CN106669837A - A method for preparing 1,1,1,4,4,4-hexafluoro-2-butene - Google Patents

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

A method for preparing 1,1,1,4,4,4-hexafluoro-2-butene

technical field

The present invention relates to the preparation of 1,1,1,4,4,4-hexafluoro-2-butene, in particular to the preparation of a Cu-containing complex catalyst, and the catalyst is used for 1,1,1, In the preparation of 4,4,4-hexafluoro-2-butene.

technical background

Within the framework of the Montreal Protocol, the use of products such as chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) will cause serious damage to the ozone layer, making them bound to fade out of refrigerants, blowing agents, solvents, fire extinguishers, etc. Agents and propellants and other product industries. At present, hydrofluorocarbons (HFCs) are widely used as good substitutes. Although they are not destructive to the stratospheric ozone layer, due to their high global warming potential (GWP), long-term large-scale use will Cause serious "greenhouse effect". Therefore, the wide application of such products will be subject to strict policy restrictions. Although the 1,1,3,3,3-pentafluoropropane (HFC-245fa) product, which is currently widely concerned in the field of polyurethane foam, has a zero ozone layer depletion potential (ODP value), due to its GWP value of 920, a large number of Use and emission will cause a serious greenhouse effect, so it can only be used as a substitute for excessive polyurethane foaming.

Hydrofluoroolefin (HFO) products, because ODP is zero, GWP value is extremely low, and this type of product shows the same performance as HFCs products in the field of refrigeration, foaming and propulsion, so it has attracted wide attention. 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 ) etc. began to be promoted and accepted by the market. Cis-1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz) has attracted widespread attention due to its good performance in the field of polyurethane foaming. And it can also be used as refrigerant, heat transfer medium and propellant to replace HFCs products.

Chinese patent CN 103626627 A discloses a preparation method using 2,2-dichloro-1,1,1-trifluoroethane and copper in the presence of amide solvent, 2,2-bipyridine and Cu(I) salt. Method for 1,1,1,4,4,4-hexafluoro-2-butene. This method 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 by-products, such The product is easy to form an azeotropic composition with HFO-1336, which will bring greater trouble to the subsequent separation of the product, as described in US Patent US 8871987 B; US Patent US 5516951 B discloses a method by combining 2,2-di A method for preparing HFO-1336 by reacting chloro-1,1,1-trifluoroethane with copper and amine, but the yield of the product of this preparation method is not high, and there are many side reactions; Chinese patent CN 102015592 B discloses a A method for preparing HFO-1336 by introducing 2,2-bipyridine and Cu(I) into a system of 2,2-dichloro-1,1,1-trifluoroethane and copper as a catalyst, although the method is better The problem of product yield is solved, but there are 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 that are difficult to separate. Although the above-mentioned methods for preparing HFO-1336 have certain advantages, they cannot simultaneously solve the problems of low yield of the target product, long reaction time, easy occurrence of side reactions, and difficulty in separating the obtained by-product from the target product.

Contents of the invention

Aiming at the defects and deficiencies of the above-mentioned prior art, the present invention provides a Cu-containing complex catalyst, a preparation method and an 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 the reaction can obtain high yield in a short time The target product; at the same time, it can reduce the occurrence of side reactions, effectively inhibit the formation of HFO-1326, HFO-1335 and other by-products; thus it can effectively improve the purity of the target product.

The first aspect of the technical solution of the present invention provides a Cu-containing complex catalyst prepared from a copper salt, a nitrogen-containing organic ligand and a Lewis acidic carrier.

In some embodiments, the mass ratio of the copper salt, the nitrogen-containing organic ligand and the Lewis acidic carrier is 1:0.15-1.22:0.13-2.22.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic support is 1:0.15:0.13.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic support is 1:0.3:0.5.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic support is 1:0.45:0.8.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic support is 1:0.6:1.1.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic support is 1:0.75:1.4.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic carrier is 1:1:1.7.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic carrier is 1:1.1:2.

In some embodiments, the mass ratio of copper salt, nitrogen-containing organic ligand and Lewis acidic support is 1:1.22:2.22.

The copper salt used in the present invention is a monovalent copper salt, and in some embodiments, the monovalent 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 present invention is selected from 2,2-bipyridine, 4,4-bipyridine or 1,10-phenanthroline.

The Lewis acid carrier used in the present invention is selected from AlF ₃ , CrF ₃ , MgF ₂ , ZnF ₂ , YF ₃ , SmF ₃ , EuF ₃ or layered structure compounds with specific surface area ≥ 10m ² /g.

The "layered structure compound with a specific surface area ≥ 10m ² /g" in the present invention refers to some natural or synthetic Lewis acidic materials with a layered structure and a specific surface area ≥ 10m ² /g, such as: bentonite, Molecular sieves, clay or silica-alumina molecular sieves, etc.

The second aspect of the technical solution of the present invention provides a method for preparing the above-mentioned Cu-containing complex catalyst, comprising the following steps:

1) Fully grind and mix the nitrogen-containing organic ligand and the Lewis acidic carrier in a mortar;

2) Place the ground mixture in 1) in a glove box, then add monovalent copper salt and continue grinding and mixing;

3) Transfer the ground mixture in 2) to a microwave oven to react for a period of time and then cool to obtain a Cu-containing complex catalyst.

In some embodiments of the present invention, the reaction period in step 3) of the method for preparing the catalyst containing the Cu complex is 5-100 min, and the microwave power is 100-1000W. In some embodiments of the present invention, the reaction time of microwave reaction is 10min, and microwave power is 450W; In some embodiments, the reaction time of microwave reaction is 100min, and microwave power is 100W; In some embodiments, microwave reaction The reaction time 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.

The third aspect of the technical solution of the present invention provides a method for preparing 1,1,1,4,4,4-hexafluoro-2-butene using the above Cu-containing complex catalyst, the 1,1,1, 4,4,4-hexafluoro-2-butene is reacted by 2,2-dichloro-1,1,1-trifluoroethane and copper powder in amide solvent under the action of Cu complex catalyst prepared.

In some embodiments of the present invention, 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.

In some embodiments, the mass ratio of 2,2-dichloro-1,1,1 trifluoroethane, copper powder and amide solvent is 1:0.8:0.65.

In some embodiments of the present invention, the mass ratio of 2,2-dichloro-1,1,1 trifluoroethane, copper powder and amide solvent is 1:0.85:1.

In other embodiments of the present invention, the mass ratio of 2,2-dichloro-1,1,1 trifluoroethane, copper powder and amide solvent is 1:1.05:5.

In some embodiments of the present invention, the content of the catalyst containing the Cu complex is 1.5%-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 solvent is selected from N,N-dimethylformamide (DMF), formamide or dimethylacetamide (DMAC).

The particle size of the copper powder in the present invention is 10-500 mesh. In some embodiments, the particle size of the copper powder is 50-350 mesh; in some embodiments, the particle size of the copper powder is 10-150 mesh; in some embodiments, the particle size of the copper powder is 250-500 mesh .

In the method for preparing 1,1,1,4,4,4,-hexafluoro-2-butene using the Cu-containing complex catalyst of the present invention, the reaction is carried out at 40-80°C for 0.5-2.0h Then the temperature was raised to 60-150° C. to continue the reaction for 0.5-6 h; the stirring rate was 500-1000 rpm.

Description of drawings

Fig. 1 is the infrared spectrogram of nitrogen-containing organic ligand 2,2-bipyridine;

Fig. 2 is the infrared spectrogram of embodiment 1 containing Cu complex;

Fig. 3 is the infrared spectrogram of embodiment 2 containing Cu complex;

Fig. 4 is the infrared spectrogram of embodiment 3 containing Cu complex;

Fig. 5 is the infrared spectrogram of embodiment 4 containing Cu complex;

Fig. 6 is the infrared spectrogram of embodiment 5 containing Cu complex;

Fig. 7 is the infrared spectrogram of the Cu-containing complex of Example 6.

Definition of Terms

The present invention is intended to cover all alternatives, modifications and equivalent technical solutions, which are included within the scope of the present invention as defined by the claims. Those skilled in the art will recognize many methods and materials similar or equivalent to those described herein, which could 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 literature, patents, and similar materials differs from or contradicts this application (including but not limited to defined terms, term usage, described techniques, etc.), this application prevail.

All ranges cited herein are inclusive of endpoints unless expressly stated to the contrary. For example, "the particle size of the copper powder is 10-500 mesh" means that the range of the particle size r of the reactive copper powder is 10 mesh≤r≤500 mesh.

The term "or" as used herein indicates alternatives, which may be combined, if appropriate, that is, the term "or" includes each listed individual alternative as well as combinations thereof. For example, "the nitrogen-containing organic compound is selected from 2,2-bipyridine, 4,4-bipyridine or 1,10-phenanthroline" means that the nitrogen-containing organic compound can be 2,2-bipyridine, 4,4-bipyridine One of pyridine and 1,10-phenanthroline, or a combination of more than one of them.

The terms "a" or "an" are used herein to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Numerals herein are approximate, regardless of whether words such as "about" or "approximately" are used. Numerical values may vary by 1%, 2%, 5%, 7%, 8%, 10%. Whenever a number with a value of N is disclosed, any number with N+/-1%, N+/-2%, N+/-3%, N+/-5%, N+/-7%, N+/-8%, or N+ Figures for values of /-10% are explicitly disclosed, where "+/-" means plus or minus, and ranges between N-10% and N+10% are also disclosed.

Unless otherwise defined, 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 invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety, unless a specific passage 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 beneficial effects of the present invention are:

(1) in the present invention, the method for preparing HFO-1336 with Cu complex catalyst catalysis can not only ensure that the target product has a higher coupling conversion rate, but also can make the yield of the target product increase equally; in the present invention The conversion rate of HCFC-123 in the medium can reach 99.925%, and the yield of the target product can reach 99.09%.

(2) In the present invention, the reaction to prepare HFO-1336 by catalyzing a Cu-containing complex catalyst is a strong exothermic reaction, and the heat release is particularly obvious at the initial stage of the reaction. Therefore, the present invention adopts a two-stage temperature control method, which can make the reaction more efficient. Moderate and gradual, it can also reduce energy consumption to a large extent in industrial production.

(3) In the present invention, a Cu complex catalyst is used to catalyze the preparation of HFO-1336, wherein the total selectivity of the HFO-1336 product can reach 99.167%. The catalyst has a good effect on suppressing the occurrence of side reactions, especially the reaction There is no R133a, HFO-1335 and other by-products that will form an azeotropic composition with Trans-HFO-1336 (E-1336) or Cis-HFO-1336 (Z-1336) in the final product, which is suitable for the separation of subsequent products in industrial production A good foundation has been laid.

detailed description

What is described below is the preferred implementation of the present invention, and the protection of the present invention is not limited to the following preferred implementation. It should be pointed out that for those skilled in the art, on the basis of the inventive concept, several modifications and improvements made belong to the protection scope of the present invention. In order to further describe the present invention, the following uses specific embodiments in conjunction with the accompanying drawings to illustrate.

Example 1

Preparation of Cu complex catalyst:

Weigh a certain amount of 2,2-bipyridine, CuI and carrier AlF ₃ according to the mass ratio CuI:2,2-bipyridine:AlF ₃ =1:1.22:0.56, add 2,2-bipyridine and AlF ₃ to the magnetic Grind in a mortar for 30 minutes and mix well; then put the mixed sample in the glove box, add the weighed CuI sample, and continue grinding for 30 minutes. After mixing evenly, transfer the ground sample to a microwave oven, set the power 450W, microwave irradiation time 10min, after the sample is cooled, take it out to obtain the supported Cu complex catalyst.

Preparation of 1,1,1,4,4,4-hexafluoro-2-butene:

At room temperature, 12.33 g of copper powder (250 mesh), 5.46 g of Cu-containing complex, and 60 ml of DMF were sequentially added to a 200 ml PEEK reactor. The reaction kettle was replaced with N ₂ for 3-5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. The temperature was raised to 40°C, and stirred at constant temperature for 2h, then the temperature was raised to 80°C, and stirred at constant temperature for 2h. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 79.557 18.998 - - 0.067 gas phase 52.713 46.454 - - 0.075 liquid phase

Example 2

Preparation of Cu complex catalyst:

Weigh a certain amount of 2,2-bipyridine, CuI and carrier AlF ₃ according to the mass ratio CuI:2,2-bipyridine:AlF ₃ =1:1.22:0.25, add 2,2-bipyridine and AlF ₃ to the magnetic Grind in a mortar for 30 minutes and mix well; then put the mixed sample in the glove box, add the weighed CuI sample, and continue grinding for 30 minutes. After mixing evenly, transfer the ground sample to a microwave oven, set the power 100W, microwave irradiation time 100min, after the sample is cooled, take it out to get the supported Cu complex catalyst.

Preparation of 1,1,1,4,4,4-hexafluoro-2-butene:

At room temperature, 20.364g of copper powder (250 mesh), 5.46g of Cu-containing complex, and 30ml of DMAC were sequentially added to a 200ml PEEK reactor. The reaction kettle was replaced with N ₂ for 3-5 times, and then 19.5g (14ml) of HCFC-123 was injected and sealed. The temperature was raised to 50°C, and stirred at constant temperature for 0.5h, then the temperature was raised to 110°C, and stirred at constant temperature for 2h. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 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 complex catalyst:

Weigh a certain amount of 2,2-bipyridine, CuI and carrier AlF ₃ according to the mass ratio CuI:2,2-bipyridine:AlF ₃ =1:0.41:0.47, add 2,2-bipyridine and AlF ₃ to the magnetic Grind in a mortar for 30 minutes and mix well; then put the mixed sample in the glove box, add the weighed CuI sample, and continue grinding for 30 minutes. After mixing evenly, transfer the ground sample to a microwave oven, set the power 500W, microwave irradiation time 15min, take out the sample after cooling to get the supported Cu complex catalyst.

Preparation of 1,1,1,4,4,4-hexafluoro-2-butene:

At room temperature, 12.33 g of copper powder (250 mesh), 1.58 g of Cu-containing complex, and 60 ml of DMF were sequentially added to a 200 ml PEEK reactor. The reaction kettle was replaced with N ₂ for 3-5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. The temperature was raised to 60°C, and stirred at constant temperature for 2h, then the temperature was raised to 80°C, and stirred at constant temperature for 4h. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 85.336 11.233 - - 2.566 gas phase 55.822 38.639 - - 4.287 liquid phase

Example 4

Preparation of Cu complex catalyst:

Weigh a certain amount of 4,4-bipyridine, CuCl and carrier CrF ₃ according to the mass ratio CuCl:4,4-bipyridine:CrF ₃ =1:1.06:0.65, add 4,4-bipyridine and CrF ₃ to the magnetic Grind in a mortar for 30 minutes and mix well; then put the mixed sample in the glove box, add the weighed CuCl sample, continue to grind for 30 minutes, after mixing evenly, transfer the ground sample to a microwave oven, set the power 750W, microwave irradiation time 10min, after taking out the sample after cooling, the supported Cu complex catalyst was obtained.

Preparation of 1,1,1,4,4,4-hexafluoro-2-butene:

At room temperature, 12.33 g of copper powder (250 mesh), 5.46 g of Cu-containing complex, and 60 ml of DMF were sequentially added to a 200 ml PEEK reactor. The reaction kettle was replaced with N ₂ for 3-5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. The temperature was raised to 40°C, and stirred at constant temperature for 1.5h, then the temperature was raised to 80°C, and stirred at constant temperature for 4h. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 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 complex catalyst:

According to the mass ratio CuCl:2,2-bipyridine:AlF ₃ :ZnF ₂ =1:0.81:0.41:0.07, weigh a certain amount of 2,2-bipyridine, CuCl and the carrier AlF ₃ , ZnF ₂ , and the carrier AlF ₃ , ZnF ₂ mixed and ground for 10 minutes to make a composite carrier B, then added 2,2-bipyridine and composite carrier B into a magnetic mortar and ground for 30 minutes, and mixed evenly; then put the mixed sample in a glove box, and added Continue to grind the measured CuCl sample for 30 minutes. After mixing evenly, transfer the ground sample to a microwave oven, set the power to 450W, and microwave irradiation time for 10 minutes. After the sample is cooled, take it out to obtain the supported Cu complex catalyst.

Preparation of 1,1,1,4,4,4-hexafluoro-2-butene:

At room temperature, 12.33 g of copper powder (250 mesh), 2.58 g of a Cu-containing complex, and 80 ml of DMF were sequentially added to a 200 ml PEEK reactor. The reaction kettle was replaced with N ₂ for 3-5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. The temperature was raised to 60° C., and stirred at a constant temperature for 2 hours, then the temperature was raised to 120° C., and the stirring was continued at a constant temperature for 4 hours. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 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 complex catalyst:

Weigh a certain amount of 2,2-bipyridine, CuI and carrier bentonite according to the mass ratio CuI:2,2-bipyridine:bentonite=1:1.22:2.22, and add 2,2-bipyridine and bentonite to the magnetic mortar Grind for 30 minutes and mix well; then put the mixed sample in the glove box, add the weighed CuI sample, continue grinding for 30 minutes, after mixing evenly, transfer the ground sample to a microwave oven, set the power to 750W, microwave The irradiation time is 30 minutes, and the supported Cu complex catalyst is obtained after the sample is cooled.

Preparation of 1,1,1,4,4,4-hexafluoro-2-butene:

At room temperature, 12.33 g of copper powder (250 mesh), 1.98 g of Cu-containing complex, and 60 ml of DMF were sequentially added to a 200 ml PEEK reactor. The reaction kettle was replaced with N ₂ for 3-5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. The temperature was raised to 55° C., and stirred at a constant temperature for 2 h, then the temperature was raised to 120° C., and the stirring was continued at a constant temperature for 4 h. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 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

At room temperature, 12.33 g of copper powder (250 mesh), 1.98 g of 2,2-bipyridine, 2.41 g of cuprous iodide, and 60 ml of DMF were sequentially added to a 200 ml PEEK reactor. The reaction kettle was replaced with N ₂ for 3-5 times, and then 13g (9ml) of HCFC-123 was injected and sealed. The temperature was raised to 40°C, and stirred at constant temperature for 2h, then the temperature was raised to 80°C, and stirred at constant temperature for 2h. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 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

At room temperature, 12.33g of copper powder (250 mesh), 1.98g of 2,2-bipyridine, 2.41g of cuprous iodide (CuI), 1.07g of aluminum trifluoride (AlF ₃ ), the DMF of 60ml. The reactor was replaced with N ₂ for 3-5 times, and then sealed. 13 g (9 ml) of HCFC-123 were injected into the autoclave. The temperature was raised to 40°C, and stirred at constant temperature for 2h, then the temperature was raised to 80°C, and stirred at constant temperature for 4h. After the reaction, use GC-MS to analyze the gas and liquid phases in the reactor. The analysis results in the following table are the proportion of the peak area (GC%), and a small amount of by-products with GC% less than 0.05 are not included in the table .

E-1336 Z-1336 _{CF3CH2Cl _} CF ₃ CH=CHCF ₂ Cl HCFC-123 Remark 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 concluded that a Cu complex catalyst developed by the present invention is used for the coupling reaction of HCFC-123 and metal copper powder to prepare HFO-1336. Modulation is carried out to maximize the efficiency of the reaction, and the yield of the product and the conversion rate of the reactant are high; in the process of the reaction, through the two-stage reaction process and the performance of the raw material are controlled, Very good to reduce the occurrence of side reactions.

Claims (10)

1. A Cu complex catalyst is characterized in that, said catalyst is prepared from copper salt, nitrogen-containing organic ligand and Lewis acidic carrier. 2. The catalyst according to claim 1, characterized in that the mass ratio of the copper salt, the nitrogen-containing organic ligand and the Lewis acidic carrier is 1:0.15-1.22:0.13-2.22. 3. The catalyst according to claim 1 or 2, characterized in that the copper salt is a monovalent copper salt. 4. The catalyst according to claim 3, characterized in that the monovalent copper salt is selected from CuI, CuCl or CuBr. 5. The catalyst according to claim 1 or 2, characterized in that the nitrogen-containing organic ligand is selected from 2,2-bipyridine, 4,4-bipyridine or 1,10-phenanthroline. 6. The catalyst according to claim 1 or 2, characterized in that, the Lewis acidic carrier is selected from AlF ₃ , CrF ₃ , MgF ₂ , ZnF ₂ , YF ₃ , SmF ₃ , EuF ₃ or a specific surface area ≥ 10m ² /g layer structure compound. 7. A method for preparing the Cu-containing complex catalyst as claimed in claim 1-6, the specific steps are as follows: 1) Fully grind and mix the nitrogen-containing organic ligand and the Lewis acidic carrier in a mortar; 2) Place the ground mixture in 1) in a glove box, then add monovalent copper salt and continue grinding and mixing; 3) Transfer the ground mixture in 2) to a microwave oven for reaction and then cool to obtain a Cu-containing complex catalyst. 8. The method according to claim 7, characterized in that, the reaction time of the step 3) is 5-100min, and the microwave power of the microwave oven is 100-1000W. 9. A method for preparing 1,1,1,4,4,4-hexafluoro-2-butene using the catalyst of claims 1-6, 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 a Cu-containing complex catalyst . 10. The method according to claim 9, characterized in that, the mass ratio of 2,2-dichloro-1,1,1 trifluoroethane, copper powder and amides solvent is 1:0.8-1.05:0.65- 5; Preferably, the amide solvent is selected from N,N-dimethylformamide, formamide or dimethylacetamide; Preferably, the particle size of the copper powder is 10-500 mesh; Further preferably, the reaction is carried out at 40-80° C. for 0.5-2.0 h and then heated to 60-150° C. for 0.5-6 h, wherein the stirring rate is 500-1000 rpm.