CN101851146B - Method for preparing trifluoroethylene - Google Patents
Method for preparing trifluoroethylene Download PDFInfo
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- CN101851146B CN101851146B CN 200910097504 CN200910097504A CN101851146B CN 101851146 B CN101851146 B CN 101851146B CN 200910097504 CN200910097504 CN 200910097504 CN 200910097504 A CN200910097504 A CN 200910097504A CN 101851146 B CN101851146 B CN 101851146B
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Abstract
The invention discloses a method for preparing trifluoroethylene. The method comprises the following steps of: in the presence of an organic solvent, performing a reaction on 1,1-dibromotetrafluoroethane and a metal dehalogenation agent to obtain a trifluoromethyl vinyl-bromide organic metal reagent; and adding water into the trifluoromethyl vinyl-bromide organic metal reagent dropwise so as to prepare a trifluoroethylene gas. The trifluoroethylene is an important high molecular monomer; and a functional high molecular fluoropolymer obtained by copolymerizing the trifluoroethylene serving as a main body and polyvinylidene fluoride has an unusual piezoelectric property and wide application on an aspect of synthesizing human organs. In addition, the trifluoroethylene is also an import intermediate for synthesizing a plurality of other compounds.
Description
Technical field
The present invention relates to a kind of method for preparing trifluoro-ethylene, particularly is the method for feedstock production trifluoro-ethylene with 1,2-dibromotetrafluoroethane.
Background technology
Trifluoro-ethylene is not only a kind of important high polymer monomer, but also is the important intermediate of synthetic other chemical compound lot.Be that the functional polymer fluoropolymer that main body and vinylidene fluoride copolymerization obtain has unusual piezoelectricity (electrostriction) characteristic with the trifluoro-ethylene, thereby aspect the synthesized human organ extensive use arranged; Trifluoro-ethylene and anhydrous hydrogen fluoride addition can obtain environment friendly refrigerating fluid Tetrafluoroethane (HFC-134a), it as the important alternative articles for use of Refrigerant 12 in equipment such as refrigerator refrigeration and automative air conditioning should be very extensive; Trifluoro-ethylene and ethanol polycondensation can make environment-friendly cleaning agent fluorine hydrogen ether; Trifluoro-ethylene and bromine addition, and then dehydrobromination just can obtain trifluoro bromine ethene, it also is an important high polymer monomer; Trifluoro-ethylene also is the important source material of high-grade pure cotton fabric finishing composition simultaneously.
In the 60 to 70's of last century, external many investigators propose the technology of Freon 113 (CFC-113) catalytic hydrogenation and dechlorination trifluorochloroethylene processed and coproduction trifluoro-ethylene, and it is main active component that catalyzer adopts precious metal.This technology CFC-113 transformation efficiency only is 20%-30%, and the trifluoro-ethylene poor selectivity is difficult to obtain high-quality trifluoro-ethylene product, and activity of such catalysts and life-span are all undesirable.In addition, because the lower and easy polymerization reaction take place of boiling point of product trifluoro-ethylene and trifluorochloroethylene adopts this technology also to have collection and the separation and purification problem of product simultaneously.
Adopt trifluorochloroethylene for what the catalytic material hydrodechlorination prepared trifluoro-ethylene technology US Patent No. 5089454, US2802887 and US3564064 and Japanese Patent etc. to be arranged, adopting the VIII metal is the catalyzer main active component, though make the yield of trifluoro-ethylene be greatly improved, exist catalyst life weak point, product to be difficult to collect and separate the purification problem.
French Patent FR2710054 and FR2729136 have reported the operational path for preparing trifluoro-ethylene with 1,1,1,2-Tetrafluoroethane (HFC-134a) for the catalytic material dehydrofluorination.This technology translation condition harshness, the HFC-134a transformation efficiency is low, and product trifluoro-ethylene yield is low.
Japanese Patent JP57026629 has reported the technology for preparing trifluoro-ethylene with 1,1,2-, three fluoro-2-chloro-1-monobromethanes for the raw material dehalogenation.This technological reaction raw material is not easy to obtain, and quantity of three wastes is big.
US Patent No. 5892135 reports are with CF
3CClFX (X is H, Cl or F) is raw material, mainly is HCFC-124, with metal Ru, and Cu, Ni, one or more in Cr or their metal oxide or the halogenide are catalyzer, the technology of preparation trifluoro-ethylene.Temperature of reaction requires high, and about 325-425 ℃, and the easy inactivation of catalyzer, also exist product to be difficult to collect and the separation and purification problem simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method of produced in high yields trifluoro-ethylene, conversion rate of products, selectivity height, technology is simple, the reaction conditions gentleness, product separates purifies simply.
For achieving the above object, the present invention takes following technical proposals:
In the presence of organic solvent, make 1 earlier, 1-dibromotetrafluoroethane and the reaction of metal agent generate trifluoro vinyl bromide organometallic reagent, make trifluoro-ethylene gas to wherein dripping water again.
Described raw material 1, the 1-dibromotetrafluoroethane can obtain by purchase.The present invention so long as water may be used to the present invention, but is preferably deionized water to the not also not requirement of described raw water.
The metal agent is the metal that can be used in the dehalogenation reaction or metallic compound, complex compound, inner complex, coordination thing etc.The preferred metal agent of the present invention is metallic zinc, and its shape can be bar-shaped, ingot shape, Powdered or particulate state etc., the preferred powder powder.
The used metallic zinc of the present invention can obtain by purchase, and the metallic zinc through buying can be directly used in this reaction, also can be by being used for the present invention after the activation treatment, preferably pass through the metallic zinc after the activation treatment.
Can use acid that metallic zinc is carried out activation treatment, remove thoroughly for the oxide compound and the dirt that make the metallic zinc surface, the acid that preferred concentration is high is as concentrated hydrochloric acid, concentrated nitric acid or the vitriol oil etc.
The activating treatment process that metal is commonly used all can be used for the present invention.The activating treatment process of the preferred metallic zinc of the present invention is, zinc powder is scattered in the deionized water, add concentrated hydrochloric acid while stirring, when treating that zinc powder presents silvery white solution is filtered, filter cake is successively with deionization, acetone and ether flushing, filter cake is placed in the vacuum drying oven then and under 40～100 ℃ of temperature, dry by the fire 5～7h, place the interior preservation of moisture eliminator standby at last.
The used organic solvent of the present invention is preferably non-proton type polar solvent, and non-proton type polar solvent is preferably one or more combinations that are selected from acid amides, ether, nitrile, sulfoxide and the ketone.The preferred N of described acid amides, dinethylformamide (DMF) and/or N,N-dimethylacetamide, described ether is preferably 1,4-dioxane and/or tetrahydrofuran (THF), and described nitrile is preferably acetonitrile and/or propionitrile, described sulfoxide is preferably methyl-sulphoxide, and described ketone is preferably N-Methyl pyrrolidone.
Organic solvent and 1 among the present invention, the mass ratio of 1-dibromotetrafluoroethane only need satisfy can make reaction get final product, and carries out preferred organic and 1 smoothly rapidly for making reaction, the mass ratio of 1-dibromotetrafluoroethane is 0.5: 1～5.5: 1, further preferred 1: 1～3: 1.Feed metal agent and 1, the add-on of 1-dibromotetrafluoroethane also only needs to satisfy reaction is got final product, and carries out preferred metal agent and 1 smoothly rapidly for making reaction, the mol ratio of 1-dibromotetrafluoroethane is 1: 1～5: 1, further preferred 2: 1～3.5: 1.
Generate in the reaction of trifluoro vinyl bromide organometallic reagent at 1,1-dibromotetrafluoroethane and the reaction of metal agent, reaction system preferably keeps dry.This reactions steps is preferably in the environment of anaerobic carries out, and can use rare gas element to replace for making the reaction system anaerobic, and the more common rare gas element that is easy to get is nitrogen.
When dropping water made trifluoro-ethylene gas in trifluoro vinyl bromide organometallic reagent, reaction system preferably kept vacuum, so that the trifluoro-ethylene gas purity of collecting is higher.
The present invention also provides a kind of preparation technology of trifluoro-ethylene, comprising:
(1) earlier with rare gas element with air displacement in the reactor totally;
(2) drop into metal agent and organic solvent;
(3) reactor heating makes the interior solution of reactor reach the temperature that is suitable for reacting, and adds 1,1-dibromotetrafluoroethane, and remains on the temperature that is suitable for reacting, and continues reaction;
(4) after question response finishes, reactor cooling to room temperature, and is vacuumized reactor;
(5) in reactor, add water, collect the trifluoro-ethylene gas that generates.
When with rare gas element with reactor in air displacement totally after, preferably reactor is remained under the atmosphere of inert gases.Rare gas element commonly used is nitrogen.
Reactor heating makes the interior solution of reactor reach the temperature that is suitable for reacting can add 1,1-dibromotetrafluoroethane, and preferably reaching the temperature that is suitable for reacting is 30～90 ℃, more preferably 50～70 ℃.After adding 1,1-dibromotetrafluoroethane, only need that solution temperature in the reactor is remained on the temperature that is suitable for reacting and get final product, be preferably 50～90 ℃, more preferably 70～90 ℃.Preferably keep temperature in the reactor when adding water in step (5) about room temperature～30 ℃, the adding mode of water also preferably adopts the form that drips, and water preferably adopts deionized water.
For making reaction be unlikely to too violent, be preferably in the mixing solutions that adds 1,1-dibromotetrafluoroethane and organic solvent in the step (3), and adopt the feed way that drips with the control speed of response, temperature of reaction is preferably controlled be no more than 90 ℃.General common organic solvent all can be used, and preferred organic is non-proton type polar solvent, and non-proton type polar solvent is preferably one or more combinations that are selected from acid amides, ether, nitrile, sulfoxide and the ketone.The preferred N of described acid amides, dinethylformamide (DMF) and/or N,N-dimethylacetamide, described ether is preferably 1,4-dioxane and/or tetrahydrofuran (THF), and described nitrile is preferably acetonitrile and/or propionitrile, described sulfoxide is preferably methyl-sulphoxide, and described ketone is preferably N-Methyl pyrrolidone.
When 1,1-dibromotetrafluoroethane and the reaction of metal agent reaction generation trifluoro vinyl bromide organometallic reagent, the reaction times is controlled at 4-12h, preferred 5-8h.
Embodiment
Specifically describe below by the present invention of embodiment.Following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention.
The activation of embodiment 1 metallic zinc
Zinc powder 100g, be scattered in the 800mL deionized water, add the 20mL concentrated hydrochloric acid while stirring in batches, stir 20min, when treating that zinc powder presents silvery white solution is filtered, filter cake is successively with the washing of 1000mL deionization, after the drip washing of 500mL acetone and 500mL ether clean, drain filter cake, then filter cake is placed in the vacuum drying oven 60 ℃ of baking 6h after, place preserve in the moisture eliminator standby.
The preparation of embodiment 2 trifluoro-ethylenes
After 250ml there-necked flask drying treatment, feed the air in the nitrogen replacement flask, treat that the clean back of air displacement keeps flask to be in nitrogen atmosphere, drop into the about 15g of zinc powder (0.23mol) and DMF35g, heating flask to the interior solution temperature of bottle reaches 70 ℃, in flask, drip 26g (0.1mol) 1, the mixing solutions that 1-dibromotetrafluoroethane and 20gDMF are made into, keep temperature of reaction at 80～90 ℃, regulate rate of addition, temperature of reaction is remained in 90 ℃, after dropwising, make bottle interior temperature react 6h remaining on about 90 ℃, then cooling.After being down to room temperature, vacuumize, make to keep negative pressure in the reaction system, when being 30 ℃, temperature of reaction drips deionized water 50g, and airbag is collected gas, obtains 4.0g gas, and trifluoro propene purity is 98.6%, productive rate 48.7%, selectivity is 98.6%.
The preparation of embodiment 3 trifluoro-ethylenes
After 250ml there-necked flask drying treatment, feed the air in the nitrogen replacement flask, treat that the clean back of air displacement keeps flask to be in nitrogen atmosphere, drop into the about 15g of zinc powder (0.23mol) and acetonitrile 25g, heating flask to the interior solution temperature of bottle reaches 70 ℃, in flask, drip 26g (0.1mol) 1, the mixing solutions that 1-dibromotetrafluoroethane and 15g acetonitrile are made into, keep temperature of reaction at 80～90 ℃, regulate rate of addition, make temperature of reaction be no more than 90 ℃, after dropwising, make bottle interior temperature react 4h remaining on about 90 ℃, then cooling.After being down to room temperature, vacuumize, make to keep negative pressure in the reaction system, drip deionized water 50g in temperature of reaction during for room temperature, airbag is collected gas, obtains 3.1g gas, and trifluoro propene purity is 96.6%, productive rate 37.8%, selectivity is 96.6%.
The preparation of embodiment 4 trifluoro-ethylenes
After 250ml there-necked flask drying treatment, feed the air in the nitrogen replacement flask, treat that the clean back of air displacement keeps flask to be in nitrogen atmosphere, drop into the about 17g of zinc powder (0.26mol) and (N-Methyl pyrrolidone) 40g, heating flask to the interior solution temperature of bottle reaches 50 ℃, in flask, drip 26g (0.1mol) 1, the mixing solutions that 1-dibromotetrafluoroethane and N-Methyl pyrrolidone 20g are made into, keep temperature of reaction at 70～80 ℃, regulate rate of addition, make temperature of reaction be no more than 80 ℃, after dropwising, make bottle interior temperature react 5h remaining on about 80 ℃, then cooling.After being down to room temperature, vacuumize, make to keep negative pressure in the reaction system, drip deionized water 50g in temperature of reaction during for room temperature, airbag is collected gas, obtains 3.5g gas, and trifluoro propene purity is 97.9%, productive rate 42.7%, selectivity is 97.9%.
The productive rate of trifluoro-ethylene is calculated by the actual product of receiving in above-described embodiment, this shows preparation of the present invention but the method conversion rate of products height of vinyl fluoride, the selectivity height, more than 96%, the product purity height of collecting, more than 96%, technological operation is simple, the reaction conditions gentleness, product is collected simple.
Claims (17)
1. method for preparing trifluoro-ethylene, it is characterized in that in the presence of organic solvent, make 1 earlier, 1-dibromotetrafluoroethane and the reaction of metal agent generate trifluoro vinyl bromide organometallic reagent, make trifluoro-ethylene gas to wherein dripping water again, described organic solvent is non-proton type polar solvent, and described metal agent is metallic zinc, anaerobic in the reaction system.
2. according to the described method for preparing trifluoro-ethylene of claim 1, the form that it is characterized in that described metallic zinc is powdery.
3. according to the described method for preparing trifluoro-ethylene of claim 2, it is characterized in that described metallic zinc handles through acid activation.
4. according to the described method for preparing trifluoro-ethylene of claim 1, it is characterized in that described non-proton type polar solvent is selected from one or more combinations in acid amides, ether, nitrile, sulfoxide and the ketone.
5. according to the described method for preparing trifluoro-ethylene of claim 4, it is characterized in that described acid amides is N, dinethylformamide (DMF) and/or N, the N-N,N-DIMETHYLACETAMIDE, described ether is 1,4-dioxane and/or tetrahydrofuran (THF), and described nitrile is acetonitrile and/or propionitrile, described sulfoxide is methyl-sulphoxide, and described ketone is N-Methyl pyrrolidone.
6. according to the described method for preparing trifluoro-ethylene of claim 1, the mass ratio that it is characterized in that described organic solvent and 1,1-dibromotetrafluoroethane is 0.5: 1～5.5: 1.
7. according to the described method for preparing trifluoro-ethylene of claim 6, the mass ratio that it is characterized in that described organic solvent and 1,1-dibromotetrafluoroethane is 1: 1～3: 1.
8. according to the described method for preparing trifluoro-ethylene of claim 1, the mol ratio that it is characterized in that described metal agent and 1,1-dibromotetrafluoroethane is 1: 1～5: 1.
9. according to the described method for preparing trifluoro-ethylene of claim 8, the mol ratio that it is characterized in that described metal agent and 1,1-dibromotetrafluoroethane is 2: 1～3.5: 1.
10. method for preparing trifluoro-ethylene is characterized in that:
(1) earlier with rare gas element with air displacement in the reactor totally;
(2) drop into metal agent and organic solvent, described metal agent is metallic zinc, and described organic solvent is non-proton type polar solvent;
(3) reactor heating makes the interior solution of reactor reach the temperature that is suitable for reacting, and adds 1,1-dibromotetrafluoroethane, and remains on the temperature that is suitable for reacting, and continues reaction;
(4) after question response finishes, reactor cooling to room temperature, and is vacuumized reactor;
(5) in reactor, add water, collect the trifluoro-ethylene gas that generates.
11. according to the described method for preparing trifluoro-ethylene of claim 10, it is characterized in that in the described step (1) with rare gas element with air displacement in the reactor totally after, keep reactor to be in atmosphere of inert gases.
12. according to the described method for preparing trifluoro-ethylene of claim 10, it is characterized in that reaching the temperature that is suitable for reacting in the described step (3) is 30-90 ℃, remaining on the temperature that is suitable for reacting is 50～90 ℃.
13. according to the described method for preparing trifluoro-ethylene of claim 12, it is characterized in that reaching the temperature that is suitable for reacting in the described step (3) is 50～70 ℃, remaining on the temperature that is suitable for reacting is 70-90 ℃.
14. according to the described method for preparing trifluoro-ethylene of claim 10, it is characterized in that keeping in the described step (5) temperature in the reactor in room temperature～30 ℃.
15. according to the described method for preparing trifluoro-ethylene of claim 10, it is characterized in that adding in the described step (3) mixing solutions of 1,1-dibromotetrafluoroethane and organic solvent.
16. according to the described method for preparing trifluoro-ethylene of claim 10, it is characterized in that continuing the reaction times in the described step (3) is 4-12h.
17. according to the described method for preparing trifluoro-ethylene of claim 16, it is characterized in that the described continuation reaction times is 5-8h.
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| CN102267866B (en) * | 2011-05-05 | 2013-11-27 | 浙江师范大学 | Preparation method for trifluoroethylene and tetrafluoroethane |
| CN102372593A (en) * | 2011-11-09 | 2012-03-14 | 常熟三爱富中昊化工新材料有限公司 | Method for preparing trichloroethylene |
| BR112015025238A2 (en) * | 2013-04-30 | 2017-07-18 | Asahi Glass Co Ltd | trifluoroethylene containing composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2340588C2 (en) * | 2006-11-15 | 2008-12-10 | Общество с ограниченной ответственностью Научно-внедренческая фирма "Окта" | Method of obtaining hexafluorobutadiene |
| CN101861322A (en) * | 2007-11-20 | 2010-10-13 | 纳幕尔杜邦公司 | Synthesis of hydrofluoroalkanols and hydrofluoroalkenes |
| CN102372593A (en) * | 2011-11-09 | 2012-03-14 | 常熟三爱富中昊化工新材料有限公司 | Method for preparing trichloroethylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5726629A (en) * | 1980-07-23 | 1982-02-12 | Daikin Ind Ltd | Preparation of trifluoroethylene |
| JP2001114710A (en) * | 1999-10-19 | 2001-04-24 | Daikin Ind Ltd | Method for producing hexafluorobutadiene |
| WO2008053811A1 (en) * | 2006-11-01 | 2008-05-08 | Daikin Industries, Ltd. | Method for producing olefin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2340588C2 (en) * | 2006-11-15 | 2008-12-10 | Общество с ограниченной ответственностью Научно-внедренческая фирма "Окта" | Method of obtaining hexafluorobutadiene |
| CN101861322A (en) * | 2007-11-20 | 2010-10-13 | 纳幕尔杜邦公司 | Synthesis of hydrofluoroalkanols and hydrofluoroalkenes |
| CN102372593A (en) * | 2011-11-09 | 2012-03-14 | 常熟三爱富中昊化工新材料有限公司 | Method for preparing trichloroethylene |
Non-Patent Citations (2)
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| JP昭57-26629A 1982.02.12 |
| JP特开2001-114710A 2001.04.24 |
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