CN106669837B - Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene - Google Patents
Method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene Download PDFInfo
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Abstract
The invention relates to a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene. The method comprises the steps of firstly preparing a copper-containing complex by using a copper salt, a nitrogen-containing organic ligand and a Lewis acid carrier as raw materials through a microwave method, and then reacting the Cu-containing complex serving as a catalyst in an amide solvent under the action of 2, 2-dichloro-1, 1, 1-trifluoroethane and copper powder to obtain the 1,1,1,4,4, 4-hexafluoro-2-butene. In the method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene, the Cu-containing complex has good catalytic performance for the reaction, so that the target product with high yield can be obtained in a short time, the side reaction can be reduced, the generation of HFO1326, HFO-1335 and other byproducts can be effectively inhibited, and the purity of the target product can be effectively improved.
Description
Technical Field
The invention relates to preparation of 1,1,1,4,4, 4-hexafluoro-2-butene, in particular to preparation of a Cu-containing complex catalyst, and application of the catalyst in preparation of 1,1,1,4,4, 4-hexafluoro-2-butene.
Technical Field
Within the framework of the montreal protocol, the use of products such as chlorofluorocarbon (CFC) and Hydrochlorofluorocarbon (HCFC) can cause serious damage to the ozone layer, so that the product industries such as refrigerants, foaming agents, solvents, fire extinguishing agents and propellants are definitely faded out. Hydrofluorocarbons (HFCs) are currently widely used as good substitutes, and although they are not destructive to the stratospheric ozone layer, they cause severe "greenhouse effect" due to their high Global Warming Potential (GWP) and large amounts used for a long time. Thus, the wide use of such products will be subject to strict policy restrictions. The 1,1,3,3, 3-pentafluoropropane (HFC-245fa) product, which is currently widely focused in the field of polyurethane foaming, can be used only as a substitute for excessive polyurethane foaming because its GWP value is 920 and large-scale use and emission cause a severe greenhouse effect, although the ozone layer depletion potential (ODP value) is zero.
Hydrofluoroolefin (HFO) products are receiving wide attention due to zero ODP, extremely low GWP, and the same performance as HFCs products in the fields of refrigeration, foaming, and propulsion, and some products such as 2,3,3, 3-tetrafluoropropene (HFO-1234yf), 1,3,3, 3-tetrafluoropropene (HFO-1234ze), and 1-chloro-3, 3, 3-trifluoropropene (HFO-1233zd) are beginning to be popularized and accepted in the market. Cis-1, 1,1,4,4, 4-hexafluoro-2-butene (HFO-1336mzz) has been widely spotlighted for its excellent properties exhibited in the field of polyurethane foaming. And can also be used as a refrigerant, a heat transfer medium, a propellant and the like to replace HFCs products.
Chinese patent CN 103626627 a discloses a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene by reacting 2, 2-dichloro-1, 1, 1-trifluoroethane with copper in the presence of an amide solvent, 2-bipyridine and a Cu (I) salt. The method preferably improves the conversion rate of 2, 2-dichloro-1, 1, 1-trifluoroethane by introducing 2, 2-bipyridine as a catalyst, but 1-chloro-1, 1,4,4, 4-pentafluoro-2-butene (HFO-1335), 1,1, 1-trifluoro-2-chloroethane (HCFC-133a) and other byproducts are generated in the reaction process, and the products easily form an azeotropic composition with HFO-1336, which causes great troubles to the subsequent separation of the products, as described in US 8871987B; U.S. Pat. No. 4, 5516951,896 discloses a method for preparing HFO-1336 by reacting 2, 2-dichloro-1, 1, 1-trifluoroethane with copper and an amine, however, the preparation method has a low product yield and a large number of side reactions; chinese patent CN 102015592B discloses a method for preparing HFO-1336 by introducing 2, 2-bipyridine and Cu (I) as catalysts into a system of 2, 2-dichloro-1, 1, 1-trifluoroethane and copper, which method, although better solving the yield problem of the product, has 1,1,1,4,4, 4-hexafluoro-2-chloro-2-butene (HFO-1326), 1,1,4,4, 4-pentafluoro-1-chloro-2-butene (HFO-1335) and other by-products which are difficult to separate. Although the methods for preparing HFO-1336 each have certain advantages, they cannot simultaneously solve the problems of low yield of the target product, long reaction time, easy occurrence of side reactions, difficult separation of the obtained by-product from the target product, and the like.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention provides a Cu-containing complex catalyst, a preparation method and application thereof. The Cu-containing complex catalyst has good catalytic performance in the reaction of preparing 1,1,1,4,4, 4-hexafluoro-2-butene, so that a target product with high yield can be obtained in a short time; meanwhile, the occurrence of side reactions can be reduced, and the generation of HFO-1326, HFO-1335 and other byproducts can be effectively inhibited; thereby effectively improving the purity of the target product.
The first aspect of the technical scheme of the invention provides a Cu-containing complex catalyst, which is prepared from copper salt, a nitrogen-containing organic ligand and a Lewis acid carrier.
In some embodiments, the copper salt, nitrogen-containing organic ligand, and Lewis acidic support are present in a mass ratio of 1:0.15 to 1.22:0.13 to 2.22.
In some embodiments, the mass ratio of the copper salt, nitrogen-containing organic ligand, and Lewis acidic support is 1:0.15: 0.13.
In some embodiments, the mass ratio of the copper salt, nitrogen-containing organic ligand, and Lewis acidic support is 1:0.3: 0.5.
In some embodiments, the mass ratio of the copper salt, nitrogen-containing organic ligand, and Lewis acidic support is 1:0.45: 0.8.
In some embodiments, the mass ratio of the copper salt, nitrogen-containing organic ligand, and Lewis acidic support is 1:0.6: 1.1.
In some embodiments, the mass ratio of the copper salt, nitrogen-containing organic ligand, and Lewis acidic support is 1:0.75: 1.4.
In some embodiments, the mass ratio of the copper salt, nitrogen-containing organic ligand, and Lewis acidic support is 1:1: 1.7.
In some embodiments, the mass ratio of the copper salt, the nitrogen-containing organic ligand, and the Lewis acidic support is 1:1.1: 2.
In some embodiments, the mass ratio of the copper salt, the nitrogen-containing organic ligand, and the Lewis acidic support is 1:1.22: 2.22.
The copper salt used in the present invention is a copper salt, in some embodiments the copper salt is CuI; in some embodiments the monovalent copper salt is CuCl; in other embodiments the monovalent copper salt is CuBr.
The nitrogen-containing organic ligand used in the invention is selected from 2, 2-bipyridine, 4-bipyridine or 1, 10-phenanthroline.
The Lewis acidic carrier used in the invention is selected from AlF3、CrF3、MgF2、ZnF2、YF3、SmF3、EuF3Or the specific surface area is more than or equal to 10m2(ii) a layered structure compound per gram.
The specific surface area of the invention is more than or equal to 10m2The term "lamellar compounds" means natural or synthetic compounds having a lamellar structure and a specific surface area of 10m or more2Lewis acidic materials per gram, such as: bentonite, molecular sieve, clay or silicon-aluminum molecular sieve, etc.
The second aspect of the technical scheme of the invention provides a method for preparing the Cu-containing complex catalyst, which comprises the following steps:
1) fully grinding and uniformly mixing the nitrogen-containing organic ligand and the Lewis acid carrier in a mortar;
2) placing the mixture ground in the step 1) in a glove box, adding cuprous salt, continuously grinding and uniformly mixing;
3) transferring the mixture ground in the step 2) to a microwave oven to react for a period of time, and cooling to obtain the Cu-containing complex catalyst.
In some embodiments of the present invention, the reaction time in step 3) of the method for preparing the above Cu complex-containing catalyst is 5 to 100min, and the microwave power is 100 to 1000W. In some embodiments of the invention, the reaction time of the microwave reaction is 10min, and the microwave power is 450W; in some embodiments, the reaction time of the microwave reaction is 100min, and the microwave power is 100W; in some embodiments, the reaction time of the microwave reaction is 15min, and the microwave power is 500W; in some embodiments, the reaction time of the microwave reaction is 10min, and the microwave power is 750W; in some embodiments, the reaction time of the microwave reaction is 30min and the microwave power is 750W.
According to the third aspect of the technical scheme, the invention provides a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene by using the Cu-containing complex catalyst, wherein the 1,1,1,4,4, 4-hexafluoro-2-butene is prepared by reacting 2, 2-dichloro-1, 1, 1-trifluoroethane with copper powder in an amide solvent under the action of the Cu-containing complex catalyst.
In some embodiments of the invention, the mass ratio of the 2, 2-dichloro-1, 1, 1-trifluoroethane to the copper powder to the amide-based solvent is from 1:0.8 to 1.05:0.65 to 5.
In some embodiments, the mass ratio of the 2, 2-dichloro-1, 1, 1-trifluoroethane to the copper powder to the amide-based solvent is 1:0.8: 0.65.
In some embodiments of the invention, the mass ratio of 2, 2-dichloro-1, 1, 1-trifluoroethane to copper powder to amide-based solvent is 1:0.85: 1.
In other embodiments of the present invention, the mass ratio of 2, 2-dichloro-1, 1, 1-trifluoroethane to copper powder to amide-based solvent is 1:1.05: 5.
In some embodiments of the present invention, the Cu complex-containing catalyst is present in an amount of 1.5% to 50% of the total mass in the reaction system for preparing 1,1,1,4,4, 4-hexafluoro-2-butene.
In some embodiments, the amide-based solvent is selected from N, N-Dimethylformamide (DMF), formamide, or Dimethylacetamide (DMAC).
The particle size of the copper powder is 10-500 meshes. In some embodiments, the copper powder has a particle size of 50-350 mesh; in some embodiments, the copper powder has a particle size of 10-150 mesh; in some embodiments, the copper powder has a particle size of 250-500 mesh.
In the method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene by using the Cu-containing complex catalyst, the reaction is carried out for 0.5 to 2.0 hours at the temperature of between 40 and 80 ℃, and then the temperature is increased to between 60 and 150 ℃ for continuous reaction for 0.5 to 6 hours; wherein the stirring speed is 500-1000 rpm.
Drawings
FIG. 1 is an infrared spectrum of a nitrogen-containing organic ligand 2, 2-bipyridine;
FIG. 2 is an IR spectrum of a Cu-containing complex of example 1;
FIG. 3 is an IR spectrum of a Cu-containing complex of example 2;
FIG. 4 is an IR spectrum of a Cu-containing complex of example 3;
FIG. 5 is an IR spectrum of a Cu-containing complex of example 4;
FIG. 6 is an IR spectrum of a Cu-containing complex of example 5;
FIG. 7 is an IR spectrum of a Cu-containing complex of example 6.
Definition of terms
The invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims. One skilled in the art will recognize that many methods and materials similar or equivalent to those described herein can be used in the practice of the present invention. The present invention is in no way limited to the methods and materials described herein. In the event that one or more of the incorporated documents, patents, and similar materials differ or contradict this application (including but not limited to defined terminology, application of terminology, described techniques, and the like), this application controls.
All ranges cited herein are inclusive, unless expressly stated to the contrary. For example, "the particle size of the copper powder is 10 to 500 mesh" means that the value of the particle size r of the reaction copper powder is in the range of 10 mesh. ltoreq. r.ltoreq.500 mesh.
The term "or" as used herein means that alternatives, if appropriate, can be combined, that is, the term "or" includes each listed individual alternative as well as combinations thereof. For example, the phrase "the nitrogen-containing organic substance is selected from 2, 2-bipyridine, 4, 4-bipyridine and 1, 10-phenanthroline" means that the nitrogen-containing organic substance may be one of 2, 2-bipyridine, 4, 4-bipyridine and 1, 10-phenanthroline, or a combination of one or more thereof.
The terms "a" or "an" are used herein to describe elements and components described herein. This is done merely for convenience and to provide a general sense of the scope of the invention. Such description should be understood to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.
The numbers in this disclosure are approximate, regardless of whether the word "about" or "approximately" is used. The numerical value of the number may have differences of 1%, 2%, 5%, 7%, 8%, 10%, etc. Whenever a number with a value of N is disclosed, any number with a value of N +/-1%, N +/-2%, N +/-3%, N +/-5%, N +/-7%, N +/-8% or N +/-10% is explicitly disclosed, wherein "+/-" means plus or minus, and a range between N-10% and N + 10% is also disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can also be used in the practice or testing of embodiments of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a specific paragraph is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
The invention has the beneficial effects that:
(1) the method for preparing HFO-1336 by using the Cu-containing complex catalyst not only can ensure that the target product has higher coupling conversion rate, but also can equally increase the yield of the target product; the conversion rate of HCFC-123 in the invention can reach 99.925%, and the yield of the target product can reach 99.09%.
(2) The reaction for preparing HFO-1336 by catalysis of the Cu-containing complex catalyst is a strong exothermic reaction, and the exothermic reaction at the initial stage is particularly obvious, so that the reaction can be milder and gradual by adopting a two-stage temperature control mode, and the energy consumption can be reduced to a greater extent in industrial production.
(3) The Cu-containing complex catalyst is adopted to catalyze and prepare the HFO-1336, wherein the total selectivity of an HFO-1336 product can reach 99.167 percent, the catalyst has better effect on inhibiting the occurrence of side reaction, particularly, R133a with azeotropic composition is not generated in the product after the reaction with Trans-HFO-1336(E-1336) or Cis-HFO-1336(Z-1336), HFO-1335 and other byproducts are not generated, and a good foundation is laid for the subsequent product separation in industrial production.
Detailed Description
The following are preferred embodiments of the present invention, and the present invention is not limited to the following preferred embodiments. It should be noted that various changes and modifications within the spirit of the invention will become apparent to those skilled in the art, and further description of the invention will be made with reference to the embodiments illustrated in the drawings.
Example 1
Preparation of Cu-containing complex catalyst:
according to the mass ratio of CuI to 2, 2-bipyridine to AlF3Weighing certain amount of 2, 2-bipyridine, CuI and carrier AlF3Reacting 2, 2-bipyridine with AlF3Adding into a magnetic mortar, grinding for 30min, and mixing; placing the mixed sample in a glove box, adding the weighed CuI sample, continuously grinding for 30min, uniformly mixing, transferring the ground sample into a microwave oven, setting the power to be 450W, radiating the microwave for 10min, and taking out the sample after cooling to obtain the supported Cu-containing complex catalystAn oxidizing agent.
Preparation of 1,1,1,4,4, 4-hexafluoro-2-butene:
to a 200ml PEEK reactor, 12.33g of copper powder (250 mesh), 5.46g of Cu-containing complex, and 60ml of DMF were added in this order at room temperature. N for the reaction kettle2The replacement was carried out 3 to 5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. Heating to 40 ℃, stirring for 2h at constant temperature, then heating to 80 ℃, and continuously stirring for 2h at constant temperature. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 79.557 | 18.998 | - | - | 0.067 | Gas phase |
| 52.713 | 46.454 | - | - | 0.075 | Liquid phase |
Example 2
Preparation of Cu-containing complex catalyst:
according to the mass ratio of CuI to 2, 2-bipyridine to AlF3Weighing a certain amount of 2, 2-bipyridine, CuI and carrier AlF3Reacting 2, 2-bipyridine with AlF3Adding into a magnetic mortar, grinding for 30min, and mixing; and then placing the mixed sample in a glove box, adding the weighed CuI sample, continuously grinding for 30min, after uniform mixing, transferring the ground sample into a microwave oven, setting the power at 100W, performing microwave radiation for 100min, and taking out the sample after cooling to obtain the supported Cu complex catalyst.
Preparation of 1,1,1,4,4, 4-hexafluoro-2-butene:
20.364g of copper powder (250 mesh), 5.46g of Cu-containing complex, and 30ml of DMAC were added sequentially to a 200ml PEEK reaction kettle at room temperature. N for the reaction kettle2The replacement was carried out 3 to 5 times, and then 19.5g (14ml) of HCFC-123 was injected and sealed. Heating to 50 ℃, stirring at constant temperature for 0.5h, then heating to 110 ℃, and continuously stirring at constant temperature for 2 h. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 84.532 | 14.579 | 0.056 | - | 0.500 | Gas phase |
| 52.234 | 46.304 | 0.167 | - | 0.279 | Liquid phase |
Example 3
Preparation of Cu-containing complex catalyst:
according to the mass ratio of CuI to 2, 2-bipyridine to AlF3Weighing 2, 2-bipyridine, CuI and AlF carrier in a certain ratio of 1:0.41:0.473Reacting 2, 2-bipyridine with AlF3Adding into a magnetic mortar, grinding for 30min, and mixing; and then placing the mixed sample in a glove box, adding the weighed CuI sample, continuously grinding for 30min, after uniform mixing, transferring the ground sample into a microwave oven, setting the power at 500W, performing microwave radiation for 15min, and taking out the sample after cooling to obtain the supported Cu complex catalyst.
Preparation of 1,1,1,4,4, 4-hexafluoro-2-butene:
at room temperature, the mixture is fed into a 200ml PEEK reaction kettle12.33g of copper powder (250 mesh), 1.58g of Cu-containing complex and 60ml of DMF were added in portions. N for the reaction kettle2The replacement was carried out 3 to 5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. Heating to 60 ℃, stirring for 2h at constant temperature, then heating to 80 ℃, and continuously stirring for 4h at constant temperature. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 85.336 | 11.233 | - | - | 2.566 | Gas phase |
| 55.822 | 38.639 | - | - | 4.287 | Liquid phase |
Example 4
Preparation of Cu-containing complex catalyst:
according to the mass ratio of CuCl to 4, 4-bipyridine to CrF3Weighing a certain amount of 4, 4-bipyridine, CuCl and a carrier CrF ═ 1:1.06:0.653Reacting 4, 4-bipyridine with CrF3Adding into a magnetic mortar, grinding for 30min, and mixing; and then placing the mixed sample in a glove box, adding the weighed CuCl sample, continuously grinding for 30min, after uniform mixing, transferring the ground sample into a microwave oven, setting the power to be 750W, performing microwave radiation for 10min, cooling the sample, and taking out the sample to obtain the supported Cu complex catalyst.
Preparation of 1,1,1,4,4, 4-hexafluoro-2-butene:
to a 200ml PEEK reactor, 12.33g of copper powder (250 mesh), 5.46g of Cu-containing complex, and 60ml of DMF were added in this order at room temperature. N for the reaction kettle2The replacement was carried out 3 to 5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. Heating to 40 ℃, stirring for 1.5h at constant temperature, then heating to 80 ℃, and continuously stirring for 4h at constant temperature. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 88.210 | 10.148 | 0.095 | - | 1.401 | Gas phase |
| 52.675 | 43.700 | 0.194 | - | 2.816 | Liquid phase |
Example 5
Preparation of Cu-containing complex catalyst:
according to the mass ratio of CuCl to 2, 2-bipyridine to AlF3:ZnF2Weighing a certain amount of 2, 2-bipyridine, CuCl and a carrier AlF3、ZnF2The carrier AlF3、ZnF2Mixing and grinding for 10min to obtain a composite carrier B, adding 2, 2-bipyridine and the composite carrier B into a magnetic mortar, grinding for 30min, and uniformly mixing; and then placing the mixed sample in a glove box, adding the weighed CuCl sample, continuously grinding for 30min, after uniform mixing, transferring the ground sample into a microwave oven, setting the power to be 450W, radiating the microwave for 10min, and taking out the sample after cooling to obtain the supported Cu complex catalyst.
Preparation of 1,1,1,4,4, 4-hexafluoro-2-butene:
to a 200ml PEEK reaction kettle at room temperature was added 12.33g of copper powder (250 mesh), 2 in order.58g of Cu-containing complex, 80ml of DMF. N for the reaction kettle2The replacement was carried out 3 to 5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. Heating to 60 ℃, stirring for 2h at constant temperature, then heating to 120 ℃, and continuously stirring for 4h at constant temperature. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 80.007 | 19.106 | 0.106 | 0.067 | 0.494 | Gas phase |
| 54.320 | 44.551 | 0.393 | 0.103 | 0.162 | Liquid phase |
Example 6
Preparation of Cu-containing complex catalyst:
weighing a certain amount of 2, 2-bipyridine, CuI and carrier bentonite according to the mass ratio of CuI to 2, 2-bipyridine to bentonite of 1:1.22:2.22, adding the 2, 2-bipyridine and the bentonite into a magnetic mortar, grinding for 30min, and uniformly mixing; and then placing the mixed sample in a glove box, adding the weighed CuI sample, continuously grinding for 30min, after uniform mixing, transferring the ground sample into a microwave oven, setting the power to be 750W, radiating the microwave for 30min, and taking out the sample after cooling to obtain the supported Cu complex catalyst.
Preparation of 1,1,1,4,4, 4-hexafluoro-2-butene:
to a 200ml PEEK reactor, 12.33g of copper powder (250 mesh), 1.98g of Cu-containing complex, and 60ml of DMF were added in this order at room temperature. N for the reaction kettle2The replacement was carried out 3 to 5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. Heating to 55 ℃, stirring for 2h at constant temperature, then heating to 120 ℃, and continuously stirring for 4h at constant temperature. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 78.633 | 18.754 | 0.306 | - | 1.442 | Gas phase |
| 50.624 | 46.752 | 0.227 | 0.304 | 1.967 | Liquid phase |
Comparative example 1
To a 200ml PEEK reactor, 12.33g of copper powder (250 mesh), 1.98g of 2, 2-bipyridine, 2.41g of cuprous iodide, 60ml of DMF were added in this order at room temperature. N for the reaction kettle2The replacement was carried out 3 to 5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. Heating to 40 ℃, stirring for 2h at constant temperature, then heating to 80 ℃, and continuously stirring for 2h at constant temperature. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 78.008 | 16.370 | 0.694 | 0.159 | 4.512 | Gas phase |
| 44.222 | 41.737 | 1.130 | 0.878 | 11.024 | Liquid phase |
Comparative example 2
To a 200ml PEEK reaction vessel at room temperature were added 12.33g of copper powder (250 mesh), 1.98g of 2, 2-bipyridine, 2.41g of copper iodide (CuI), 1.07g of aluminum trifluoride (AlF) in this order3) 60ml of DMF. N for the reaction kettle2Replacing 3-5 times, and sealing. 13g (9ml) of HCFC-123 were injected into the reactor. Heating to 40 ℃, stirring for 2h at constant temperature, then heating to 80 ℃, and continuously stirring for 4h at constant temperature. After the completion of the reaction, the gas and liquid phases in the reaction vessel were analyzed by GC-MS, and the results of the analysis in the following table show the peak area ratio (GC%) where a small amount of by-products having a GC% of less than 0.05 were not included in the table.
| E-1336 | Z-1336 | CF3CH2Cl | CF3CH＝CHCF2Cl | HCFC-123 | Remarks for note |
| 76.906 | 16.082 | 0.140 | 0.106 | 5.720 | Gas phase |
| 45.022 | 41.587 | 1.137 | 0.799 | 10.615 | Liquid phase |
From the comparison of the above examples and comparative examples, it can be seen that the Cu-containing complex catalyst developed by the present invention is used for the coupling reaction of HCFC-123 and copper metal powder to prepare HFO-1336, and the acidic center of the catalyst is modulated, so that the reaction efficiency is improved to the maximum extent, and the yield of the product and the conversion rate of the reactant are both high; in the reaction process, the occurrence of side reactions is well reduced by a two-stage reaction process and the control of the performance of the raw materials.
Claims (10)
1. The application of a Cu-containing complex catalyst in preparation of 1,1,1,4,4, 4-hexafluoro-2-butene is characterized in that the 1,1,1,4,4, 4-hexafluoro-2-butene is prepared by reacting 2, 2-dichloro-1, 1, 1-trifluoroethane with copper powder in an amide solvent under the action of the Cu-containing complex catalyst;
the Cu-containing complex catalyst is prepared from copper salt, a nitrogen-containing organic ligand and a Lewis acid carrier; wherein the copper salt is a cuprous salt; the nitrogen-containing organic ligand is selected from 2, 2-bipyridine, 4-bipyridine or 1, 10-phenanthroline.
2. The use according to claim 1, wherein the mass ratio of the copper salt, the nitrogen-containing organic ligand and the Lewis acidic support is 1:0.15-1.22: 0.13-2.22.
3. The use according to claim 1, wherein the monovalent copper salt is selected from the group consisting of CuI, CuCl, and CuBr.
4. The use according to claim 1, wherein the Lewis acidic carrier is selected from the group consisting of AlF3、CrF3、MgF2、ZnF2、YF3、SmF3、EuF3Or the specific surface area is more than or equal to 10m2(ii) a layered structure compound per gram.
5. The application of claim 1, wherein the preparation method of the Cu-containing complex catalyst comprises the following specific steps:
1) fully grinding and uniformly mixing the nitrogen-containing organic ligand and the Lewis acid carrier in a mortar;
2) placing the mixture ground in the step 1) in a glove box, adding cuprous salt, continuously grinding and uniformly mixing;
3) transferring the mixture ground in the step 2) into a microwave oven for reaction, and cooling to obtain the Cu-containing complex catalyst.
6. The use of claim 5, wherein the reaction time of step 3) is 5-100min, and the microwave power of the microwave oven is 100-1000W.
7. The use according to claim 1, characterized in that the mass ratio of 2, 2-dichloro-1, 1, 1-trifluoroethane, copper powder and amide solvent is 1:0.8-1.05: 0.65-5.
8. The use according to claim 1 or 7, wherein the amide solvent is selected from N, N-dimethylformamide, formamide or dimethylacetamide.
9. Use according to claim 1 or 7, characterized in that the particle size of the copper powder is 10-500 mesh.
10. The use according to claim 1, wherein the reaction for the preparation of 1,1,1,4,4, 4-hexafluoro-2-butene is carried out at 40-80 ℃ for 0.5-2.0h and then at 60-150 ℃ for 0.5-6h with a stirring speed of 500-1000 rpm.
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