CN115611701A - Method for synthesizing difluorobromopropylene - Google Patents
Method for synthesizing difluorobromopropylene Download PDFInfo
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- CN115611701A CN115611701A CN202211251390.0A CN202211251390A CN115611701A CN 115611701 A CN115611701 A CN 115611701A CN 202211251390 A CN202211251390 A CN 202211251390A CN 115611701 A CN115611701 A CN 115611701A
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Abstract
The invention relates to a method for synthesizing difluorobromopropylene, belonging to the field of organic chemical synthesis. A method for synthesizing difluorobromopropene is characterized by comprising the following steps: bromotrifluoromethane (CF) 3 Br) and ethylene gas (CH) 2 ＝CH 2 ) Generating difluorobromopropene (molecular formula CF) under the action of catalyst 2 Br‑CH 2 ＝CH 2 )。CBrF 3 +H 2 C＝CH 2 →H 2 C＝CH‑CF 2 Br the invention has cheap raw materials and convenient sources; the catalyst has good stability and long service life; the product is simple to separate and purify; is easy for industrialized production.
Description
Technical Field
The invention discloses a method for synthesizing difluorobromopropene, and relates to a method for synthesizing difluorobromopropene by an easily industrialized method.
Background
Difluorobromopropene (CAS: 460-33-3, 1-bromo-3, 3-trifluoropropene) is a nonflammable bromofluoroolefin liquid, has a boiling point of 40 ℃, and has the advantages of low toxicity, low global warming potential, low ozone depletion potential, and the like. Laboratory tests show that after the 1-bromo-3, 3-trifluoropropene is mixed with inert gas, the fire extinguishing effect is similar to that of a BTP fire extinguishing agent, the extinguishing time can be effectively shortened when the extinguishing agent is mixed with a dry powder fire extinguisher, and the using process is safer and more reliable. By virtue of safety, high efficiency and environmental friendliness, the 1-bromo-3, 3-trifluoropropene has the potential of replacing perfluorohexanone, heptafluoropropane and other clean fire extinguishing agents, and has a large market in the future.
At present, the synthesis methods of 1-bromo-3, 3-trifluoropropene are reported earlier, and related researches in China are few. Patent (CN 104936934A) reports that 3,3,3-trifluoropropyne is put in a Lewis acid environment, and heated to 50-350 ℃ for 2 hours by using hydrogen bromide as a catalyst, and then the product is collected by a cooling trap at-78 ℃. The yield of 1-bromo-3, 3-trifluoropropene under this method is around 74%, but the product is accompanied by various by-products such as 2-bromo-3, 3-trifluoropropene and 1, 2-dibromo-3, 3-trifluoropropene, etc. A method for producing l-bromo-3, 3-trifluoropropene by mixing 3, 3-trifluoropropyne with hydrogen bromide at 0 ℃ is reported in the Journal of the American Chemical Society,1952, vol.74, p.650, in a yield of between 83 and 91%, and the reaction temperature can be lowered to around-25 ℃ by adding aluminum bromide. However, this method needs to be carried out in a low-temperature environment, is relatively expensive, and is not suitable for commercial production.
In summary, the existing synthetic route of 1-bromo-3, 3-trifluoropropene has the characteristics of harsh environmental requirements, expensive raw material cost, low product purity and the like, which all limit the industrial production of 1-bromo-3, 3-trifluoropropene.
Disclosure of Invention
The invention aims to prepare high-yield tetrafluoro monobromo butene by using a simple reaction system and suitable reaction conditions, and the invention has the advantages of cheap raw materials and convenient source; the catalyst has good stability and long service life; the product is simple to separate and purify; the synthesis process is safe and suitable for industrial production.
The invention relates to a method for synthesizing difluorobromopropylene, which is characterized by comprising the following steps: bromotrifluoromethane (CF) 3 Br) and ethylene gas (CH) 2 ＝CH 2 ) Generating difluorobromopropene (molecular formula CF) under the action of catalyst 2 Br-CH＝CH 2 )
The bromotrifluoromethane and ethylene gas generate difluorobromopropylene under the action of a catalyst, wherein the catalyst is at least one of Mg, mn, fe, pd and Al, or a compound formed by at least one of Mg, mn, fe, pd and Al and one of Bi, ti, ni and other metals.
The bromotrifluoromethane and ethylene gas generate difluorobromopropylene under the action of a catalyst, and the reaction temperature is-20-300 ℃.
Generating difluorobromopropylene from bromotrifluoromethane and ethylene gas under the action of a catalyst, wherein the molar ratio of the bromotrifluoromethane to the ethylene is 1: 1-10.
And (3) generating difluorobromopropylene from bromotrifluoromethane and ethylene gas under the action of a catalyst, wherein the reaction contact time is 1-20s.
The invention has the following beneficial effects:
1. the invention has cheap raw materials and convenient sources.
2. The catalyst has good stability and can be repeatedly recycled.
3. The product is simple to separate and purify.
4. Safe synthesis process and suitability for industrial production
Detailed Description
The present invention is further illustrated by the following description of the specific embodiments, which is not intended to limit the present invention, and those skilled in the art can make various modifications or improvements based on the basic idea of the present invention, but within the scope of the present invention, unless departing from the basic idea of the present invention.
Example 1
Mixing the components in a molar ratio of 50:40:5: mgCl of 5 2 ，Mn(NO 3 ) 2 ，PdCl 2 ，ZnCl 2 The solutions were mixed, and 30wt.% aqueous ammonia was added dropwise to the mixed solution, and the pH was adjusted =11.0. And (3) filtering the precipitate, washing with deionized water, drying, and pressing for forming to obtain a catalyst precursor Mg-Mn-Pd-Zn. The specific surface area is 425m measured by the BET method 2 /g。
50ml of catalyst Mg-Mn-Pd-Zn precursor is added into a fixed bed reactor, and the fixed bed reactor is heated by an open tubular heating furnace. The catalyst was first raised to 200 ℃ at 5 ℃/min under a nitrogen blanket of 100ml/min and dried at this temperature for 10 hours, after which the temperature was lowered to 100 ℃. This completes the drying process of the catalyst. The reactor was heated to 200 ℃ and the catalyst was activated with 100ml/min pure hydrogen chloride for 10 hours. Thus completing the activation process of the Mg-Mn-Pd-Zn catalyst.
The reactor was heated to 150 ℃ and 22.4ml/min of bromotrifluoromethane and 30ml/min of ethylene were fed into a mixing chamber using a mass flow meter and mixed uniformly. Then, the reaction product passes through the reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed that the product collected contained 45% difluoromonobromopropene.
Example 2
Mixing the components in a molar ratio of 50:40:5: mgCl of 5 2 ，Mn(NO 3 ) 2 ，BiCl 3 ，FeCl 3 The solutions were mixed, and 30wt.% aqueous ammonia was added dropwise to the mixed solution, and the pH was adjusted =11.0. And (4) precipitating and filtering, washing with deionized water, drying, and pressing for forming to obtain a catalyst precursor Mg-Mn-Bi-Fe. The specific surface area is 385m measured by a BET method 2 /g。
50ml of catalyst Mg-Mn-Bi-Fe precursor is added into a fixed bed reactor, and the fixed bed reactor is heated by an open tubular heating furnace. The catalyst was first raised to 200 ℃ at 5 ℃/min under a nitrogen blanket of 100ml/min and dried at this temperature for 10 hours, after which the temperature was lowered to 100 ℃. This completes the drying process of the catalyst. The reactor was heated to 200 ℃ and the catalyst was activated with 100ml/min pure hydrogen chloride for 10 hours. This completes the activation process of the Mg-Mn-Bi-Fe catalyst.
The reactor was heated to 250 ℃ and 22.4ml/min bromotrifluoromethane was mixed with 56.2ml/min ethylene in a mixing chamber using a mass flow meter. Then, the reaction product passes through the reactor to a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed that the product collected contained 65% difluoromonobromopropene.
Example 3
Mixing the components in a molar ratio of 50:30:20 MgCl 2 ，Mn(NO 3 ) 2 ，FeCl 3 The solutions were mixed, and 30wt.% aqueous ammonia was added dropwise to the mixed solution, and the pH was adjusted =11.0. And (4) precipitating and filtering, washing with deionized water, drying, and pressing for forming to obtain a catalyst precursor Mg-Mn-Fe. The specific surface area of the powder is 352m measured by a BET method 2 /g。
50ml of catalyst Mg-Mn-Fe precursor is added into a fixed bed reactor, and the fixed bed reactor is heated by an open tubular heating furnace. The catalyst was first raised to 200 ℃ at 5 ℃/min under a nitrogen blanket of 100ml/min and dried at this temperature for 10 hours, after which the temperature was lowered to 100 ℃. This completes the drying process of the catalyst. The reactor was heated to 200 ℃ and the catalyst was activated with 100ml/min pure hydrogen chloride for 10 hours. This completes the activation process of the Mg-Mn-Fe catalyst.
The reactor was heated to 180 ℃ and 22.4ml/min of bromotrifluoromethane and 32.6ml/min of ethylene were mixed together in a mixing chamber using a mass flow meter. Then, the reaction solution passes through the reactor to reach a buffer bottle, a water washing bottle, a concentrated alkali absorber and a cooling collector. After the experiment was completed, the product was mainly distributed in the cooling accumulator. The collected product was subjected to GC analysis. The GC results showed that the product collected contained 55% difluorobromopropene.
Claims (5)
1. A method for synthesizing difluorobromopropene is characterized by comprising the following steps: monobromotrifluoromethane (CF) 3 Br) and ethylene gas (CH) 2 ＝CH 2 ) Generating difluorobromopropene (molecular formula CF) under the action of catalyst 2 Br-CH＝CH 2 )。
2. The method of claim 1, wherein the difluorobromopropene is produced from bromotrifluoromethane and ethylene gas over a catalyst selected from the group consisting of at least one of Mg, mn, fe, pd, and Al, or a composite of at least one of Mg, mn, fe, pd, and Al and one of Bi, ti, and Ni.
3. The process of claim 1, wherein the reaction temperature of bromotrifluoromethane and ethylene gas is-20 to 300 ℃ under the action of a catalyst to produce difluorobromopropene.
4. The method according to claim 1, wherein the difluorobromopropene is generated from bromotrifluoromethane and ethylene gas in the presence of a catalyst, and the molar ratio of the bromotrifluoromethane to the ethylene is 1: 1-10.
5. The process of claim 1, wherein the reaction contact time of the bromotrifluoromethane and the ethylene gas in the presence of the catalyst is 1-20s.
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