CN104844411B - A kind of method for synthesizing the butadiene of hexafluoro 1,3 - Google Patents
A kind of method for synthesizing the butadiene of hexafluoro 1,3 Download PDFInfo
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- CN104844411B CN104844411B CN201510157823.XA CN201510157823A CN104844411B CN 104844411 B CN104844411 B CN 104844411B CN 201510157823 A CN201510157823 A CN 201510157823A CN 104844411 B CN104844411 B CN 104844411B
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Abstract
The present invention relates to " method of one kind synthesis butadiene of hexafluoro 1,3 ", belong to organic chemical synthesis field.The method of the butadiene of synthesis hexafluoro 1,3 is：HFC-134a (HFC 134a) dehydrofluorination under catalyst action generates trifluoro-ethylene.Then, trifluoro-ethylene reacts rapidly the HFC-143a of 1,2 dibromo of generation 1,1,2 with bromine, then dehydrobromination obtains bromotrifluoroethylene in the basic conditions.Bromotrifluoroethylene and activated zinc powder, N, N dimethylformamides reaction generation trifluoro vinyl zinc, trifluoro vinyl zinc is in Fe3+In the presence of occur coupled reaction generation the butadiene of hexafluoro 1,3.After reaction, solvent can be recycled.Raw material of the present invention is cheap, source facility；Catalyst stability is good, service life is long；Product separating-purifying is simple；It is easy to industrialized production.
Description
Technical field
The present invention is a kind of method for synthesizing hexafluoro -1,3-butadiene, is related to a kind of easy industrial method synthesis hexafluoro -1,
The method of 3- butadiene.
Background technology
Hexafluoro -1,3-butadiene has very high industrial value, is a kind of widely used raw material of industry, downstream product
Available for precise electronic pcb cleaning agent, agricultural chemical insecticide, while being closed in fluoride-containing PMMAs such as fluorine-containing medicines intermediates
There is higher application value into aspect.In terms of fluoro containing polymerses synthesis, it can prepare poly- hexafluoro as high polymer monomer
Butadiene, can also synthesize fluorine-containing rubber and the resin of excellent electrical properties with other monomers.At present test result indicates that, hexafluoro-
1,3- butadiene has huge application potential in terms of the dry etching of ultra-large integrated circuit.
At present, many researchers have carried out correlative study to the preparation method of hexafluoro -1,3-butadiene.
US2894043 reports one kind dichlorodifluoroethylene dimerization under fluorine gas and synthesizes intermediate product tetrachloro-hexafluoro fourth
Alkane, then, dechlorination obtains target product hexafluoro -1,3-butadiene in the presence of zinc powder.The shortcoming of this method is fluorination dimerization
Stage needs lower temperature and the gas fluorine gas using high-risk.
Above-mentioned technique is optimized US2676193, and feed stock conversion is 77% under optimum condition, and product yield is
87%.The reaction has four reactions steps, and it is longer, it is necessary to HTHP that the telomerisation stage expends the time, and accessory substance is more,
Difficulty is brought to product purification.In addition, catalyst SbF3Cl2Costly.
US3046304 reports a kind of process route using CTFE as Material synthesis hexafluoro-1,3-butadiene.Should
Technique avoids the condition of telomerisation HTHP, but needs stoichiometric mercury to participate in reaction, and a product is iodate in addition
Mercury, toxicity is larger.
A kind of WO2006026400 patent reports with HFC-134a and LDA (lithium diisopropylamine) are that raw material prepares six
The method of fluoro- 1,3- butadiene.In terms of HFC-134a, total recovery is between 65-70%.The technique synthesis step is simple.But,
Very expensive and active higher lithium diisopropylamine is used in reaction.Production process is abnormally dangerous, is not suitable for industrialization.
It can be seen from more than when preparing hexachlorobutadiene as raw material using four halogen perfluorinated butanes, route is long, and condition is severe
Carve, expensive iodine, poisonous fluorine gas.Equipment requirement is high, and the three wastes are more, and cost is higher.When even with trifluoro vinyl halogenation zincon
When connection prepares hexachlorobutadiene, yield is all than relatively low, or to use the reagent of difficult operation, such as LDA.These all limit six
The industrialized production of fluoroprene.
The content of the invention
The present invention seeks to the hexafluoro -1,3- fourths of high yield are prepared using simple reaction system and suitable reaction condition
Diene, raw material of the present invention is cheap, source facility；Product separating-purifying is simple；Building-up process safety, is suitable for industrialized production.
A kind of method for synthesizing hexafluoro -1,3-butadiene, comprises the following steps：
(1) HFC-134a HFC-134a gas phase dehydrofluorination generation trifluoro-ethylene CF under catalyst action2=CFH；Production
Thing mixture, which is passed through in bromine, occurs the addition reaction generation bromo- 1,1,2- HFC-143as of 1,2- bis-；
(2) the bromo- 1,1,2- HFC-143as of 1,2- bis- dehydrobromination in the presence of alkali generates bromotrifluoroethylene；
(3) bromotrifluoroethylene is with after zinc powder, DMF reaction, being directly added into Fe3+It is anti-that coupling occurs for reagent
Hexafluoro-1,3-butadiene should be generated；
The catalyst is Mg, Cr, at least one of Fe, or at least one of Mg, Cr, Fe and Bi, Ti metal
In a kind of formation compound, HFC-134a HFC-134a dehydrofluorinations generation trifluoro-ethylene CF2=CFH reaction temperatures are
100—500℃。
The HFC-134a HFC-134a dehydrofluorinations generation trifluoro-ethylene reaction temperature is 300-400 DEG C, HFC-134a
HFC-134a dehydrofluorinations generation trifluoro-ethylene reaction time of contact be：0.1—20s.
During the gas phase reaction, HFC-134a HFC-134a presses 5 with nitrogen：1 volume ratio enters reactor.
Need to be activated before the catalyst reaction, the activation process is：Cr-Mg catalyst under nitrogen protection,
Dried at a temperature of first rising to 200 DEG C with 10 DEG C/min 2 hours, then, 400 DEG C of dryings 2 hours risen to 10 DEG C/min speed,
Then, 330 DEG C are cooled to, then passes to hydrogen fluoride HF gas activations catalyst 2 hours.
Alkali in the step (2) is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus
In one kind or its combination.
Described (3) step operation process is：A) the N,N-dimethylformamide solution stirring of zinc powder is mixed and cold
But to -70 DEG C, then the importing bromotrifluoroethylene CF into solution2=CFBr gases, keep reaction temperature to be no more than 70 DEG C, during reaction
Between 1-3 hours, B) at -10 DEG C -10 DEG C, by Fe3+The N,N-dimethylformamide solution of reagent adds A) reactant mixture
In, react 1-3 hours, collect product gas.
Bromotrifluoroethylene in the step (3)：Zn：Fe3+Mol ratio is 1：1：0.5.
The Fe3+Reagent is anhydrous ferric chloride or anhydrous ferric bromide.
The zinc powder is using preceding needing to activate, and the activation method is：Zn powder is washed with 10% hydrochloric acid, then with third
Ketone is washed, filtering, and 150 DEG C dry 3 hours.
Also include the recycling step of solvent after the step (3).
The application is using raw material is cheap, originate easily HFC-134a (HFC-134a).HFC-134a (HFC-134a) exists
Dehydrofluorination generates trifluoro-ethylene under catalyst action.Then, bromine and trifluoro-ethylene reaction generation 1,2- bis- bromo- 1,1,2- tri-
Fluoroethane.1,2- bis- bromo- 1,1,2- HFC-143a generates bromotrifluoroethylene in the presence of alkali, then with zinc powder, N, N- dimethyl
Formamide, Fe3+Generation coupling reaction obtains product.The application method reactor product yield is high, and product separating-purifying is simple, synthesis
Process safety, and catalyst is partially suitable, solvent can be recycled, and be particularly suitable for use in industrialized production.
The total process of synthesis technique of the present invention is：
Beneficial effects of the present invention are as follows：
1. raw material of the present invention is cheap, source facility.
2. catalyst stability is good, repeatable recycling.
3. solvent can be recycled.
4. product separating-purifying is simple.
5. building-up process is safe, it is suitable for industrialized production
Specific embodiment
Below by way of the description of embodiment, the invention will be further described, but this is not the limit to the present invention
System, those skilled in the art are according to the basic thought of the present invention, and various modifications may be made or improves, but without departing from this
The basic thought of invention, within the scope of the present invention.
Embodiment 1
(1) 20ml Cr-Mg catalyst is loaded into fixed bed reactors.Catalyst is under the protection of 50ml nitrogen, first with 10
DEG C/min dries 2 hours at a temperature of rising to 200 DEG C, then, 400 DEG C of dryings 2 hours is risen to 10 DEG C/min speed, then,
It is cooled to 330 DEG C, then passes to 50ml/min hydrogen fluoride (HF) gas activation catalyst 2 hours.So complete catalyst
Activation process.
Reactor is heated to 350 DEG C, then, 50ml/min HFC-134as and 10ml/min nitrogen enter hybrid chamber together
It is well mixed.Afterwards, by reactor until surge flask, washing bottle, high alkali liquid, bromine absorption cell, are tested after terminating, product master
It is distributed in cooling collector.The product being collected into is subjected to GC analyses.GC results are shown, 95.0%1,2- are contained in product
Two bromo- 1,1,2- HFC-143as.Because trifluoro-ethylene and bromine react very fast, in order to shorten reaction scheme.HFC-134a with
Catalyst reaction deviates from HF, generates trifluoro-ethylene.Then, the reaction product directly passes through bromine absorption cell.So reaction terminates
Afterwards, bromine absorption cell color fade.
(2) in 150ml three-necked flasks, addition above-mentioned 1, the 2- bis- bromo- 1 of 32.7g, 1,2- HFC-143a mixture [liquid,
46 degree or so of boiling point].10% sodium hydroxide ethanol solution is added thereto, until no longer producing gas.Product is collected into altogether
14.4g.GC results show that wherein bromotrifluoroethylene content is 98.0%.
(3) in 150ml three-necked flasks, 2.0g zinc powders, 47.0g DMFs, using ethanol liquid nitrogen are added
Mixture controlling reaction temperature is -70 DEG C or so, and the rotating speed of magnetic stirring apparatus is 200r/min.After stirring 2 hours, lead thereto
Enter 6.4g bromotrifluoroethylenes.Then ethanol nitrogen mixture is removed, the reactant temperature in three-necked flask is controlled using ice-water bath
Degree is within 70 DEG C.After stirring 2 hours, the DMF solution of 21.6g anhydrous ferric chlorides is added dropwise thereto.This is molten
Liquid 5.4g containing anhydrous ferric chloride.Temperature of charge in three-necked flask is kept to be in 0 DEG C or so.The rotating speed of magnetic stirring apparatus is
100r/min.Strict control reactor internal pressure, makes it slowly successively decrease, until 100mTorr simultaneously.Gaseous products collect to
Condensing collector.React after a few hours, until the weight of condensing collector is not further added by.After reaction terminates, 1.54g is collected into altogether
Organic matter.GC analysis results show, wherein 87.0% is hexafluoro -1,3-butadiene.In terms of bromotrifluoroethylene, yield is
56.0%.
Embodiment 2
(1) 20ml Cr-Fe-Zn catalyst is loaded into fixed bed reactors, fixed bed reactors are heated with open-type pipe
Stove heat.Catalyst is dried 2 hours, then, with 10 under the protection of 50ml nitrogen at a temperature of first rising to 200 DEG C with 10 DEG C/min
DEG C/min speed rises to 400 DEG C of dryings 2 hours, then, is cooled to 330 DEG C, then pass to 50ml/min hydrogen fluoride (HF) gas
Body activated catalyst 2 hours.So complete the activation process of catalyst.
Reactor is heated to 350 DEG C, then, 50ml/min HFC-134as and 10ml/min nitrogen enter hybrid chamber together
It is well mixed.Afterwards, by reactor until surge flask, washing bottle, high alkali liquid, bromine absorption cell.After experiment terminates, product master
It is distributed in cooling collector.The product being collected into is subjected to GC analyses.GC results are shown, 90.0%1,2- are contained in product
Two bromo- 1,1,2- HFC-143as.
(2) in 150ml three-necked flasks, above-mentioned 1, the 2- bis- bromo- 1 of 41.0g, 1,2- HFC-143a mixture are added.Xiang Qi
15% carbonic acid sodium ethoxide solution of middle addition, until no longer producing gas.Product 8.5g is collected into altogether.GC results are shown, wherein three
Fluorine bromine ethylene contents are 97.0%.
(3) in 150ml three-necked flasks, 2.0g zinc powders, 47.0g DMFs, using ethanol liquid nitrogen are added
Mixture controlling reaction temperature is -70 DEG C or so, and the rotating speed of magnetic stirring apparatus is 200r/min.After stirring 2 hours, lead thereto
Enter 6.4g bromotrifluoroethylenes.Then ethanol nitrogen mixture is removed, the reactant temperature in three-necked flask is controlled using ice-water bath
Degree is within 70 DEG C.After stirring 2 hours, the DMF solution of 21.6g anhydrous ferric chlorides is added dropwise thereto.This is molten
Liquid 5.4g containing anhydrous ferric chloride.Three-necked flask internal-response thing temperature is kept to be in 0 DEG C or so.The rotating speed of magnetic stirring apparatus is
100r/min.Strict control reactor internal pressure, makes it slowly successively decrease, until 100mTorr simultaneously.Gaseous products collect to
Condensing collector.After reaction 4 hours, until the weight of condensing collector is not further added by.After reaction terminates, 1.47g is collected into altogether
Organic matter.GC analysis results show, wherein 90.0% is hexafluoro -1,3-butadiene.In terms of bromotrifluoroethylene, yield is
55.0%.
Claims (4)
1. a kind of method for synthesizing hexafluoro -1,3-butadiene, comprises the following steps：
(1) HFC-134a HFC-134a gas phase dehydrofluorination generation trifluoro-ethylene CF under catalyst action2=CFH；Product is mixed
Thing, which is passed through in bromine, occurs the addition reaction generation bromo- 1,1,2- HFC-143as of 1,2- bis-；
(2) the bromo- 1,1,2- HFC-143as of 1,2- bis- dehydrobromination in the presence of alkali generates bromotrifluoroethylene；
(3) bromotrifluoroethylene is with after zinc powder, DMF reaction, being directly added into Fe3+Coupling reaction life occurs for reagent
Into hexafluoro-1,3-butadiene；
The catalyst is Cr-Mg catalyst,
The HFC-134a HFC-134a dehydrofluorinations generation trifluoro-ethylene reaction temperature is 300-400 DEG C, HFC-134a HFC-
134a dehydrofluorinations generation trifluoro-ethylene reaction time of contact be：0.1—20s；
During the gas phase reaction, HFC-134a HFC-134a presses 5 with nitrogen：1 volume ratio enters reactor；
Need to be activated before the catalyst reaction, the activation process is：Cr-Mg catalyst under nitrogen protection, first with
10 DEG C/min is dried 2 hours at a temperature of rising to 200 DEG C, then, rises to 400 DEG C of dryings 2 hours with 10 DEG C/min speed, so
Afterwards, 330 DEG C are cooled to, then passes to hydrogen fluoride HF gas activations catalyst 2 hours；
Alkali in the step (2) is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, in saleratus
A kind of or its combination；
Described (3) step operation process is：A) mix and be cooled to the stirring of the N,N-dimethylformamide solution of zinc powder-
70 DEG C, then the importing bromotrifluoroethylene CF into solution2=CFBr gases, keep reaction temperature to be no more than 70 DEG C, reaction time 1-3
Hour, B) at -10 DEG C -10 DEG C, by Fe3+The DMF solution of reagent adds A) reactant mixture in, reaction
1-3 hours, collect product gas；
Bromotrifluoroethylene in the step (3)：Zn：Fe3+Mol ratio is 1：1：0.5.
2. according to the method described in claim 1, the Fe3+Reagent is anhydrous ferric chloride or anhydrous ferric bromide.
3. according to the method described in claim 1, the zinc powder is using preceding needing to activate, the activation method is：Zn powder is used
10% hydrochloric acid is washed, and is then washed with acetone, filtering, and 150 DEG C dry 3 hours.
4. according to the method described in claim 1, also include the recycling step of solvent after the step (3).
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| CN106380371B (en) * | 2016-08-17 | 2019-04-26 | 山东东岳化工有限公司 | A kind of method of chlorofluorocarbons resource utilization |
| CN106495982B (en) * | 2016-10-17 | 2018-09-18 | 邵武华航新材料有限公司 | A kind of method that catalysis prepares hexafluoro-1,3-butadiene |
| JP6963263B2 (en) * | 2019-12-27 | 2021-11-05 | ダイキン工業株式会社 | Method for Producing Halogenated Fluorine-Containing (Cyclo) Alkenyl Zinc Compound |
| CN111675597B (en) | 2020-06-17 | 2022-03-29 | 浙江省化工研究院有限公司 | Preparation method of hexafluoro-1,3-butadiene and intermediate thereof |
| CN114591154A (en) * | 2022-03-17 | 2022-06-07 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of tetrafluorocyclobutenyl dimethyl ether |
| CN116120146B (en) * | 2022-08-18 | 2024-01-16 | 浙江省化工研究院有限公司 | Production method and system of hexafluorobutadiene |
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| CN103288589A (en) * | 2013-06-04 | 2013-09-11 | 同济大学 | Method for co-production of trifluoroethylene and hydrogen fluoride |
| CN104475080A (en) * | 2014-11-20 | 2015-04-01 | 西安近代化学研究所 | Mesoporous chromium-oxide-based catalyst for dehydrohalogenation reaction |
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| US3046304A (en) * | 1956-09-06 | 1962-07-24 | Haszeldine Robert Neville | Coupling of halogenated organic compounds |
| WO2006033771A2 (en) * | 2004-08-26 | 2006-03-30 | Great Lakes Chemical Corporation | Chemical production processes and systems |
| CN104437567A (en) * | 2014-11-20 | 2015-03-25 | 西安近代化学研究所 | Magnesium fluoride-based catalyst and application of magnesium fluoride-based catalyst |
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| CN103288589A (en) * | 2013-06-04 | 2013-09-11 | 同济大学 | Method for co-production of trifluoroethylene and hydrogen fluoride |
| CN104475080A (en) * | 2014-11-20 | 2015-04-01 | 西安近代化学研究所 | Mesoporous chromium-oxide-based catalyst for dehydrohalogenation reaction |
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