CN114014782A - Method for continuously preparing heptafluoroisobutyronitrile through amination-dehydration one-pot gas phase - Google Patents

Method for continuously preparing heptafluoroisobutyronitrile through amination-dehydration one-pot gas phase Download PDF

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CN114014782A
CN114014782A CN202111222131.0A CN202111222131A CN114014782A CN 114014782 A CN114014782 A CN 114014782A CN 202111222131 A CN202111222131 A CN 202111222131A CN 114014782 A CN114014782 A CN 114014782A
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权恒道
张呈平
刘冬鹏
庆飞要
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Guangdong Laboratory Of Chemistry And Fine Chemicals
Beijing Yuji Science and Technology Co Ltd
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Beijing Yuji Science and Technology Co Ltd
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Abstract

The invention discloses a method for continuously preparing heptafluoroisobutyronitrile by amination-dehydration one-pot gas phase method, which is characterized in that (CF)3)2CFC(O)‑R1Or isomer 2-R thereof1-2-fluoro-3, 3-bis (trifluoromethyl) oxirane (R)1Is any one of F, Cl, Br, I or C1-C4 alkoxy) as a raw material, and is subjected to amination-dehydration one-pot gas phase continuous reaction with ammonia gas or primary amine in a tubular reactor in the presence of a catalyst to obtain the heptafluoroisobutyronitrile, wherein the catalyst is one or more of aluminum fluoride, iron fluoride, magnesium fluoride, calcium fluoride, barium fluoride and chromium fluoride. The invention simplifies the traditional amination and dehydration two-step liquid phase intermittent reaction into one-pot gas phase continuous preparation of heptafluoroisobutyronitrile, adopts the same catalyst to complete continuous amination-dehydration gas phase reaction, shortens the reaction route, has high one-way yield of the heptafluoroisobutyronitrile, and is easy for continuous industrialization.

Description

Method for continuously preparing heptafluoroisobutyronitrile through amination-dehydration one-pot gas phase
Technical Field
The invention relates to a method for preparing heptafluoroisobutyronitrile continuously in gas phase by amination-dehydration one-pot method, in particular to a method for preparing (CF)3)2CFC(O)-R1Or isomer 2-R thereof1-2-fluoro-3, 3-bis (trifluoromethyl) oxirane (R)1Is F, Cl, Br, I or C1-C4 alkoxy) as raw material, and the raw material (CF), and ammonia gas or primary amine are subjected to amination-dehydration reaction to obtain the heptafluoroisobutyronitrile by a one-pot gas phase continuous method3)2CFC(O)-R1Or isomer 2-R thereof1A method for synthesizing (E) -2-fluoro-3, 3-bis (trifluoromethyl) oxirane.
Background
At present, in many reported synthetic routes of heptafluoroisobutyronitrile, the most common route is to synthesize heptafluoroisobutyronitrile by using heptafluoroisobutyryl fluoride as a raw material through three steps of reactions of esterification, amination and dehydration, and the specific steps are as follows: (1) esterification reaction: reaction of heptafluoroisobutyryl fluoride with methanol at 0 ℃ gives methyl heptafluoroisobutyrate (see "Journal of Polymer Science, Part B: Polymer Letters,1966,4(4), p.283-286"); (2) amination reaction: in a methanol solvent, methyl heptafluoroisobutyrate reacts with ammonia gas to obtain heptafluoroisobutyramide with the yield of 81.1% (see Chinese patent CN 104662617A); (3) and (3) dehydration reaction: heptafluoroisobutyronitrile is obtained by dehydration reaction of heptafluoroisobutyramide in DMF solvent in the presence of pyridine and trifluoroacetic anhydride with a yield of 74.9% (see Chinese patent CN 104662617A). The equations are shown in equations (1) - (3).
Figure BDA0003312993530000011
Figure BDA0003312993530000012
Figure BDA0003312993530000013
The above reaction route has the following problems: (1) all the methods are intermittent liquid phase methods, and a large amount of solvents are adopted, so that a large amount of waste liquid is generated, and the environment is seriously polluted; (2) the method takes heptafluoro isobutyryl fluoride as a raw material, comprises three steps of reactions including esterification, amination and dehydration, and has a long route; (3) the method takes methyl heptafluoroisobutyrate as a raw material, and comprises two steps of reactions including amination and dehydration, and the route is still long.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the background technology and provides a method for preparing heptafluoroisobutyronitrile continuously in a gas phase manner by adopting a gas phase continuous route and simplifying the traditional two-step reaction of amination and dehydration in an intermittent liquid phase into a one-pot method.
The invention also provides the starting material (CF)3)2CFC(O)-R1Or isomers thereof2-R1-2-fluoro-3, 3-bis (trifluoromethyl) oxirane (R)1F, Cl, Br, I or C1-C4 alkoxy).
In order to achieve the object of the invention, the invention
Figure BDA0003312993530000021
Or isomers thereof
Figure BDA0003312993530000022
(R1Is F, Cl, Br, I or C1-C4 alkoxy) as raw material, and amination reagent ammonia gas or primary amine R-NH2(R is-C)nH2n+1Group, n is a positive integer set) to undergo a gas-phase continuous amination-dehydration reaction in a one-pot process to obtain heptafluoroisobutyronitrile, and the main reactions occurring are classified into the following two types:
(1) when the amination reagent is ammonia, the following reaction occurs:
Figure BDA0003312993530000023
(2) when the amination reagent is a primary amine, the following reaction occurs:
Figure BDA0003312993530000031
a method for continuously preparing heptafluoroisobutyronitrile by an amination-dehydration one-pot gas phase method comprises the following steps:
a. provided with a general formula of
Figure BDA0003312993530000032
Or isomers thereof
Figure BDA0003312993530000033
Wherein R is1Is F, Cl, Br, I or C1-C4 alkoxy;
b. in the presence of a catalyst, in a tubular reactor,
Figure BDA0003312993530000034
or isomers thereof
Figure BDA0003312993530000035
With aminating reagents ammonia or primary amine compounds R-NH2Carrying out gas-phase continuous amination-dehydration one-pot reaction to obtain heptafluoroisobutyronitrile, wherein the catalyst is one or more of aluminum fluoride, ferric fluoride, magnesium fluoride, calcium fluoride, barium fluoride and chromium fluoride; wherein R is-CnH2n+1And n is a positive integer set.
The tubular reactor in the step b consists of relatively independent heating sections which are connected end to end, the temperature of the tubular reactor in the length direction from the inlet to the outlet is sequentially increased, the temperature in the tubular reactor is 100-550 ℃, the contact time is 1-300 s, and R is-CnH2n+1And n is a positive integer set from 1 to 8.
The tubular reactor consists of 2 to 7 relatively independent heating sections and comprises a catalyst,
Figure BDA0003312993530000041
or isomers thereof
Figure BDA0003312993530000042
With aminating reagents ammonia or primary amine compounds R-NH2The ratio of the amounts of substances (1): 1-30 ℃, the reaction temperature of each heating section is 100-550 ℃, and the contact time is 1-300 s.
The step b is a tubular reactor consisting of 3 relatively independent heating sections with equal length, in the presence of a catalyst,
Figure BDA0003312993530000043
or isomers thereof
Figure BDA0003312993530000044
With aminating reagents ammonia or primary amine compounds R-NH2The ratio of the amounts of substances (1): 5-20 ℃, the reaction temperature of the heating section 1 is 100-300 ℃, the reaction temperature of the heating section 3 is 300-550 ℃, and the heating section 2The reaction temperature of the sections is the average value of the sections 1 and 3, the reactant flows sequentially pass through the section 1 heating section, the section 2 heating section and the section 3 heating section, and the contact time is 1-300 s.
The step b is a step of reacting in a tubular reactor with 3 relatively independent heating sections with equal length, in the presence of a catalyst,
Figure BDA0003312993530000045
or isomers thereof
Figure BDA0003312993530000046
With aminating reagents ammonia or primary amine compounds R-NH2The ratio of the amounts of substances (1): 5-20 ℃, the reaction temperature of the heating section 1 is 120-300 ℃, the reaction temperature of the heating section 3 is 300-450 ℃, the reaction temperature of the heating section 2 is the average value of the heating sections 1 and 3, the reactant material flows sequentially pass through the heating section 1, the heating section 2 and the heating section 3, the contact time is 10-200 s, wherein R is-CnH2n+1Group, n ═ 1,2 or 3, R1F, Cl, methoxy or ethoxy.
In the step a
Figure BDA0003312993530000051
The synthesis method comprises the following steps: in the presence of an isomerization catalyst, the catalyst,
Figure BDA0003312993530000052
the gas phase isomerization reaction is carried out, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃,
Figure BDA0003312993530000053
the contact time of (a) is 0.1 to 100 s; wherein the isomerization catalyst is one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride; alternatively, the first and second electrodes may be,
in the presence of a halogenation catalyst, heptafluoroisobutyraldehyde and a halogen simple substance are subjected to halogenation reaction to obtain
Figure BDA0003312993530000054
Wherein the halogen is F2、Cl2、Br2Or I2，R1F, Cl, Br or I; the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, the ratio of the amount of heptafluoroisobutyraldehyde to the halogen simple substance is 1: 1-10, and the contact time is 0.1-100 s, wherein the halogenated catalyst is at least one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride.
In the step a
Figure BDA0003312993530000055
The synthesis method comprises the following steps: under the condition of stirring, in an organic solvent A, a catalyst A catalyzes
Figure BDA0003312993530000061
Reacting with sodium hypochlorite to obtain
Figure BDA0003312993530000062
The reaction conditions are as follows:
Figure BDA0003312993530000063
the ratio of the amount of sodium hypochlorite to the amount of the catalyst A is 1: 5-20: 0.01-0.05, the reaction temperature is 0-50 ℃, and the reaction time is 3-48 h, wherein the organic solvent A is any one of toluene, xylene, trimethylbenzene, acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile, and the catalyst A is any one of tetrabutylammonium bromide or tetrabutylphosphonium bromide.
In the step a
Figure BDA0003312993530000064
The synthesis method comprises the following steps: in the presence of a fluorination catalyst, hexafluoropropylene and
Figure BDA0003312993530000065
the hydrogen fluoride is subjected to fluorination reaction to obtain the heptafluoro isobutyryl fluoride, and the reaction conditions are as follows: reaction pressure 0.1About 1.5MPa, the reaction temperature is 50-300 ℃, hexafluoropropylene and
Figure BDA0003312993530000066
the mass ratio of hydrogen fluoride is 1: 1 to 5: 0 to 20, and the contact time is 0.1 to 100s, wherein R2、R3Respectively is any one of F, Cl, Br or I; when R is2、R3Meanwhile, when F is adopted, HF can be zero or not; when R is2、R3When not being F, HF is not zero; alternatively, the first and second electrodes may be,
in the presence of a fluorination catalyst, hexafluoropropylene and
Figure BDA0003312993530000067
the hydrogen fluoride and the elementary halogen are subjected to halogen fluorination reaction to obtain the heptafluoro isobutyryl fluoride, wherein the elementary halogen is F2、Cl2、Br2Or I2The reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, and the hexafluoropropylene and the propylene are mixed
Figure BDA0003312993530000068
The ratio of the hydrogen fluoride to the halogen simple substance is 1: 1 to 5: 0 to 20: 1 to 5, and a contact time of 0.1 to 100s, wherein R4Is F, Cl, Br or I; when the elementary halogen is F2HF may or may not be zero; when the halogen is Cl2、Br2Or I2HF is not zero;
alternatively, the first and second electrodes may be,
in the presence of a fluorination catalyst,
Figure BDA0003312993530000071
carrying out fluorination reaction with hydrogen fluoride to obtain heptafluoro isobutyryl fluoride, wherein the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃,
Figure BDA0003312993530000072
the amount of the hydrogen fluoride is 1: 1 to 20, and the contact time is 0.1 to 100s, wherein R5Is Cl, Br or I.
In the step a
Figure BDA0003312993530000073
The synthesis method comprises the following steps: in the presence of a fluorination catalyst, hexafluoropropylene and
Figure BDA0003312993530000074
an addition reaction occurs to obtain
Figure BDA0003312993530000075
Wherein R is5Is Cl, Br or I, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, and the hexafluoropropylene and the propylene are mixed
Figure BDA0003312993530000076
The amount ratio of the substances is 1: 1 to 10, and the contact time is 0.1 to 100 s; alternatively, the first and second electrodes may be,
the synthetic method of the heptafluoroisobutyraldehyde comprises the following steps: in the presence of a fluorination catalyst, hexafluoropropylene and
Figure BDA0003312993530000077
the hydrogen fluoride performs halogen fluorination reaction to obtain heptafluoroisobutyraldehyde, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, and the hexafluoropropylene and the propylene are mixed
Figure BDA0003312993530000078
The mass ratio of hydrogen fluoride is 1: 1 to 10: 0 to 20, and the contact time is 0.1 to 100s, wherein R4Is F, Cl, Br or I; when R is4When F is contained, HF may be zero or not; when R is4When Cl, Br or I, HF is not zero; or
In the presence of an isomerization catalyst, the catalyst,
Figure BDA0003312993530000081
the gas phase isomerization reaction is carried out to obtain heptafluoroisobutyraldehyde, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃,
Figure BDA0003312993530000082
the contact time of (3) is 0.1 to 100 seconds.
The fluorination catalyst is a chromium-based catalyst, a molybdenum-based catalyst or a tungsten-based catalyst modified by taking at least one element of magnesium, iron, cobalt, nickel, zinc and aluminum as an auxiliary agent, and the mass percentage of the auxiliary agent element to the chromium, molybdenum or tungsten element is 1-20%: 80-99%, and the metal element exists in the form of metal fluoride or metal oxyfluoride.
The isomerization catalyst is one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride.
The above-mentioned
Figure BDA0003312993530000083
The synthesis method comprises the following steps: under the condition of stirring, in organic solvent B, catalyst B catalyzes
Figure BDA0003312993530000084
Reacting with sodium hypochlorite to obtain
Figure BDA0003312993530000085
The reaction conditions are as follows:
Figure BDA0003312993530000086
the mass ratio of sodium hypochlorite to the mass of the catalyst B is 1: 5-20: 0.01-0.05, the reaction temperature is 0-50 ℃, and the reaction time is 3-48 h, wherein the organic solvent B is any one of toluene, xylene, trimethylbenzene, acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile, and the catalyst B is any one of tetrabutylammonium bromide or tetrabutylphosphonium bromide.
In the step a
Figure BDA0003312993530000091
(R1Is C1-C4 alkoxy) is prepared by the following steps: in the presence of the catalyst C,
Figure BDA0003312993530000092
with C1-C4 alcoholsEsterification reaction is carried out to obtain
Figure BDA0003312993530000093
(R1Is C1-C4 alkoxy), the reaction conditions are as follows:
Figure BDA0003312993530000094
or
Figure BDA0003312993530000095
The mass ratio of C1-C4 alcohol to substance is 1: 1-20 ℃, the reaction temperature is 50-300 ℃, and the contact time is 0.1-100 s; wherein the catalyst C is one or more of magnesium fluoride, ferric fluoride, calcium fluoride, barium fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride.
The catalyst for amination-dehydration one-pot reaction, fluorination catalyst, halogenation catalyst, isomerization catalyst and esterification catalyst involved in the present invention can be prepared by the following methods: dissolving soluble salt in water according to the mass percentage of the catalyst, adding ammonia water as a precipitant at 60 ℃, controlling the pH value of the solution within the range of 7-9, fully precipitating the solution under stirring, then aging for 10-24 hours, filtering the formed slurry, washing the slurry to be neutral by deionized water, then drying the slurry at 150 ℃ for 10-24 hours to obtain a solid, crushing the solid, pressing and forming to obtain a catalyst precursor, then roasting the catalyst precursor at 450 ℃ for 10-24 hours in a nitrogen atmosphere, and using the substances at 300 ℃ in a ratio of 1: 2, activating for 10-24 hours by using mixed gas consisting of hydrogen fluoride and nitrogen to prepare the catalyst. The soluble salt is chloride, nitrate or acetate of metal. The catalysts for amination-dehydration one-pot reaction, fluorination catalysts, halogenation catalysts, isomerization catalysts, esterification catalysts referred to in this patent can be prepared according to the above-mentioned methods. The soluble salt is chloride, nitrate or acetate of metal. Wherein: (1) the catalyst for the amination-dehydration one-pot reaction is one or more of aluminum fluoride, ferric fluoride, magnesium fluoride, calcium fluoride, barium fluoride and chromium fluoride; (2) the halogenation catalyst is at least one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride; (3) the fluorination catalyst is a chromium-based catalyst, a molybdenum-based catalyst or a tungsten-based catalyst modified by taking at least one element of magnesium, iron, cobalt, nickel, zinc and aluminum as an auxiliary agent, and the mass percentage of the auxiliary agent element to the chromium, molybdenum or tungsten element is 1-20%: 80-99%; (4) the catalyst for esterification is one or more of magnesium fluoride, ferric fluoride, calcium fluoride, barium fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride; (5) the isomerization catalyst is one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride. In the above-mentioned metals, except for molybdenum and tungsten, which are in the form of metal oxyfluoride, the other metals are metal fluorides, and the activation time can also be shortened, and the oxyfluoride of the other metals can be obtained by shortening the activation time from 10-24 hours to 3-6 hours.
The catalyst of the present invention may be a commercially available metal fluoride in addition to the catalyst prepared as described above.
The gas phase preparation of heptafluoroisobutyronitrile by the one-pot method of amination-dehydration reaction of the invention can realize continuous flow, for example: when the organic raw material is heptafluoro isobutyryl fluoride: (1) if the amination reagent is a primary amine R-NH2When the reaction stream of step b contains heptafluoroisobutyronitrile, R-F, water, excess R-NH2And a small amount of heptafluoroisobutyramide, wherein R-F is a fluorine-containing gas, the heptafluoroisobutyramide in a molten state is continuously circulated to the reactor for dehydration reaction through a simple gas-liquid phase separator, and the heptafluoroisobutyronitrile in a gas phase state, R-F, water and excess R-NH are subjected to dehydration reaction2Can be subjected to subsequent separation and drying to obtain R-NH2The amine can be circulated to the reactor for continuous reaction, the crude product of the heptafluoroisobutyronitrile can be extracted out of the system, and the high-purity heptafluoroisobutyronitrile (the boiling point is-3.9 ℃) can be obtained by continuous rectification; (2) if the amination reagent is ammonia, the reaction stream of step b contains heptafluoroisobutyronitrile, ammonium fluoride, water, excess NH3And a small amount of heptafluoroisobutyramide, and fluorinating the mixture in a molten state by a simple gas-liquid phase separatorThe mixture of ammonium and heptafluoro isobutyryl ammonium is transferred to a liquid-solid phase separator for continuous separation, while the gas phase of heptafluoro isobutyronitrile, water and NH3Can be subjected to subsequent separation and drying, NH3Continuously circulating to the reactor for continuous reaction, collecting the crude product of heptafluoroisobutyronitrile, and continuously rectifying to obtain high-purity heptafluoroisobutyronitrile (the boiling point is-3.9 ℃); in addition, in the liquid-solid phase separator, the lower layer is solid ammonium fluoride, the upper layer is molten heptafluoro isobutyryl ammonium, heptafluoro isobutyramide can circulate to the reactor for continuous reaction, when the lower layer of solid ammonium fluoride reaches a sufficient amount, the inlet material flow is switched to another standby liquid-solid phase separator, the original phase separator which is filled with sufficient solid ammonium fluoride is heated, the ammonium fluoride is in a molten state, the system is collected, and when the collection of the ammonium fluoride is finished, the original phase separator is converted into the role of the standby phase separator. When the organic raw material is
Figure BDA0003312993530000101
In the case, the case is almost completely similar to the case where heptafluoroisobutyryl fluoride is used as a raw material, and only the organic raw material needs to be replaced. When the organic raw material is heptafluoroisobutyryl chloride or
Figure BDA0003312993530000111
In this case, the organic material was replaced with HCl and ammonium fluoride with ammonium chloride, similarly to the case of heptafluoroisobutyryl fluoride. When the organic raw material is methyl heptafluoroisobutyrate or ethyl heptafluoroisobutyrate, the situation is simpler than the above organic raw material because no ammonium fluoride or ammonium chloride is produced and only a simple separation method is required to achieve effective separation.
The amination reagent primary amine R-NH used in step b of the invention2Besides methylamine, ethylamine and propylamine, other primary amines can also be used.
The type of reactor used in the step a and step b of the present invention may be a 316 tubular reactor, a Monel reactor, or the like.
The invention has the advantages that:
(1) the synthetic route of the invention is novel, the traditional two-step liquid phase intermittent reaction of amination and dehydration is simplified into a one-pot gas phase continuous process, the two-step gas phase reaction adopts the same catalyst and the intermediate product does not need to be separated;
(2) starting materials such as hexafluoropropylene, acyl halides, and fluoroolefins are readily available;
(3) compared with the prior art, the one-pot gas-phase continuous process has the advantages that the total yield of the heptafluoroisobutyronitrile is high, and continuous circulation can be realized, so that the industrial synthesis cost of the heptafluoroisobutyronitrile is greatly reduced.
Drawings
The invention is described in further detail below with reference to the accompanying drawings.
FIG. 1 shows a flow chart of a preparation process for preparing heptafluoroisobutyronitrile from hexafluoropropylene, phosgene and hydrogen fluoride as starting materials via an intermediate of heptafluoroisobutyryl fluoride.
The reference numerals in fig. 1 have the following meanings. Pipeline: 1. 2,3, 4, 6, 8, 9, 11, 12, 14, 15, 17, 18, 19, 21, 22, 24, 25, 27, 28, 29, 30, 32, 33, 35, 37, 38, and 39; a first reactor: 5; a second reactor: 13; a first distillation column: 7; a second distillation column: 10; a third distillation column: 13; a fourth distillation column: 20; a fifth distillation column: 31; a sixth distillation column: 36; a phase splitter: 23; a standby phase splitter: 26; a drying tower: 34.
Detailed Description
The present invention is described in further detail with reference to fig. 1. But not to limit the invention. Fresh hexafluoropropene via line 1 with fresh hydrogen fluoride via line 2, and fresh COCl via line 32And hydrogen fluoride and COCl recycled via line 122The mixture of (a) and hexafluoropropylene recycled via line 14 are fed via line 4 to a first reactor 5 packed with a fluorination catalyst bed, and the product stream is heptafluoroisobutyryl fluoride, hydrogen chloride and excess hexafluoropropylene, COCl2And hydrogen fluoride, the product stream being passed via line 6 to a first distillation column 7 for separation; the top component of the first distillation tower 7 is hydrogen chloride (boiling point is-85 ℃/760mmHg), and the bottom component is heptafluoro isobutyryl fluoride, hydrogen chloride and sodium chlorideRemaining hexafluoropropylene and COCl2The tower top component is extracted from the system through a pipeline 8, can be used as a byproduct, namely hydrogen chloride for sale after further rectification and purification, can also be prepared into hydrochloric acid with different concentrations for sale, and the tower bottom component enters a second distillation tower 10 through a pipeline 9 for separation; the second distillation column 10 had an overhead composition of heptafluoroisobutyryl fluoride and hexafluoropropylene and a bottom composition of hydrogen fluoride (boiling point 19.5 ℃ C./760 mmHg) and COCl2(boiling point is 8.3 ℃/760mmHg), the bottom component is recycled to the first reactor 5 through the pipeline 12 and the pipeline 4 for continuous reaction, and the overhead component enters the third distillation tower 13 through the pipeline 11 for continuous separation; the overhead component of the third distillation tower 13 is hexafluoropropylene (boiling point is-29.6 ℃/760mmHg), the bottom component is heptafluoro isobutyryl fluoride (boiling point is 0-2 ℃/760mmHg), and the overhead component is circulated to the first reactor 5 through the pipeline 14 and the pipeline 4 to continue the reaction; the bottom components of the third distillation column 13 are fed via line 15 together with fresh ammonia gas via line 18 and heptafluoroisobutyramide recycled via line 30 via line 17 into a second reactor 16 (tubular reactor for one-pot reaction) packed with a catalyst bed, and the product stream is heptafluoroisobutyronitrile, ammonium fluoride, water, excess NH3And heptafluoroisobutyramide, the product flows through a pipeline 19 and enters a fourth distillation tower 20 for continuous separation, ammonium fluoride and heptafluoroisobutyramide are arranged at the tower bottom, and heptafluoroisobutyronitrile, water and excess NH are arranged at the tower top3The tower bottom components in the molten state enter the phase separator 23 through a pipeline 22 and a pipeline 24 to be continuously separated, at the moment, a pipeline 27 is in a closed state, the temperature of the phase separator is controlled, the lower layer of the phase separator 23 is solid ammonium fluoride, the upper layer of the phase separator 23 is molten heptafluoro isobutyryl ammonium (melting point is 46-51 ℃), and after the heptafluoro isobutyryl amide is dried, recycled to the second reactor 16 via lines 39, 30 and 17 for further reaction, when a sufficient amount of lower solid ammonium fluoride is present, line 24 is closed, simultaneously, a pipeline 27 is opened, tower bottom components of the fourth distillation tower 20 in a molten state enter a phase separator 26 through the pipeline 22 and the pipeline 27 to be continuously separated, the phase separator 23 filled with enough solid ammonium fluoride is heated, the ammonium fluoride (the melting point is 100 ℃) is in a molten state, the ammonium fluoride is collected out of a system, and when the ammonium fluoride is collected, the phase separator 23 is converted into a standby phase separator; top group of fourth distillation column 20The mixture enters a fifth distillation tower 31 through a pipeline 21 to be continuously separated, the tower bottom component is ammonia water (the boiling point is 24.7 ℃/760mmHg), the tower top component is ammonia gas, heptafluoroisobutyronitrile and a small amount of water vapor, the tower bottom component can be prepared into ammonia water with corresponding concentration to be sold, the tower top component enters a drying tower 34 filled with molecular sieves through a pipeline 32 to be dried and dehydrated, the material from the drying tower 34 flows into a sixth distillation tower 36 through a pipeline 35 to be separated, the tower top component is ammonia gas (the boiling point is-33.34 ℃/760mmHg), the tower bottom component is heptafluoroisobutyronitrile (the boiling point is-3.9 ℃/760mmHg), the tower top component circulates to a second reactor 16 through a pipeline 37 and a pipeline 17 to be continuously reacted, and the tower bottom component can obtain a target product, namely heptafluoroisobutyronitrile, through deacidification, dehydration and rectification.
An analytical instrument: shimadzu GC-2010, column InterCap1 (i.d.0.25mm; length 60 m; J & W Scientific Inc.).
GC analysis method: the temperature of the detector is 250 ℃, the temperature of the vaporization chamber is 250 ℃, the initial temperature of the column is 40 ℃, the temperature is kept for 10 minutes, the temperature is increased to 230 ℃ at the speed of 15 ℃/min, and the temperature is kept for 8 minutes.
The present invention will be described in further detail with reference to the following examples, which are not intended to limit the scope of the present invention.
Preparation of the catalyst: dissolving soluble salt in water according to the mass percentage of the catalyst, adding ammonia water as a precipitant at 60 ℃, controlling the pH value of the solution within the range of 7-9, fully precipitating the solution under stirring, then aging for 10-24 hours, filtering the formed slurry, washing the slurry to be neutral by deionized water, then drying the slurry at 150 ℃ for 10-24 hours to obtain a solid, crushing the solid, pressing and forming to obtain a catalyst precursor, then roasting the catalyst precursor at 450 ℃ for 10-24 hours in a nitrogen atmosphere, and using the substances at 300 ℃ in a ratio of 1: 2, activating for 10-24 hours by using mixed gas consisting of hydrogen fluoride and nitrogen to prepare the catalyst. The soluble salt is chloride, nitrate or acetate of metal. The catalysts for amination-dehydration one-pot reaction, fluorination catalysts, halogenation catalysts, isomerization catalysts, esterification catalysts referred to in this patent can be prepared according to the above-mentioned methods. Wherein: (1) the catalyst for amination-dehydration reaction is one or more of aluminum fluoride, ferric fluoride, magnesium fluoride, calcium fluoride, barium fluoride and chromium fluoride; (2) the halogenation catalyst is at least one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride; (3) the fluorination catalyst is a chromium-based catalyst, a molybdenum-based catalyst or a tungsten-based catalyst modified by taking at least one element of magnesium, iron, cobalt, nickel, zinc and aluminum as an auxiliary agent, and the mass percentage of the auxiliary agent element to the chromium, molybdenum or tungsten element is 1-20%: 80-99%; (4) the catalyst for esterification is one or more of magnesium fluoride, ferric fluoride, calcium fluoride, barium fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride; (5) the isomerization catalyst is one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride. In the above-mentioned metals, except for molybdenum and tungsten, which are metal oxyfluorides, the other metals are metal fluorides, and the activation time can be shortened to 3 to 6 hours, and then oxyfluorides of the other metals can be obtained.
Example 1
Preparation of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane
Figure BDA0003312993530000131
In an autoclave, in an o-xylene solvent, the ratio of the amounts of the materials added in sequence is 1: 15: 0.02 of octafluoroisobutylene, sodium hypochlorite and tetrabutylphosphonium bromide, the reaction temperature is 25 ℃, the reaction time is 24 hours, and after the reaction is finished, the distillation is carried out to obtain the 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane, wherein the yield is 93.1 percent.
Example 2
Preparation of 2-chloro-2-fluoro-3, 3-bis (trifluoromethyl) oxirane
Figure BDA0003312993530000141
In an autoclave, in an acetonitrile solvent, the ratio of the amounts of the materials added in sequence was 1: 15: 0.02 of 1-chloro-1, 3,3, 3-tetrafluoro-2- (trifluoromethyl) propene, sodium hypochlorite and tetrabutyl phosphonium bromide, the reaction temperature is 25 ℃, the reaction time is 24 hours, and after the reaction is finished, distillation is carried out to obtain the 2-chloro-2-fluoro-3, 3-bis (trifluoromethyl) oxirane, wherein the yield is 87.2%.
Example 3
Preparation of 2-fluoro-2-methoxy-3, 3-bis (trifluoromethyl) oxirane
Figure BDA0003312993530000142
In an autoclave, in an acetonitrile solvent, the ratio of the amounts of the materials added in sequence was 1: 15: 0.02 of 1,3,3, 3-tetrafluoro-1-methoxy-2- (trifluoromethyl) propene, sodium hypochlorite and tetrabutyl phosphonium bromide, at the reaction temperature of 25 ℃ for 24 hours, and after the reaction is finished, distilling to obtain the 2-fluoro-2-methoxy-3, 3-bis (trifluoromethyl) oxirane with the yield of 72.4 percent.
Example 4
Preparation of 3-fluoro-2, 2-bis (trifluoromethyl) oxirane
Figure BDA0003312993530000143
In an autoclave, 1,3, 5-trimethylbenzene solvent is added with the mass ratio of 1: 15: 0.02 of 1,3,3, 3-tetrafluoro-2- (trifluoromethyl) propene, sodium hypochlorite and tetrabutylammonium bromide, the reaction temperature is 25 ℃, the reaction time is 24 hours, and after the reaction is finished, distillation is carried out to obtain the 3-fluoro-2, 2-bis (trifluoromethyl) oxirane, wherein the yield is 83.5%.
Example 5
Preparation of heptafluoroisobutyraldehyde
Figure BDA0003312993530000151
The method comprises the following steps: at an inner diameter of 1/2 inches and a length of 30cmA tubular reactor made of Kangalloyed steel was filled with 10 ml of a prepared chromium-based catalyst (Mg is present in the form of MgF) which is a fluorination catalyst composed of 10% by mass of Mg and 90% by mass of Cr2Cr is present in the form of CrF3). Raising the temperature of the reactor to 175 ℃, introducing hexafluoropropylene and formyl fluoride to carry out halogen fluorination reaction when HF is zero, and controlling the mass ratio of the hexafluoropropylene to the formyl fluoride to be 1: 5, the contact time is 50 seconds, the reaction pressure is 0.1MPa, after 20 hours of reaction, the reaction product is washed by water and alkali, organic matters are obtained by separation, after drying and dewatering, a sample is taken for GC analysis, and the analysis result is as follows: the conversion of hexafluoropropylene was 99.2%, and the selectivity to heptafluoroisobutyraldehyde was 98.3%.
Figure BDA0003312993530000152
The method 2 comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was packed with 10 ml of a tungsten-based catalyst (Co present in the form of CoF) as a fluorination catalyst consisting of 10% by mass of Co and 90% by mass of W2W is present in the form of tungsten oxyfluoride). Raising the temperature of the reactor to 175 ℃, introducing hexafluoropropylene, formyl chloride and hydrogen fluoride to carry out halogen fluorination reaction, controlling the mass ratio of the hexafluoropropylene to the formyl chloride to the hydrogen fluoride to be 1: 5: 15, controlling the contact time to be 50 seconds, controlling the reaction pressure to be 0.1MPa, reacting for 20 hours, washing the reaction product with water and alkali, separating to obtain an organic matter, drying to remove water, sampling to carry out GC analysis, and obtaining an analysis result: the conversion of hexafluoropropylene was 98.5%, and the selectivity to heptafluoroisobutyraldehyde was 99.3%.
Figure BDA0003312993530000153
The method 3 comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of molybdenum oxyfluoride as a prepared isomerization catalyst. Heating the reactor to 200 ℃, introducing 3-fluoro-2, 2-bis (trifluoromethyl) ethylene oxide to perform isomerization reaction, wherein the contact time is 60 seconds, the reaction pressure is 0.1MPa, after the reaction is carried out for 20 hours, washing and alkaline washing reaction products, separating to obtain organic matters, drying to remove water, sampling to carry out GC analysis, and the analysis result is as follows: the conversion of 3-fluoro-2, 2-bis (trifluoromethyl) oxirane was 100% and the selectivity to heptafluoroisobutyraldehyde was 99.5%.
Example 6
Preparation of heptafluoroisobutyryl chloride
Figure BDA0003312993530000161
The method comprises the following steps: a tubular reactor of 30cm length and 1/2 inches in inside diameter was charged with 10 ml of a prepared chromium-based catalyst, a fluorination catalyst consisting of 10% by mass of Zn and 90% by mass of Cr (Zn is present in the form of ZnF)2Cr is present in the form of CrF3). Heating the reactor to 175 ℃, introducing hexafluoropropylene and fluoroformyl chloride for addition reaction, and controlling the mass ratio of the hexafluoropropylene to the fluoroformyl chloride to be 1: 5, the contact time is 50 seconds, the reaction pressure is 0.1MPa, after 20 hours of reaction, a reaction product is sampled and subjected to GC analysis, and the analysis result is as follows: the conversion of hexafluoropropylene was 99.2%, and the selectivity to heptafluoroisobutyryl chloride was 99.5%.
Figure BDA0003312993530000162
The method 2 comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of chromium fluoride as a prepared halogenation catalyst. Heating the reactor to 250 ℃, introducing heptafluoroisobutyraldehyde and chlorine to carry out halogenation reaction, and controlling the mass ratio of the heptafluoroisobutyraldehyde to the chlorine to be 1: and 5, the contact time is 50 seconds, the reaction pressure is 0.1MPa, after the reaction is carried out for 20 hours, the reaction product is rectified to obtain the heptafluoroisobutyryl chloride, the yield is 97.2 percent, and the purity is 99.2 percent (GC analysis).
Figure BDA0003312993530000163
The method 3 comprises the following steps: a tubular reactor of Yincang alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of tungsten oxyfluoride as a catalyst for isomerization prepared. Heating the reactor to 200 ℃, introducing 2-chloro-2-fluoro-3, 3-bis (trifluoromethyl) ethylene oxide to perform isomerization reaction, wherein the contact time is 60 seconds, the reaction pressure is 0.1MPa, directly sampling for GC analysis after 20 hours of reaction, and the analysis result is as follows: the conversion of 2-chloro-2-fluoro-3, 3-bis (trifluoromethyl) oxirane was 100% and the selectivity to heptafluoroisobutyryl chloride was 99.6%.
Example 7
Preparation of heptafluoro isobutyryl fluoride
Figure BDA0003312993530000171
The method comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of a tungsten-based catalyst (Zn in the form of ZnF) as a fluorination catalyst consisting of 10% by mass of Zn and 90% by mass of W2W is present in the form of tungsten oxyfluoride). The temperature of the reactor is raised to 175 ℃, and hexafluoropropylene and COCl are introduced2The hydrogen fluoride generates halogen fluorination reaction to control hexafluoropropylene and COCl2The mass ratio of the hydrogen fluoride and the hydrogen fluoride is 1: 2: 15, the contact time is 50 seconds, the reaction pressure is 0.1MPa, and after 20 hours of reaction, the heptafluoro isobutyryl fluoride is obtained by rectification, the yield is 99.2%, and the purity is 99.5% (GC analysis).
Figure BDA0003312993530000172
The method 2 comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of a molybdenum-based catalyst (Ni in the form of NiF) as a fluorination catalyst consisting of 10% of Ni and 90% of Mo2Mo is present in the form of molybdenum oxyfluoride). Raising the temperature of the reactor to 200 ℃, introducing hexafluoropropylene, formyl chloride, hydrogen fluoride and chlorine to perform halogen fluorination reaction, and controlling the mass ratio of the hexafluoropropylene to the formyl chloride to the hydrogen fluoride to the chlorine to be 1: 2: 15: 3, contact time 50 seconds, reactionThe pressure is 0.1MPa, after 20 hours of reaction, the heptafluoro isobutyryl fluoride is obtained by rectification, the yield is 95.7%, and the purity is 99.1% (GC analysis).
Figure BDA0003312993530000173
The method 3 comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of a tungsten-based catalyst (Zn in the form of ZnF) as a fluorination catalyst consisting of 5% of Zn and 95% of W2W is present in the form of tungsten oxyfluoride). Heating the reactor to 200 ℃, introducing heptafluoroisobutyraldehyde, hydrogen fluoride and chlorine to perform halogen fluorination reaction, and controlling the mass ratio of the heptafluoroisobutyraldehyde to the hydrogen fluoride to the chlorine to be 1: 15: and 2, the contact time is 50 seconds, the reaction pressure is 0.1MPa, and after 20 hours of reaction, the heptafluoro isobutyryl fluoride is obtained by rectification, the yield is 97.2 percent, and the purity is 99.3 percent (GC analysis).
Figure BDA0003312993530000181
The method 4 comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of a prepared chromium-based catalyst, a fluorination catalyst composed of 10% Ni and 90% Cr (Ni was present in the form of NiF)2Cr is present in the form of CrF3). Heating the reactor to 200 ℃, introducing heptafluoro isobutyryl chloride to perform fluorination reaction with hydrogen fluoride, controlling the mass ratio of the heptafluoro isobutyryl chloride to the hydrogen fluoride to be 1: 15, controlling the contact time to be 50 seconds, controlling the reaction pressure to be 0.1MPa, and rectifying after 20 hours of reaction to obtain the heptafluoro isobutyryl fluoride, wherein the yield is 98.9 percent, and the purity is 99.6 percent (GC analysis).
Figure BDA0003312993530000182
The method 5 comprises the following steps: a tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10 ml of the prepared isomerization catalyst aluminum fluoride. Heating the reactor to 175 ℃, introducing 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to perform an isomerization reaction, wherein the contact time is 50 seconds, the reaction pressure is 0.1MPa, directly sampling for GC analysis after 20 hours of reaction, and the analysis result is as follows: the conversion of 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane was 100% and the selectivity to heptafluoroisobutyrylfluoride was 99.8%.
Example 8
Preparation of methyl heptafluoroisobutyrate
Figure BDA0003312993530000183
The method comprises the following steps: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of the prepared calcium fluoride catalyst for the esterification reaction. Heating the reactor to 200 ℃, introducing heptafluoro isobutyryl fluoride and methanol for reaction, and controlling the mass ratio of the heptafluoro isobutyryl fluoride to the methanol to be 1: 10, the contact time is 50 seconds, the reaction pressure is normal pressure, after 20 hours of reaction, the reaction product is washed by water and alkali, an organic matter is obtained by separation, and after drying and water removal, the composition of the organic matter is analyzed by gas chromatography, so that the methyl heptafluoroisobutyrate is obtained, the yield is 98.7%, and the purity is 99.6% (GC analysis).
The method 2 comprises the following steps:
Figure BDA0003312993530000191
a tubular reactor of 30cm length having an inner diameter of 1/2 inches was charged with 10 ml of the prepared isomerization catalyst aluminum fluoride. Heating the reactor to 175 ℃, introducing 2-fluoro-2-methoxy-3, 3-bis (trifluoromethyl) ethylene oxide to perform isomerization reaction, wherein the contact time is 50 seconds, the reaction pressure is 0.1MPa, directly sampling for GC analysis after 20 hours of reaction, and the analysis result is as follows: the conversion of 2-fluoro-2-methoxy-3, 3-bis (trifluoromethyl) oxirane was 100%, and the selectivity to methyl heptafluoroisobutyrate was 99.1%.
Example 9
Preparation of ethyl heptafluoroisobutyrate
Figure BDA0003312993530000192
A tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of tungsten oxyfluoride as a catalyst for the esterification reaction. Heating the reactor to 200 ℃, introducing heptafluoroisobutyryl chloride and ethanol for reaction, and controlling the mass ratio of the heptafluoroisobutyryl chloride to the ethanol to be 1: 10, the contact time is 50 seconds, the reaction pressure is normal pressure, after 20 hours of reaction, the reaction product is washed by water and alkali, an organic matter is obtained by separation, and after drying and water removal, the composition of the organic matter is analyzed by gas chromatography, so that the methyl heptafluoroisobutyrate is obtained, the yield is 95.4%, and the purity is 99.7% (GC analysis).
Example 10
Preparation of heptafluoroisobutyronitrile
Figure BDA0003312993530000201
The method comprises the following steps: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of the prepared catalyst aluminum fluoride for amination-dehydration reaction. The reaction temperature of the heating section 1 is 140 ℃, the reaction temperature of the heating section 2 is 270 ℃, the reaction temperature of the heating section 3 is 400 ℃, heptafluoro isobutyryl fluoride and ammonia gas are introduced for reaction, and the ratio of the amount of the heptafluoro isobutyryl fluoride to the amount of the ammonia gas is controlled to be 1: 10, the contact time is 100 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after the reaction is carried out for 20 hours, the reaction product is washed by water, pickled, dried and collected to obtain the heptafluoroisobutyronitrile, the yield is 99.6%, and the purity is 99.7% (GC analysis).
Figure BDA0003312993530000202
The method 2 comprises the following steps: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of magnesium fluoride as a catalyst for the amination-dehydration reaction prepared. The reaction temperature of the heating section 1 is 160 ℃, the reaction temperature of the heating section 2 is 330 ℃, the reaction temperature of the heating section 3 is 500 ℃, heptafluoroisobutyryl chloride and methylamine are introduced for reaction, and the ratio of the amount of the heptafluoroisobutyryl chloride to the amount of the methylamine is controlled to be 1: 10, the contact time is 100 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after the reaction is carried out for 20 hours, the reaction product is washed by water, pickled and dried, and the heptafluoroisobutyronitrile is obtained by collection, wherein the yield is 98.2 percent, and the purity is 99.4 percent (GC analysis).
Figure BDA0003312993530000203
The method 3 comprises the following steps: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of calcium fluoride as a catalyst for amination-dehydration reaction. The reaction temperature of the heating section 1 is 180 ℃, the reaction temperature of the heating section 2 is 290 ℃, the reaction temperature of the heating section 3 is 400 ℃, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane and ammonia gas are introduced for reaction, and the mass ratio of the 2, 2-difluoro-3, 3-bis (trifluoromethyl) oxirane to the ammonia gas is controlled to be 1: 10, the contact time is 100 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after the reaction is carried out for 20 hours, the reaction product is washed by water, pickled and dried, and the heptafluoroisobutyronitrile is obtained by collection, the yield is 99.7%, and the purity is 99.8% (GC analysis).
Figure BDA0003312993530000211
The method 4 comprises the following steps: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of the prepared barium fluoride catalyst for amination-dehydration reaction. The reaction temperature of the heating section 1 is 200 ℃, the reaction temperature of the heating section 2 is 300 ℃, the reaction temperature of the heating section 3 is 400 ℃, 2-chloro-2-fluoro-3, 3-bis (trifluoromethyl) oxirane and ammonia gas are introduced for reaction, and the mass ratio of the 2-chloro-2-fluoro-3, 3-bis (trifluoromethyl) oxirane to the ammonia gas is controlled to be 1: 10, the contact time is 100 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after the reaction is carried out for 20 hours, the reaction product is washed by water, pickled, dried and collected to obtain the heptafluoroisobutyronitrile, the yield is 99.3 percent, and the purity is 99.1 percent (GC analysis).
The method 5 comprises the following steps: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of the prepared catalyst aluminum fluoride for amination-dehydration reaction. The reaction temperature of the heating section 1 is 140 ℃, the reaction temperature of the heating section 2 is 270 ℃, the reaction temperature of the heating section 3 is 400 ℃, heptafluoro isobutyryl fluoride and ammonia gas are introduced for reaction, and the ratio of the amount of the 2-fluoro-2-methoxy-3, 3-bis (trifluoromethyl) ethylene oxide to the amount of the ammonia gas is controlled to be 1: 10, the contact time is 100 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after the reaction is carried out for 20 hours, the reaction product is washed by water, pickled and dried, and the heptafluoroisobutyronitrile is obtained by collection, the yield is 99.0%, and the purity is 98.5% (GC analysis).
Figure BDA0003312993530000212
The method 6 comprises the following steps: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of the prepared ferric fluoride catalyst for the amination-dehydration reaction. The reaction temperature of the heating section 1 is 240 ℃, the reaction temperature of the heating section 2 is 320 ℃, the reaction temperature of the heating section 3 is 400 ℃, methyl heptafluoroisobutyrate and ammonia gas are introduced for reaction, and the mass ratio of methyl heptafluoroisobutyrate to ammonia gas is controlled to be 1: 10, the contact time is 140 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after the reaction is carried out for 20 hours, the reaction product is washed by water, pickled, dried and collected to obtain the heptafluoroisobutyronitrile, the yield is 98.4%, and the purity is 99.2% (GC analysis).
Figure BDA0003312993530000221
The method 7 comprises the following steps: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of chromium fluoride as a catalyst for amination-dehydration reaction. The reaction temperature of the heating section 1 is 280 ℃, the reaction temperature of the heating section 2 is 340 ℃, the reaction temperature of the heating section 3 is 400 ℃, ethyl heptafluoroisobutyrate and ammonia gas are introduced for reaction, and the mass ratio of ethyl heptafluoroisobutyrate to ammonia gas is controlled to be 1: and 10, the contact time is 180 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after the reaction is carried out for 20 hours, the reaction product is washed by water, pickled and dried, and the heptafluoroisobutyronitrile is obtained by collection, wherein the yield is 95.7%, and the purity is 98.4% (GC analysis).
Comparative example 1
The preparation of heptafluoroisobutyronitrile comprises three steps:
Figure BDA0003312993530000222
step 1: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of a tungsten-based catalyst (Zn in the form of ZnF) as a fluorination catalyst consisting of 10% by mass of Zn and 90% by mass of W2W is present in the form of tungsten oxyfluoride). The temperature of the reactor is raised to 175 ℃, and hexafluoropropylene and COCl are introduced2The addition reaction is carried out to control the hexafluoropropylene and the COCl2The mass ratio of the substances is 1: 5, the contact time is 50 seconds, the reaction pressure is 0.1MPa, after 20 hours of reaction, 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionyl chloride is obtained by rectification, the yield is 98.1 percent, and the purity is 99.6 percent (GC analysis))。
Figure BDA0003312993530000231
Step 2: a tubular reactor of 316 material having an inner diameter of 1/2 inches and a length of 30cm and divided into 3 relatively independent heating zones was charged with 10 ml of the prepared catalyst aluminum fluoride for amination-dehydration reaction. The reaction temperature of the heating section at the 1 st section is 140 ℃, the reaction temperature of the heating section at the 2 nd section is 270 ℃, the reaction temperature of the heating section at the 3 rd section is 400 ℃, 2-chlorine-3, 3, 3-trifluoro-2- (trifluoromethyl) propionyl chloride and ammonia gas are introduced for reaction, and the mass ratio of the 2-chlorine-3, 3, 3-trifluoro-2- (trifluoromethyl) propionyl chloride to the ammonia gas is controlled to be 1: 10, the contact time is 100 seconds, the reaction pressure is normal pressure, the reactant flow sequentially passes through the heating section 1, the heating section 2 and the heating section 3, after 20 hours of reaction, the reaction product is washed, pickled, dried and rectified to obtain the 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionitrile, the yield is 91.5 percent, and the purity is 98.2 percent (GC analysis).
Figure BDA0003312993530000232
And step 3: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of a tungsten-based catalyst (Zn in the form of ZnF) as a fluorination catalyst consisting of 10% of Zn and 90% of W2W is present in the form of tungsten oxyfluoride). The temperature of the reactor is raised to 420 ℃, HF and 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionitrile are introduced for reaction, and the mass ratio of HF to 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionitrile is controlled to be 20: 1, the contact time is 11.4 seconds, the reaction pressure is normal pressure, after 20 hours of reaction, the reaction product is washed by water and alkali, an organic matter is obtained by separation, after drying and dewatering, the composition of the organic matter is analyzed by gas chromatography, the conversion rate of 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionitrile is 35.4 percent, and the selectivity of 2,3,3, 3-trifluoro-2- (trifluoromethyl) propionitrile is 96.1 percent.
The synthetic route adopted in comparative example 1 is a method of adding, aminating, dehydrating and fluorinating, which is abbreviated as route a, and the conversion rate of the third step is low, so that the total yield per pass of heptafluoroisobutyronitrile in route a based on the starting material hexafluoropropylene is very low, and is only 30.5%.
The synthesis route constituted by "method 1" of example 6 and "method 1" of example 8, namely by hexafluoropropylene and COCl2HF firstly undergoes gas-phase halogen fluorination reaction to obtain heptafluoro isobutyryl fluoride, and then the heptafluoro isobutyryl fluoride and ammonia gas undergo amination-dehydration one-pot gas-phase continuous reaction to obtain heptafluoro isobutyronitrile, which is called as a route B for short, wherein the total yield per pass of the heptafluoro isobutyronitrile is 98.8% based on the starting material of hexafluoropropylene.
The starting materials for the reactions of scheme A and scheme B are identical, with the exception of the reaction intermediates, which are hexafluoropropylene and COCl2Five raw materials of HF, a fluorination catalyst and ammonia gas; in addition, route B is equivalent to the first step of gas phase halogen fluorination in route B by combining the first step of gas phase addition reaction and the third step of gas phase fluorination in route A, and hexafluoropropylene and COCl are involved2HF and fluorination catalyst. The method has the advantages that the route B shortens the synthesis route, and perfectly avoids the gas phase fluorination reaction of the 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionitrile with higher difficulty and temperature, so that the total yield of the heptafluoroisobutyronitrile per pass is greatly improved. Therefore, compared with the route A, the route B has incomparable superiority and has more industrial value.
Comparative example 2
The preparation of heptafluoroisobutyronitrile comprises three steps:
Figure BDA0003312993530000241
step 1: in accordance with "step 1" of "comparative example 1".
Figure BDA0003312993530000242
Step 2: a tubular reactor made of Incan alloy having an inner diameter of 1/2 inches and a length of 30cm was charged with 10 ml of a tungsten-based catalyst (Zn in the form of ZnF) as a fluorination catalyst consisting of 10% of Zn and 90% of W2W is present in the form of tungsten oxyfluoride). The reactor is heated to 200 ℃, 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionyl chloride and hydrogen fluoride are introduced to carry out fluorination reaction, the mass ratio of the 2-chloro-3, 3, 3-trifluoro-2- (trifluoromethyl) propionyl chloride to the hydrogen fluoride is controlled to be 1: 15, the contact time is 50 seconds, the reaction pressure is 0.1MPa, and after 20 hours of reaction, the heptafluoro isobutyryl fluoride is obtained by rectification, the yield is 97.2 percent, and the purity is 99.3 percent (GC analysis).
Figure BDA0003312993530000251
And step 3: in accordance with "method 1" of example 8.
The synthetic route adopted in comparative example 2 is a one-pot method of addition, fluorination, and amination-dehydration, referred to as route C. The total yield per pass of heptafluoroisobutyronitrile from route C was 95.0% based on the starting material, hexafluoropropylene.
Compared with the route C, the total yield of the heptafluoroisobutyronitrile in the route B is higher (the total yield of the route B is 98.8 percent), the reaction steps are shorter, and the method has higher reaction efficiency and higher industrial value.
By replacing the starting material fluoroisobutylene of the present invention with other halogenated isobutylene (e.g., hexafluoroisobutylene, dichlorohexafluoroisobutylene, etc.), or replacing the C1 acid halide with other formaldehyde halide (e.g., carbonyl fluoride, carbonyl bromide, carbonyl iodide, formyl bromide, formyl iodide, fluoroformyl bromide, fluoroformyl iodide, chloroformyl bromide, chloroformyl iodide, bromoformyl iodide, etc.), or replacing hexafluoropropylene with other propylene halide (e.g., 1,3,3, 3-pentafluoropropene, 3-bromo-1, 1-difluoro-1-propene, 1, 3-trifluoro-1-propene, 1,3, 3-trifluoro-1-propene, 1,2, 3-tetrafluoro-1-propene, 1,2,3, 3-pentafluoropropene, etc.), or replacing hexafluoropropylene with other propylene halide (e.g., 1,3, 3-trifluoro-1-propene, 1,2,3, 3-pentafluoropropene, etc.) 1,1,2, 3-tetrafluoropropene, 1, 2-trifluoro-1-propene, etc.), and a method of synthesizing heptafluoroisobutyronitrile through an intermediate heptafluoroisobutyric acid halide, heptafluoroisobutyrate, or 2-halo-2-fluoro-3, 3-bis (trifluoromethyl) oxirane by an addition reaction, a halogenation reaction, a fluorination reaction, a halofluorination reaction, etc., are included in the scope of protection of the present patent. In addition, the synthetic method for synthesizing heptafluoroisobutyronitrile of the invention can also be used for synthesizing other halogenated nitriles or non-halogenated nitriles such as trifluoroacetonitrile, pentafluoropropionitrile, heptafluoron-butyronitrile and the like by using a similar 'amination-dehydration one-pot' technology, and the invention also belongs to the protection scope of the invention.

Claims (11)

1. The method for continuously preparing heptafluoroisobutyronitrile by amination-dehydration one-pot gas phase comprises the following steps:
a. provided with a general formula of
Figure FDA0003312993520000011
Or isomers thereof
Figure FDA0003312993520000012
Wherein R is1Is F, Cl, Br, I or C1-C4 alkoxy;
b. in the presence of a catalyst, in a tubular reactor,
Figure FDA0003312993520000013
or isomers thereof
Figure FDA0003312993520000014
With aminating reagents ammonia or primary amine compounds R-NH2Carrying out gas-phase continuous amination-dehydration one-pot reaction to obtain heptafluoroisobutyronitrile, wherein the catalyst is one or more of aluminum fluoride, ferric fluoride, magnesium fluoride, calcium fluoride, barium fluoride and chromium fluoride; wherein R is-CnH2n+1And n is a positive integer set.
2. The method according to claim 1, wherein the tubular reactor in the step b consists of relatively independent heating sections which are connected end to end, the temperature of the tubular reactor is increased in the length direction from the inlet to the outlet, and the temperature in the tubular reactor is from 100 ℃ to 550 DEG CThe contact time is 1 to 300s, wherein R is-CnH2n+1And n is a positive integer set from 1 to 8.
3. The process according to claim 2, the tubular reactor consisting of 2 to 7 relatively independent heating stages in the presence of a catalyst,
Figure FDA0003312993520000015
or isomers thereof
Figure FDA0003312993520000016
With aminating reagents ammonia or primary amine compounds R-NH2The ratio of the amounts of substances (1): 1-30 ℃, the reaction temperature of each heating section is 100-550 ℃, and the contact time is 1-300 s.
4. The method according to claim 3, wherein step b is carried out in a tubular reactor consisting of 3 relatively independent heating sections with equal length, in the presence of a catalyst,
Figure FDA0003312993520000021
or isomers thereof
Figure FDA0003312993520000022
With aminating reagents ammonia or primary amine compounds R-NH2The ratio of the amounts of substances (1): 5-20 ℃, the reaction temperature of the heating section 1 is 100-300 ℃, the reaction temperature of the heating section 3 is 300-550 ℃, the reaction temperature of the heating section 2 is the average value of the heating section 1 and the heating section 3, and the reactant material flows sequentially pass through the heating section 1, the heating section 2 and the heating section 3, and the contact time is 1-300 s.
5. The process of claim 4, wherein step b is carried out in a tubular reactor having 3 relatively independent heating zones of equal length,
Figure FDA0003312993520000023
or isomers thereof
Figure FDA0003312993520000024
With aminating reagents ammonia or primary amine compounds R-NH2The ratio of the amounts of substances (1): 5-20 ℃, the reaction temperature of the heating section 1 is 120-300 ℃, the reaction temperature of the heating section 3 is 300-450 ℃, the reaction temperature of the heating section 2 is the average value of the heating sections 1 and 3, the reactant material flows sequentially pass through the heating section 1, the heating section 2 and the heating section 3, the contact time is 10-200 s, wherein R is-CnH2n+1Group, n ═ 1,2 or 3, R1F, Cl, methoxy or ethoxy.
6. The method according to any one of claims 1 to 5, wherein in step a
Figure FDA0003312993520000025
The synthesis method comprises the following steps: in the presence of an isomerization catalyst, the catalyst,
Figure FDA0003312993520000026
the gas phase isomerization reaction is carried out, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃,
Figure FDA0003312993520000031
the contact time of (a) is 0.1 to 100 s; wherein the isomerization catalyst is one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride; alternatively, the first and second electrodes may be,
in the presence of a halogenation catalyst, heptafluoroisobutyraldehyde and a halogen simple substance are subjected to halogenation reaction to obtain
Figure FDA0003312993520000032
Wherein the halogen is F2、Cl2、Br2Or I2，R1F, Cl, Br or I; inverse directionThe conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, the ratio of the amount of heptafluoroisobutyraldehyde to the amount of the halogen simple substance is 1: 1-10, and the contact time is 0.1-100 s, wherein the halogenated catalyst is at least one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride;
in the step a
Figure FDA0003312993520000033
The synthesis method comprises the following steps: under the condition of stirring, in an organic solvent A, a catalyst A catalyzes
Figure FDA0003312993520000034
Reacting with sodium hypochlorite to obtain
Figure FDA0003312993520000035
The reaction conditions are as follows:
Figure FDA0003312993520000036
the ratio of the amount of sodium hypochlorite to the amount of the catalyst A is 1: 5-20: 0.01-0.05, the reaction temperature is 0-50 ℃, and the reaction time is 3-48 h, wherein the organic solvent A is any one of toluene, xylene, trimethylbenzene, acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile, and the catalyst A is any one of tetrabutylammonium bromide or tetrabutylphosphonium bromide.
7. The method of claim 1, in step a
Figure FDA0003312993520000041
The synthesis method comprises the following steps: in the presence of a fluorination catalyst, hexafluoropropylene and
Figure FDA0003312993520000042
the hydrogen fluoride is subjected to fluorination reaction to obtain the heptafluoro isobutyryl fluoride, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, and the hexafluoropropylene and the propylene are mixed
Figure FDA0003312993520000043
The mass ratio of hydrogen fluoride is 1: 1 to 5: 0 to 20, and the contact time is 0.1 to 100s, wherein R2、R3Respectively is any one of F, Cl, Br or I; when R is2、R3And when F is the same, HF is zero or not zero; when R is2、R3When not being F, HF is not zero; alternatively, the first and second electrodes may be,
in the presence of a fluorination catalyst, hexafluoropropylene and
Figure FDA0003312993520000044
the hydrogen fluoride and the elementary halogen are subjected to halogen fluorination reaction to obtain the heptafluoro isobutyryl fluoride, wherein the elementary halogen is F2、Cl2、Br2Or I2The reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, and the hexafluoropropylene and the propylene are mixed
Figure FDA0003312993520000045
The ratio of the hydrogen fluoride to the halogen simple substance is 1: 1 to 5: 0 to 20: 1 to 5, and a contact time of 0.1 to 100s, wherein R4Is F, Cl, Br or I; when the elementary halogen is F2HF is zero or non-zero; when the halogen is Cl2、Br2Or I2HF is not zero;
alternatively, the first and second electrodes may be,
in the presence of a fluorination catalyst,
Figure FDA0003312993520000046
carrying out fluorination reaction with hydrogen fluoride to obtain heptafluoro isobutyryl fluoride, wherein the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃,
Figure FDA0003312993520000051
the amount of the hydrogen fluoride is 1: 1 to 20, and the contact time is 0.1 to 100s, wherein R5Is Cl, Br or I;
in the step a
Figure FDA0003312993520000052
The synthesis method comprises the following steps: in the presence of a fluorination catalyst, hexafluoropropylene and
Figure FDA0003312993520000053
an addition reaction occurs to obtain
Figure FDA0003312993520000054
Wherein R is5Is Cl, Br or I; the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, and the hexafluoropropylene and the propylene are mixed
Figure FDA0003312993520000055
The amount ratio of the substances is 1: 1 to 10, and the contact time is 0.1 to 100 s.
8. The method of claim 6, wherein the heptafluoroisobutyraldehyde is synthesized by: in the presence of a fluorination catalyst, hexafluoropropylene and
Figure FDA0003312993520000056
the hydrogen fluoride performs halogen fluorination reaction to obtain heptafluoroisobutyraldehyde, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, the reaction temperature is 50-300 ℃, and the hexafluoropropylene and the propylene are mixed
Figure FDA0003312993520000057
The amount ratio of hydrogen fluoride is 1: 1 to 10: 0 to 20, the contact time is 0.1 to 100s, R4Is F, Cl, Br or I; when R is4When F, HF is zero or not zero; when R is4When Cl, Br or I, HF is not zero; or
In the presence of an isomerization catalyst, the catalyst,
Figure FDA0003312993520000061
the gas phase isomerization reaction is carried out to obtain heptafluoroisobutyraldehyde, and the reaction conditions are as follows: the reaction pressure is 0.1-1.5 MPa, and the reaction is carried outThe temperature is 50-300 ℃,
Figure FDA0003312993520000062
the contact time of the catalyst is 0.1-100 s, and the isomerization catalyst is one or more of magnesium fluoride, ferric fluoride, cobalt fluoride, nickel fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride.
9. The method according to any one of claims 7 to 8, wherein the fluorination catalyst is a chromium-based catalyst, a molybdenum-based catalyst or a tungsten-based catalyst modified by taking at least one element of magnesium, iron, cobalt, nickel, zinc and aluminum as an auxiliary agent, and the mass percentage composition of the auxiliary agent element and the chromium or molybdenum or tungsten element is 1-20%: 80-99%, and the metal element exists in the form of metal fluoride or metal oxyfluoride.
10. The method of claim 8, the
Figure FDA0003312993520000063
The synthesis method comprises the following steps: under the condition of stirring, in organic solvent B, catalyst B catalyzes
Figure FDA0003312993520000064
Reacting with sodium hypochlorite to obtain
Figure FDA0003312993520000065
The reaction conditions are as follows:
Figure FDA0003312993520000066
the mass ratio of sodium hypochlorite to the mass of the catalyst B is 1: 5-20: 0.01-0.05, the reaction temperature is 0-50 ℃, and the reaction time is 3-48 h, wherein the organic solvent B is any one of toluene, xylene, trimethylbenzene, acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile, and the catalyst B is any one of tetrabutylammonium bromide or tetrabutylphosphonium bromide.
11.The method of claim 1, in step a
Figure FDA0003312993520000071
In which R is1Is C1-C4 alkoxy, and the method comprises the following steps: in the presence of the catalyst C,
Figure FDA0003312993520000072
esterification reaction with C1-C4 alcohol to obtain
Figure FDA0003312993520000073
The reaction conditions are as follows:
Figure FDA0003312993520000074
Figure FDA0003312993520000075
the mass ratio of C1-C4 alcohol to substance is 1: 1-20 ℃, the reaction temperature is 50-300 ℃, and the contact time is 0.1-100 s; wherein the catalyst C is one or more of magnesium fluoride, ferric fluoride, calcium fluoride, barium fluoride, zinc fluoride, aluminum fluoride, chromium fluoride, molybdenum oxyfluoride and tungsten oxyfluoride.
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