne was 23.47%, and the selectivity of 1-chloro-2, 3-tetrafluoropropene was 76.53%.
Example 48
The same operation as in example 29 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-trichloro-3, 3-trifluoropropane in the same amount. The reaction results were as follows: the conversion of 1, 2-trichloro-3, 3-trifluoropropane was 100%, the selectivity for 1-chloro-3, 3-trifluoro-1-propyne was 36.78%, and the selectivity for 1, 2-dichloro-3, 3-trifluoropropene was 63.22%.
Example 49
The same operation as in example 29 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-trichloro-3, 3-trifluoropropane in the same amount. The reaction results were as follows: the conversion of 1, 2-trichloro-3, 3-trifluoropropane was 100%, the selectivity for 1-chloro-3, 3-trifluoro-1-propyne was 34.25%, and the selectivity for 1, 2-dichloro-3, 3-trifluoropropene was 65.75%.
Example 50
The same operation as in example 29 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-dichloro-3, 3-trifluoropropane in the same amount as the above-mentioned substance. The reaction results were as follows: the conversion of 1, 2-dichloro-3, 3-trifluoropropane was 100%, the selectivity for 3, 3-trifluoro-1-propyne was 21.33%, and the selectivity for 2-chloro-3, 3-trifluoropropene was 78.67%.
Example 51
The same operations as in example 29 were conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-dibromo-1, 3-tetrafluoropropane in the same amount. The reaction results were as follows: the conversion of 1, 2-dibromo-1, 3-tetrafluoropropane was 100%, the selectivity to 1, 3-tetrafluoro-1-propyne was 57.26% and the selectivity to 2-bromo-1, 3-tetrafluoropropene was 42.74%.
EXAMPLE 52 preparation of Fluoroalkynes
Adding 30% of KOH aqueous solution with mass percent concentration, tetrabutylammonium bromide and 1, 2-dichloro-1, 3-tetrafluoropropane into an autoclave, wherein the ratio of the 1, 2-dichloro-1, 3-tetrafluoropropane to the substances of KOH and tetrabutylammonium bromide is 1:5:0.02, the reaction temperature is 30 ℃, the reaction time is 10 hours, the reaction is cooled to room temperature, the gas is collected to obtain 1, 3-tetrafluoro-1-propyne, the residual 1, 2-dichloro-1, 3-tetrafluoropropane in the reaction kettle is recovered, and the following results are obtained through weighing and GC analysis: the conversion of 1, 2-dichloro-1, 3-tetrafluoropropane was 99.2%, and the selectivity of 1, 3-tetrafluoro-1-propyne was 99.4%.
Example 53
The same operation as in example 52 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-dichloro-2, 3-tetrafluoropropane in the same amount as the above, and the following results were obtained: the conversion of 1, 2-dichloro-2, 3-tetrafluoropropane was 100%, and the selectivity of 1-chloro-3, 3-trifluoro-1-propyne was 99.6%.
Example 54
The same operation as in example 52 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-trichloro-3, 3-trifluoropropane in the same amount as the above, and the following results were obtained: the conversion of 1, 2-trichloro-3, 3-trifluoropropane was 100%, and the selectivity of 1-chloro-3, 3-trifluoro-1-propyne was 99.3%.
Example 55
The same operation as in example 52 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-trichloro-3, 3-trifluoropropane in the same amount as the above, and the following results were obtained: the conversion of 1, 2-trichloro-3, 3-trifluoropropane was 100%, and the selectivity of 1-chloro-3, 3-trifluoro-1-propyne was 99.5%.
Example 56
The same operation as in example 52 was conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-dichloro-3, 3-trifluoropropane in the same amount as the above, and the following results were obtained: the conversion of 1, 2-dichloro-3, 3-trifluoropropane was 100%, and the selectivity of 3, 3-trifluoro-1-propyne was 99.3%.
Example 57
The same operations as in example 52 were conducted except that 1, 2-dichloro-1, 3-tetrafluoropropane was changed to 1, 2-dibromo-1, 3-tetrafluoropropane in the same amount as the above, and the following results were obtained: the conversion of 1, 2-dibromo-1, 3-tetrafluoropropane was 100%, and the selectivity of 1, 3-tetrafluoro-1-propyne was 99.8%.
Although described above in connection with the embodiments of the present application, the present application is not limited to the specific embodiments and fields of application described above, which are intended to be illustrative, instructive, and not limiting. Those skilled in the art, having the benefit of this disclosure, may make numerous forms, and equivalents thereof, without departing from the scope of the invention as defined by the claims.

Claims (17)

1. A preparation method of fluorine-containing alkyne uses a compound of formula (I) or a compound of formula (II) as a raw material to carry out dehydrohalogenation reaction to obtain the fluorine-containing alkyne,
wherein the structure of the compound of formula (I) is shown below,
Figure FDA0004274131570000011
wherein R is 1 Is C m F 2m+1 ，R 2 H, cl or C n F 2n+1 M and n are non-negative integers, m+n is more than or equal to 0 and less than or equal to 12, the structural formula of the obtained fluorine-containing alkyne is shown as a formula (III),
Figure FDA0004274131570000012
the dehydrohalogenation reaction is a gas phase dehydrohalogenation reaction;
the raw materials react in the presence of a catalyst A, wherein the catalyst A is a catalyst consisting of alkali metal halides and alkaline earth metal oxides;
the reaction pressure is 0.1-0.5 MPa, the reaction temperature is 300-600 ℃, and the contact time of raw materials is 5-200 s;
the structure of the compound of formula (II) is shown below,
Figure FDA0004274131570000013
wherein R is 3 Is C p F 2p+1 ，R 4 F, cl or Br, p is a non-negative integer, and p is more than or equal to 0 and less than or equal to 12; the structural formula of the obtained fluorine-containing alkyne is shown as a formula (IV),
Figure FDA0004274131570000014
the dehydrohalogenation reaction is a liquid phase dehydrohalogenation reaction;
the raw materials react with alkali in the presence of a catalyst B, wherein the catalyst B is any one of tetrabutylammonium bromide, benzyl triethylammonium chloride, chain polyethylene glycol, 18-crown ether-6, 15-crown ether-5 and cyclodextrin;
The reaction pressure is 0.1-0.5 MPa, the reaction temperature is 25-100 ℃, and the reaction time is 2-20 h;
x is Cl or Br.
2. The method of claim 1, wherein the alkali metal halide and alkaline earth metal oxide are 1-70% and 30-99% by mass.
3. The method according to claim 2, wherein the alkali metal halide is any one or two or more of lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, lithium chloride, sodium chloride, potassium chloride, rubidium chloride, cesium chloride, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, rubidium iodide, cesium iodide, or
The alkaline earth metal oxide is any one or more than two of magnesium oxide, calcium oxide, strontium oxide and barium oxide.
4. The method according to claim 1 or 2, wherein the catalyst a is prepared by mixing an alkali metal halide and an alkaline earth metal oxide powder, tabletting, drying at 100-200 ℃ under nitrogen atmosphere, and then calcining.
5. The method according to claim 4, wherein the drying time is 5 to 10 hours, or the firing temperature is 400 ℃, or the firing time is 5 to 20 hours.
6. The process according to claim 1 or 2, wherein the reaction pressure is 0.1 to 0.5MPa, the reaction temperature is 400 to 550 ℃, and the contact time of the raw materials is 30 to 100s.
7. The method according to claim 1 or 2, wherein the base is any one or two or more of potassium hydroxide, sodium hydroxide, rubidium hydroxide, and cesium hydroxide.
8. The process according to claim 1 or 2, wherein the ratio of the amounts of the materials of the raw material, the base and the catalyst B is 1: (2 to 10): (0.005 to 0.05).
9. The process according to claim 1 or 2, wherein the reaction is carried out in an autoclave.
10. The process according to claim 1 or 2, wherein the starting material is prepared from a compound of formula (V) or (VI) and X 2 Is obtained by gas phase addition reaction in the presence of a catalyst C,
wherein the structure of the compound of formula (V) is as follows,
Figure FDA0004274131570000021
wherein R is 1 Is C m F 2m+1 ，R 2 H, cl or C n F 2n+1 M and n are non-negative integers, and m+n is more than or equal to 0 and less than or equal to 12;
the structure of the compound of formula (VI) is shown below,
Figure FDA0004274131570000031
wherein R is 3 Is C p F 2p+1 ，R 4 F, cl or Br, p is a non-negative integer, and p is more than or equal to 0 and less than or equal to 12;
x is Cl or Br.
11. The method according to claim 10, wherein the reaction pressure is 0.1 to 0.5MPa and the reaction temperature is 150 to 300 ℃ in the reaction conditions of the gas phase addition reaction.
12. The method of claim 11, wherein the reaction pressure is 0.1-0.5 MPa and the reaction temperature is 200-250 ℃.
13. The method of claim 10, wherein the compound of formula (V) or formula (VI) is mixed with X 2 The mass ratio of the substances is 1:1-5.
14. The method of claim 13, wherein the amount of the substance is 1:1-3.
15. The process according to claim 10, wherein the residence time of the compound of formula (V) or (VI) in the reactor is from 5 to 100s.
16. The method of claim 15, wherein the residence time is 10 to 60 seconds.
17. The method according to claim 10, wherein the catalyst C is any one or two or more of chromium fluoride, magnesium fluoride, aluminum fluoride, iron fluoride, and calcium fluoride.
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