CN110590494A - Method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in illumination environment - Google Patents
Method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in illumination environment Download PDFInfo
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
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- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Abstract
The invention discloses a method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene under an illumination environment, which comprises the following synthesis steps: (1) introducing 1,1,1,4,4, 4-hexafluorobutane and chlorine into a reactor, wherein the molar ratio of the chlorine to the 1,1,1,4,4, 4-hexafluorobutane is 0.5-1.5: 1, performing photochlorination in an illumination environment, the reaction temperature is 10-90 ℃, the reaction residence time is 10-100 s, and obtaining an intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane after water washing and alkali washing; (2) and (2) introducing the intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor for heating reaction at the reaction temperature of 200-400 ℃ for 5-35 s, and washing with water and alkali in the presence of a catalyst to obtain the target product 1,1,1,4,4, 4-hexafluoro-2-butene. The synthesis method has the advantages of simple and easily obtained raw materials, simple process route, less pollution to reaction environment, less by-products and high yield.
Description
Technical Field
The invention relates to the field of synthesis of fluoroolefin, in particular to a preparation method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene under a lighting environment.
Background
1,1,1,4,4, 4-hexafluoro-2-butene, which is a cis isomer and a trans isomer, is a colorless and odorless gas in general, and can be used as a novel foaming agent, a refrigerant and a fire extinguishing agent. The hexafluoro-2-butene is considered as one of ideal substitutes of the foaming agent HCFC-141b, the foaming agent product is environment-friendly, has remarkable heat insulation and preservation characteristics, is nonflammable, does not consume ozone, can replace other liquid foaming agents at low conversion cost, and has wide application prospect.
Currently, 1,1,1,4,4, 4-hexafluoro-2-butene mainly has the following synthesis methods:
a method for preparing 1,1,1,4,4, 4-hexafluoro-2-butene is disclosed in U.S. Pat. No. 5, 2011288349A1, published as 2011, 11 months and 24 days, and uses hexafluoropropylene and trichloromethane as raw materials to synthesize the 1,1,1,4,4, 4-hexafluoro-2-butene. Hexafluoropropylene and trichloromethane are subjected to addition reaction to generate 1,1, 1-trichloro-2, 2,3,4,4, 4-hexafluorobutane, the 1,1,2, 2,3,4,4, 4-nonafluorobutane is obtained through fluorination, dehydrofluorination and reduction dehalogenation are carried out on the 1,1,1,4,4, 4-hexafluoro-2-butene. The synthesis method has multiple synthesis steps and complex process.
A production process of hexafluoro-2-butene, disclosed as WO2011119388A2, disclosed as 29/09/2011, adopts carbon tetrachloride and ethylene as raw materials to synthesize 1,1,1,4,4, 4-hexafluoro-2-butene. The addition reaction of carbon tetrachloride and ethylene produces 1,1,1, 4-tetrachloropropane, the dehydrochlorination of 1,1,1, 4-tetrachloropropane, the addition of 1,1,1,2,4,4, 4-heptachlorobutane and carbon tetrachloride produces 1,1,1,2,4,4, 4-heptachlorobutane, which is fluorinated and dehydrochlorinated to produce 1,1,1,4,4, 4-hexafluoro-2-butene with total yield of 69%. The synthesis method has long synthesis steps, complex process and low yield.
A production method of a fluorine-containing olefin compound is disclosed as JP2010001244, wherein the publication date is 2010, 01-month and 07-year, and 1,1, 1-trifluoro-2-bromo-2-chloroethane is adopted as a raw material to synthesize 1,1,1,4,4, 4-hexafluoro-2-butene. 1,1, 1-trifluoro-2-bromo-2-chloroethane is coupled by zinc powder to obtain 1,1,1,4,4, 4-hexafluoro-2, 3-chlorobutane, and the 1,1,1,4,4, 4-hexafluoro-2-butene is obtained by dechlorinating with zinc powder, wherein the yield is 42-69%. The synthesis method has the advantages of difficult obtainment of required raw materials and low yield.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the method for synthesizing the 1,1,1,4,4, 4-hexafluoro-2-butene under the illumination environment, which has the advantages of simple process route, less byproducts and high yield.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in a lighting environment comprises the following synthesis steps:
(1) introducing 1,1,1,4,4, 4-hexafluorobutane and chlorine into a reactor, wherein the molar ratio of the chlorine to the 1,1,1,4,4, 4-hexafluorobutane is 0.5-1.5: 1, performing photochlorination in an illumination environment, the reaction temperature is 10-90 ℃, the reaction residence time is 10-100 s, and obtaining an intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane after water washing and alkali washing;
(2) and (2) introducing the intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor for heating reaction at the reaction temperature of 200-400 ℃ for 5-35 s, and washing with water and alkali in the presence of a catalyst to obtain the target product 1,1,1,4,4, 4-hexafluoro-2-butene.
Preferably, the lighting environment in the step (1) is a long-wave ultraviolet light source or a low-pressure steam mercury lamp or a near ultraviolet fluorescent lamp.
Preferably, the long-wave ultraviolet light source is a long-wave ultraviolet lamp, an ultraviolet high-pressure mercury lamp, an ultraviolet xenon lamp or an ultraviolet metal halide lamp.
Preferably, in the step (1), the molar ratio of the chlorine gas to the 1,1,1,4,4, 4-hexafluorobutane is 0.8-1.1: 1, the reaction temperature is 30-60 ℃, the reaction residence time is 30-50 s, and in the step (2), the reaction temperature is 250-350 ℃ and the reaction residence time is 8-15 s.
Preferably, the catalyst in the step (2) is a supported catalyst, the carrier is activated carbon or fluorinated activated carbon or silica or molecular sieve or alumina or magnesium fluoride or aluminum fluoride or calcium fluoride, and the loading amount of the metal chloride is 0.2-3% of the total weight of the catalyst.
Preferably, the catalyst is CoCl3C orNiCl2/C or CsCl/C or ZnCl2/MgF2Or BaCl2/MgF2Or KCl/MgF2Or PdCl2/MgF2One or a combination mixture of two or more of them.
Preferably, the loading amount of the metal chloride is 0.5-2% of the total weight of the catalyst.
The invention has the beneficial effects that: the synthesis method disclosed by the invention has the advantages of simple and easily-obtained required raw materials, energy conservation and environmental protection due to the adoption of a lighting environment, simple process route, less pollution to the reaction environment, less byproducts and high yield.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in a lighting environment comprises the following synthesis steps:
(1) introducing chlorine and 1,1,1,4,4, 4-hexafluorobutane into a quartz glass reactor according to a molar ratio of 1:1, allowing the reaction to stay for 30s, adopting an ultraviolet xenon lamp as a light source, controlling the reaction temperature to be 50 ℃, after reacting for 30min, washing with water and alkali to obtain an intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane, sampling, and analyzing by GC, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluorobutane is 48.3%, and the selectivity of the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane is 96.5%;
(2) introducing the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor, wherein the catalyst is BaCl2/MgF2，BaCl2The loading amount is 0.2 percent of the total weight of the catalyst, the reaction temperature is 300 ℃, the retention time is 10s, after the reaction is carried out for 1h, the target product 1,1,1,4,4, 4-hexafluoro-2-butene is obtained by water washing and alkali washing, the sample is taken, the GC analysis shows that the conversion rate of the 2-chloro-1, 1,1,4,4, 4-hexafluoro-butane is 65.8 percent, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butene is 65 percent94.2％。
Example 2
A method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in a lighting environment comprises the following synthesis steps:
(1) introducing chlorine and 1,1,1,4,4, 4-hexafluorobutane into a quartz glass reactor in a molar ratio of 0.5:1, keeping the reaction time for 10s, adopting a low-pressure vapor mercury lamp as a light source, controlling the reaction temperature to be 10 ℃, after reacting for 30min, washing with water and alkali to obtain an intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane, sampling, and analyzing by GC, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluorobutane is 47.2 percent, and the selectivity of the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane is 95.7 percent;
(2) introducing the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor, wherein the catalyst is CoCl3Mixtures of/C and CsCl/C, CoCl3And CsCl loading is 0.5 percent of the total weight of the catalyst, the reaction temperature is 200 ℃, the retention time is 8s, after the reaction is carried out for 1h, the target product 1,1,1,4,4, 4-hexafluoro-2-butene is obtained through water washing and alkali washing, sampling is carried out, and the conversion rate of 2-chloro-1, 1,1,4,4, 4-hexafluoro-butane is 65.8 percent and the selectivity of 1,1,1,4,4, 4-hexafluoro-2-butene is 94.2 percent through GC analysis.
Example 3
A method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in a lighting environment comprises the following synthesis steps:
(1) introducing chlorine and 1,1,1,4,4, 4-hexafluorobutane into a quartz glass reactor in a molar ratio of 0.8:1, keeping the reaction time for 100s, adopting a near ultraviolet fluorescent lamp as a light source, controlling the reaction temperature to be 90 ℃, after reacting for 30min, washing with water and alkali to obtain an intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane, sampling, and analyzing by GC, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluorobutane is 48.8 percent, and the selectivity of the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane is 96.7 percent;
(2) introducing the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor, wherein the catalyst is NiCl2/C，NiCl2The loading amount is 2 percent of the total weight of the catalyst, the reaction temperature is 400 ℃, the retention time is 15s, after the reaction is carried out for 1h, the target product 1,1,1,4,4, 4-hexafluoro-2-one-wall material is obtained by water washing and alkali washingButene was sampled and analyzed by GC with 65.8% conversion of 2-chloro-1, 1,1,4,4, 4-hexafluorobutane and 94.2% selectivity to 1,1,1,4,4, 4-hexafluoro-2-butene. .
Example 4
A method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in a lighting environment comprises the following synthesis steps:
(1) introducing chlorine and 1,1,1,4,4, 4-hexafluorobutane into a quartz glass reactor according to a molar ratio of 1.1:1, keeping the reaction time for 50s, adopting a long-wave ultraviolet lamp as a light source, controlling the reaction temperature to be 30 ℃, after reacting for 30min, washing with water and alkali to obtain an intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane, sampling, and analyzing by GC, wherein the conversion rate of the 1,1,1,4,4, 4-hexafluorobutane is 48.3 percent, and the selectivity of the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane is 96.5 percent;
(2) introducing the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor, wherein the catalyst is ZnCl2/MgF2，ZnCl2The loading amount is 3% of the total weight of the catalyst, the reaction temperature is 250 ℃, the retention time is 5s, after the reaction is carried out for 1h, the target product 1,1,1,4,4, 4-hexafluoro-2-butene is obtained through water washing and alkali washing, a sample is taken, the conversion rate of 2-chloro-1, 1,1,4,4, 4-hexafluoro-butane is 65.8% through GC analysis, and the selectivity of 1,1,1,4,4, 4-hexafluoro-2-butene is 94.2%.
Example 5
A method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in a lighting environment comprises the following synthesis steps:
(1) introducing chlorine and 1,1,1,4,4, 4-hexafluorobutane into a quartz glass reactor according to a molar ratio of 1:1, wherein the reaction residence time is 40s, a light source adopts an ultraviolet metal halide lamp, the reaction temperature is controlled to be 60 ℃, after reaction for 30min, the intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane is obtained through water washing and alkali washing, sampling is carried out, the conversion rate of the 1,1,1,4,4, 4-hexafluorobutane is 48.3% through GC analysis, and the selectivity of the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane is 96.5%;
(2) introducing the 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor, wherein the catalyst is KCl/MgF2And PdCl2/MgF2The mixture of (a) and (b),KCl and PdCl2The loading amount is 1.5 percent of the total weight of the catalyst, the reaction temperature is 350 ℃, the retention time is 35s, after the reaction is carried out for 1h, the target product 1,1,1,4,4, 4-hexafluoro-2-butene is obtained by water washing and alkali washing, a sample is taken, the conversion rate of the 2-chloro-1, 1,1,4,4, 4-hexafluoro-butane is 65.8 percent by GC analysis, and the selectivity of the 1,1,1,4,4, 4-hexafluoro-2-butene is 94.2 percent
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (7)
1. A method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in a lighting environment is characterized in that: the method comprises the following synthetic steps:
(1) introducing 1,1,1,4,4, 4-hexafluorobutane and chlorine into a reactor, wherein the molar ratio of the chlorine to the 1,1,1,4,4, 4-hexafluorobutane is 0.5-1.5: 1, performing photochlorination in an illumination environment, the reaction temperature is 10-90 ℃, the reaction residence time is 10-100 s, and obtaining an intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane after water washing and alkali washing;
(2) and (2) introducing the intermediate product 2-chloro-1, 1,1,4,4, 4-hexafluorobutane obtained in the step (1) into a tubular reactor for heating reaction at the reaction temperature of 200-400 ℃ for 5-35 s, and washing with water and alkali in the presence of a catalyst to obtain the target product 1,1,1,4,4, 4-hexafluoro-2-butene.
2. The method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in the illumination environment according to claim 1, wherein: the illumination environment in the step (1) is a long-wave ultraviolet light source or a low-pressure vapor mercury lamp or a near ultraviolet fluorescent lamp.
3. The method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in the illumination environment according to claim 2, wherein: the long-wave ultraviolet light source is a long-wave ultraviolet lamp or an ultraviolet high-pressure mercury lamp or an ultraviolet xenon lamp or an ultraviolet metal halide lamp.
4. The method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in the illumination environment according to claim 1, wherein: the mol ratio of the chlorine to the 1,1,1,4,4, 4-hexafluorobutane in the step (1) is 0.8-1.1: 1, the reaction temperature is 30-60 ℃, the reaction residence time is 30-50 s, and the reaction temperature in the step (2) is 250-350 ℃, and the reaction residence time is 8-15 s.
5. The method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in the illumination environment according to claim 1, wherein: the catalyst in the step (2) is a supported catalyst, the carrier is activated carbon or fluorinated activated carbon or silicon dioxide or molecular sieve or alumina or magnesium fluoride or aluminum fluoride or calcium fluoride, and the loading amount of the metal chloride is 0.2-3% of the total weight of the catalyst.
6. The method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in the illumination environment according to claim 5, wherein: the catalyst is CoCl3C or NiCl2/C or CsCl/C or ZnCl2/MgF2Or BaCl2/MgF2Or KCl/MgF2Or PdCl2/MgF2One or a combination mixture of two or more of them.
7. The method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in the illumination environment according to claim 5, wherein: the loading amount of the metal chloride is 0.5-2% of the total weight of the catalyst.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981686A (en) * | 2019-12-31 | 2020-04-10 | 中国船舶重工集团公司第七一八研究所 | Preparation method and preparation device of 1,1,2, 2-tetradeuteroethylene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7829748B1 (en) * | 2009-09-21 | 2010-11-09 | Honeywell International Inc. | Process for the manufacture of 1,3,3,3-tetrafluoropropene |
| CN103172489A (en) * | 2013-03-14 | 2013-06-26 | 巨化集团技术中心 | Synthesis method of 1,1,1,4,4,4-hexafluorine-2-butene |
| CN104370690A (en) * | 2014-11-20 | 2015-02-25 | 西安近代化学研究所 | Synthetic method of trans-1, 1, 1, 4, 4, 4-hexafluoro-2-butene |
| CA3068057A1 (en) * | 2017-07-27 | 2019-01-31 | The Chemours Company Fc, Llc | Process for preparing (z)-1,1,1,4,4,4-hexafluoro-2-butene |
-
2019
- 2019-09-24 CN CN201910903487.7A patent/CN110590494A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7829748B1 (en) * | 2009-09-21 | 2010-11-09 | Honeywell International Inc. | Process for the manufacture of 1,3,3,3-tetrafluoropropene |
| CN103172489A (en) * | 2013-03-14 | 2013-06-26 | 巨化集团技术中心 | Synthesis method of 1,1,1,4,4,4-hexafluorine-2-butene |
| CN104370690A (en) * | 2014-11-20 | 2015-02-25 | 西安近代化学研究所 | Synthetic method of trans-1, 1, 1, 4, 4, 4-hexafluoro-2-butene |
| CA3068057A1 (en) * | 2017-07-27 | 2019-01-31 | The Chemours Company Fc, Llc | Process for preparing (z)-1,1,1,4,4,4-hexafluoro-2-butene |
Non-Patent Citations (2)
| Title |
|---|
| 吴世清: "1种1,1,1,4,4,4-六氟-2-丁烯的合成方法", 《化工生产与技术》 * |
| 彭银仙，等: "《化学工艺学》", 31 July 2018 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981686A (en) * | 2019-12-31 | 2020-04-10 | 中国船舶重工集团公司第七一八研究所 | Preparation method and preparation device of 1,1,2, 2-tetradeuteroethylene |
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