CN104844411A - Method for synthesizing hexafluoro-1,3-butadiene - Google Patents
Method for synthesizing hexafluoro-1,3-butadiene Download PDFInfo
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Abstract
The invention relates to a method for synthesizing hexafluoro-1,3-butadiene, and belongs to the field of organic chemistry synthesis. The method for synthesizing hexafluoro-1,3-butadiene comprises the following steps: removing hydrogen fluoride from tetrafluoro ethane (HFC-134a) under the action of a catalyst to generate trifluoroethylene; rapidly reacting trifluoroethylene with liquid bromine to generate 1,2-dibromo-1,1,2-trifluoroethane, and removing hydrogen bromide under alkaline conditions to obtain trifluorobromoethylene; and reacting trifluorobromoethylene with activated zinc powder and N,N-dimethyl formamide to generate trifluorovinylzinc, and carrying out a coupling reaction on trifluorovinylzinc under the action of Fe<3+> to generate hexafluoro-1,3-butadiene. A solvent can be recovered after above reactions. The method has the advantages of low price and convenient source of raw materials, good stability and long service of the catalyst, simple separation and purification of the above product, and easy industrial production.
Description
Technical field
The present invention is a kind of method of synthesizing hexafluoro-1,3-butadiene, relates to a kind of method of easy industrial method synthesis hexafluoro-1,3-butadiene.
Background technology
Hexafluoro-1,3-divinyl has very high industrial value, and be a kind of broad-spectrum industrial raw material, its derived product can be used for precise electronic pcb cleaning agent, agricultural chemical insecticide, has higher using value simultaneously in the fluoride-containing PMMA synthesis such as fluorine-containing medicines intermediate.In fluoro containing polymers synthesis, it can as the poly-hexachlorobutadiene of high polymer monomer preparation, also can with other monomer synthesize fluorine-containing rubbers and the excellent resin of electrical property.Current experimental result shows, hexafluoro-1,3-butadiene has huge application potential in the dry etching of ultra-large integrated circuit.
At present, a lot of researchist has carried out correlative study to the preparation method of hexafluoro-1,3-butadiene.
US2894043 reports one dichlorodifluoroethylene dimerization synthetic mesophase product tetrachloro-hexafluoro butane under fluorine gas, and then, under the effect of zinc powder, dechlorination obtains target product hexafluoro-1,3-butadiene.The shortcoming of the method fluoridizes the gas fluorine gas that the dimerization stage needs lesser temps and use high-risk.
US2676193 is optimized above-mentioned technique, and under top condition, feed stock conversion is 77%, and product yield is 87%.This reaction has four reactions steps, and the telomerization stage expends time in longer, needs High Temperature High Pressure, and by product is more, and purifying to product brings difficulty.In addition, catalyst S bF
3cl
2costly.
It take trifluorochloroethylene as the operational path of Material synthesis hexafluoro-1,3-butadiene that US3046304 reports a kind of.Process avoids the condition of telomerization High Temperature High Pressure, but need stoichiometric mercury to participate in reaction, an other product is red mercury iodide, and toxicity is larger.
WO2006026400 patent reports a kind of with Tetrafluoroethane and LDA (lithium diisopropylamine) for the method for hexafluoro-1,3-butadiene prepared by raw material.In Tetrafluoroethane, total recovery is between 65-70%.This technique synthesis step is simple.But, in reaction, adopt very expensive and active higher lithium diisopropylamine.Production process is abnormally dangerous, is not suitable for industrialization.
As can be seen from above, when preparing hexachlorobutadiene with four halogen perfluorinated butanes for raw material, route is long, and condition is harsh, expensive iodine, poisonous fluorine gas.Equipment requirements is high, and the three wastes are many, and cost is higher.When preparing hexachlorobutadiene with the coupling of trifluoro vinyl zinc halide reagent, productive rate is all lower, or will use the reagent of difficult operation, as LDA etc.These all limit the suitability for industrialized production of hexachlorobutadiene.
Summary of the invention
The present invention seeks to utilize simple reaction system and applicable reaction conditions to prepare the hexafluoro-1,3-butadiene of high yield, cheaper starting materials of the present invention, source facility; Product separation is purified simple; Building-up process safety, is suitable for suitability for industrialized production.
Synthesize a method for hexafluoro-1,3-butadiene, comprise the steps:
(1) Tetrafluoroethane HFC-134a gas phase dehydrofluorination under catalyst action generates trifluoro-ethylene CF
2=CFH; Product mixtures passes in bromine and bromo-1,1, the 2-Halothane of addition reaction generation 1,2-bis-occurs;
Bromo-1,1, the 2-Halothane of (2) 1,2-bis-dehydrobromination under the effect of alkali generates bromotrifluoroethylene;
(3), after bromotrifluoroethylene and zinc powder, DMF react, directly Fe is added
3+reagent generation linked reaction generates hexafluoro-1,3-butadiene;
Described catalyzer is at least one in Mg, Cr, Fe, or the mixture of at least one in Mg, Cr, Fe and a kind of formation in Bi, Ti metal, and Tetrafluoroethane HFC-134a dehydrofluorination generates trifluoro-ethylene CF
2=CFH temperature of reaction is 100-500 DEG C.
Described Tetrafluoroethane HFC-134a dehydrofluorination generates trifluoro-ethylene temperature of reaction and is 300-400 DEG C, and the duration of contact that Tetrafluoroethane HFC-134a dehydrofluorination generates trifluoro-ethylene reaction is: 0.1-20s.
During described gas-phase reaction, Tetrafluoroethane HFC-134a and nitrogen enter reactor by 5:1 volume ratio.
Need to activate before described catalyst reaction; described reactivation process is: Cr-Mg catalyzer under nitrogen protection; first to rise at 200 DEG C of temperature dry 2 hours with 10 DEG C/min; then; 400 DEG C of dryings 2 hours are risen to the speed of 10 DEG C/min; then, be cooled to 330 DEG C, then pass to hydrogen fluoride HF gas activation catalyzer 2 hours.
Alkali in described step (2) is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, the one in saleratus or its combination.
Described (3) step operation process is: A) the DMF solution stirring of zinc powder mixed and be cooled to-70 DEG C, then import bromotrifluoroethylene CF in solution
2=CFBr gas, keeps temperature of reaction to be no more than 70 DEG C, reaction times 1-3 hour, B) at-10 DEG C-10 DEG C, by Fe
3+the DMF solution of reagent adds A) reaction mixture in, reaction 1-3 hour, collect product gas.
Bromotrifluoroethylene: Zn:Fe in described step (3)
3+mol ratio is 1:1:0.5.
Described Fe
3+reagent is Anhydrous Ferric Chloride or anhydrous iron bromide.
Described zinc powder needs activation before using, and described activation method is: Zn powder 10% hydrochloric acid washs, and then uses washing with acetone, filters, and dries 3 hours for 150 DEG C.
The recycling step of solvent is also comprised after described step (3).
The application adopts cheaper starting materials, Tetrafluoroethane (HFC-134a) easily of originating.Tetrafluoroethane (HFC-134a) dehydrofluorination under catalyst action generates trifluoro-ethylene.Then, bromine and trifluoro-ethylene react bromo-1,1, the 2-Halothane of generation 1,2-bis-.Bromo-1,1, the 2-Halothane of 1,2-bis-generates bromotrifluoroethylene under the effect of alkali, then with zinc powder, DMF, Fe
3+there is linked reaction and obtain product.The application's method reactor product yield is high, and product separation is purified simple, building-up process safety, and catalyzer is partially suitable, and solvent can be recycled, and is specially adapted to suitability for industrialized production.
The total process of synthesis technique of the present invention is:
Beneficial effect of the present invention is as follows:
1. cheaper starting materials of the present invention, source facility.
2. catalyst stability good, can recirculation use.
3. solvent can be recycled.
4. product separation is purified simple.
5. building-up process safety, is suitable for suitability for industrialized production
Concrete embodiment
Below by way of the description of embodiment, the invention will be further described, but this is not limitation of the present invention, those skilled in the art are according to basic thought of the present invention, various amendment or improvement can be made, but only otherwise depart from basic thought of the present invention, all within the scope of the present invention.
Embodiment 1
(1) 20ml Cr-Mg catalyzer is loaded fixed-bed reactor.Catalyzer, under 50ml nitrogen protection, first to rise at 200 DEG C of temperature dry 2 hours with 10 DEG C/min, then; 400 DEG C of dryings 2 hours are risen to the speed of 10 DEG C/min; then, be cooled to 330 DEG C, then pass to hydrogen fluoride (HF) the gas activation catalyzer 2 hours of 50ml/min.Complete the reactivation process of catalyzer like this.
Reactor is heated to 350 DEG C, then, 50ml/min Tetrafluoroethane enters hybrid chamber and mixes together with 10ml/min nitrogen.Afterwards, by reactor until surge flask, washing bottle, high alkali liquid, bromine cuvette, after experiment terminates, product is mainly distributed in cooling collector.The product collected is carried out GC analysis.GC result shows, containing bromo-1,1, the 2-Halothane of 95.0%1,2-bis-in product.Because trifluoro-ethylene and bromine are reacted quickly, in order to shorten reaction scheme.Tetrafluoroethane and catalyst reaction deviate from HF, generate trifluoro-ethylene.Then, this reaction product is directly by bromine cuvette.After such reaction terminates, bromine cuvette color fade.
(2) in 150ml there-necked flask, above-mentioned 1,2-bis-bromo-1,1, the 2-Halothane mixture [liquid, boiling point about 46 degree] of 32.7g is added.Add 10% sodium hydroxide ethanolic soln wherein, until no longer produce gas.Collect product 14.4g altogether.GC result shows, and wherein bromotrifluoroethylene content is 98.0%.
(3) in 150ml there-necked flask, add 2.0g zinc powder, 47.0g DMF, adopt ethanol nitrogen mixture to control temperature of reaction and be about-70 DEG C, the rotating speed of magnetic stirring apparatus is 200r/min.Stir after 2 hours, import 6.4g bromotrifluoroethylene wherein.Then removed by ethanol nitrogen mixture, the temperature of charge in employing ice-water bath control there-necked flask is within 70 DEG C.Stir after 2 hours, drip the DMF solution of 21.6g Anhydrous Ferric Chloride wherein.This solution is containing Anhydrous Ferric Chloride 5.4g.Temperature of charge in there-necked flask is kept to be in about 0 DEG C.The rotating speed of magnetic stirring apparatus is 100r/min.Strictly control reactor internal pressure simultaneously, make it slowly successively decrease, until 100mTorr.Gaseous product is collected into condensing collector.After stoichiometric number hour, until the weight of condensing collector no longer increases.After reaction terminates, collect 1.54g organism altogether.GC analytical results shows, wherein 87.0% is hexafluoro-1,3-butadiene.In bromotrifluoroethylene, yield is 56.0%.
Embodiment 2
(1) 20ml Cr-Fe-Zn catalyzer is loaded fixed-bed reactor, fixed-bed reactor open-type pipe process furnace heats.Catalyzer, under 50ml nitrogen protection, first to rise at 200 DEG C of temperature dry 2 hours with 10 DEG C/min, then; 400 DEG C of dryings 2 hours are risen to the speed of 10 DEG C/min; then, be cooled to 330 DEG C, then pass to hydrogen fluoride (HF) the gas activation catalyzer 2 hours of 50ml/min.Complete the reactivation process of catalyzer like this.
Reactor is heated to 350 DEG C, then, 50ml/min Tetrafluoroethane enters hybrid chamber and mixes together with 10ml/min nitrogen.Afterwards, by reactor until surge flask, washing bottle, high alkali liquid, bromine cuvette.After experiment terminates, product is mainly distributed in cooling collector.The product collected is carried out GC analysis.GC result shows, containing bromo-1,1, the 2-Halothane of 90.0%1,2-bis-in product.
(2) in 150ml there-necked flask, above-mentioned 1,2-bis-bromo-1,1, the 2-Halothane mixture of 41.0g is added.Add 15% sodium carbonate ethanolic soln wherein, until no longer produce gas.Collect product 8.5g altogether.GC result shows, and wherein bromotrifluoroethylene content is 97.0%.
(3) in 150ml there-necked flask, add 2.0g zinc powder, 47.0g DMF, adopt ethanol nitrogen mixture to control temperature of reaction and be about-70 DEG C, the rotating speed of magnetic stirring apparatus is 200r/min.Stir after 2 hours, import 6.4g bromotrifluoroethylene wherein.Then removed by ethanol nitrogen mixture, the temperature of charge in employing ice-water bath control there-necked flask is within 70 DEG C.Stir after 2 hours, drip the DMF solution of 21.6g Anhydrous Ferric Chloride wherein.This solution is containing Anhydrous Ferric Chloride 5.4g.There-necked flask internal-response thing temperature is kept to be in about 0 DEG C.The rotating speed of magnetic stirring apparatus is 100r/min.Strictly control reactor internal pressure simultaneously, make it slowly successively decrease, until 100mTorr.Gaseous product is collected into condensing collector.React after 4 hours, until the weight of condensing collector no longer increases.After reaction terminates, collect 1.47g organism altogether.GC analytical results shows, wherein 90.0% is hexafluoro-1,3-butadiene.In bromotrifluoroethylene, yield is 55.0%.
Claims (10)
1. synthesize a method for hexafluoro-1,3-butadiene, comprise the steps:
(1) Tetrafluoroethane HFC-134a gas phase dehydrofluorination under catalyst action generates trifluoro-ethylene CF
2=CFH; Product mixtures passes in bromine and bromo-1,1, the 2-Halothane of addition reaction generation 1,2-bis-occurs;
Bromo-1,1, the 2-Halothane of (2) 1,2-bis-dehydrobromination under the effect of alkali generates bromotrifluoroethylene;
(3), after bromotrifluoroethylene and zinc powder, DMF react, directly Fe is added
3+reagent generation linked reaction generates hexafluoro-1,3-butadiene;
Described catalyzer is at least one in Mg, Cr, Fe, or the mixture of at least one in Mg, Cr, Fe and a kind of formation in Bi, Ti metal, and Tetrafluoroethane HFC-134a dehydrofluorination generates trifluoro-ethylene CF
2=CFH temperature of reaction is 100-500 DEG C.
2. method according to claim 1, described Tetrafluoroethane HFC-134a dehydrofluorination generates trifluoro-ethylene temperature of reaction and is 300-400 DEG C, and the duration of contact that Tetrafluoroethane HFC-134a dehydrofluorination generates trifluoro-ethylene reaction is: 0.1-20s.
3. method according to claim 2, during described gas-phase reaction, Tetrafluoroethane HFC-134a and nitrogen enter reactor by 5:1 volume ratio.
4. method according to claim 1; need to activate before described catalyst reaction; described reactivation process is: Cr-Mg catalyzer under nitrogen protection; first to rise at 200 DEG C of temperature dry 2 hours with 10 DEG C/min; then, 400 DEG C of dryings 2 hours are risen to the speed of 10 DEG C/min, then; be cooled to 330 DEG C, then pass to hydrogen fluoride HF gas activation catalyzer 2 hours.
5. method according to claim 1, the alkali in described step (2) is sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, sodium bicarbonate, the one in saleratus or its combination.
6. method according to claim 1, described (3) step operation process is: A) the DMF solution stirring of zinc powder mixed and be cooled to-70 DEG C, then import bromotrifluoroethylene CF in solution
2=CFBr gas, keeps temperature of reaction to be no more than 70 DEG C, reaction times 1-3 hour, B) at-10 DEG C-10 DEG C, by Fe
3+the DMF solution of reagent adds A) reaction mixture in, reaction 1-3 hour, collect product gas.
7. method according to claim 6, bromotrifluoroethylene: Zn:Fe in described step (3)
3+mol ratio is 1:1:0.5.
8. method according to claim 6, described Fe
3+reagent is Anhydrous Ferric Chloride or anhydrous iron bromide.
9. method according to claim 6, described zinc powder needs activation before using, and described activation method is: Zn powder 10% hydrochloric acid washs, and then uses washing with acetone, filters, and dries 3 hours for 150 DEG C.
10. method according to claim 1, also comprises the recycling step of solvent after described step (3).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380371A (en) * | 2016-08-17 | 2017-02-08 | 山东东岳化工有限公司 | A resource utilization method of chlorofluorocarbons |
| CN106495982A (en) * | 2016-10-17 | 2017-03-15 | 邵武华航新材料有限公司 | A kind of method that catalysis prepares 1,3 butadiene of hexafluoro |
| WO2021254372A1 (en) * | 2020-06-17 | 2021-12-23 | 浙江省化工研究院有限公司 | Method for preparing 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 |
| CN114901667A (en) * | 2019-12-27 | 2022-08-12 | 大金工业株式会社 | Process for producing fluorine-containing (cyclo) alkenyl halide zinc compound |
| CN116120146A (en) * | 2022-08-18 | 2023-05-16 | 浙江省化工研究院有限公司 | Production method and system of hexafluorobutadiene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3046304A (en) * | 1956-09-06 | 1962-07-24 | Haszeldine Robert Neville | Coupling of halogenated organic compounds |
| WO2006026400A1 (en) * | 2004-08-26 | 2006-03-09 | Great Lakes Chemical Corporation | Chemical production processes and systems |
| CN103288589A (en) * | 2013-06-04 | 2013-09-11 | 同济大学 | Method for co-production of trifluoroethylene and hydrogen fluoride |
| 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 |
| 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 |
-
2015
- 2015-04-03 CN CN201510157823.XA patent/CN104844411B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3046304A (en) * | 1956-09-06 | 1962-07-24 | Haszeldine Robert Neville | Coupling of halogenated organic compounds |
| WO2006026400A1 (en) * | 2004-08-26 | 2006-03-09 | Great Lakes Chemical Corporation | Chemical production processes and systems |
| CN102086144A (en) * | 2004-08-26 | 2011-06-08 | 纳幕尔杜邦公司 | Chemical production processes and systems |
| CN103288589A (en) * | 2013-06-04 | 2013-09-11 | 同济大学 | Method for co-production of trifluoroethylene and hydrogen fluoride |
| 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 |
| 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 |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380371A (en) * | 2016-08-17 | 2017-02-08 | 山东东岳化工有限公司 | A resource utilization method of chlorofluorocarbons |
| 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 |
| CN106495982A (en) * | 2016-10-17 | 2017-03-15 | 邵武华航新材料有限公司 | A kind of method that catalysis prepares 1,3 butadiene of hexafluoro |
| 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 |
| CN114901667A (en) * | 2019-12-27 | 2022-08-12 | 大金工业株式会社 | Process for producing fluorine-containing (cyclo) alkenyl halide zinc compound |
| WO2021254372A1 (en) * | 2020-06-17 | 2021-12-23 | 浙江省化工研究院有限公司 | Method for preparing hexafluoro-1,3-butadiene and intermediate thereof |
| JP7411124B2 (en) | 2020-06-17 | 2024-01-10 | 浙江省化工研究院有限公司 | Method for producing hexafluoro-1,3-butadiene and its intermediates |
| 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 |
| CN116120146A (en) * | 2022-08-18 | 2023-05-16 | 浙江省化工研究院有限公司 | Production method and system of hexafluorobutadiene |
| 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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