CN104829415B - A kind of method synthesizing hexafluoro-1,3-butadiene - Google Patents
A kind of method synthesizing hexafluoro-1,3-butadiene Download PDFInfo
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- CN104829415B CN104829415B CN201510156081.9A CN201510156081A CN104829415B CN 104829415 B CN104829415 B CN 104829415B CN 201510156081 A CN201510156081 A CN 201510156081A CN 104829415 B CN104829415 B CN 104829415B
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- dibromotetrafluoroethane
- butadiene
- tetrafluoroethane
- hexafluoro
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- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The present invention relates to " a kind of method of synthesis hexafluoro 1,3 butadiene ", belong to organic chemical synthesis field.The method uses tetrafluoroethane HFC 134a gas phase bromination to generate dibromotetrafluoroethane CF3CBr2F, then, dibromotetrafluoroethane and activated zinc powder, N, N dimethylformamide, at Fe3+Effect under occur coupling reaction generate hexafluoro 1,3 butadiene.After reaction, solvent can recycle.Cheaper starting materials of the present invention, source facility；Product yield is high；Product separating-purifying is simple；It is prone to industrialized production.
Description
Technical field
The present invention is a kind of method synthesizing hexafluoro-1,3-butadiene, relates to a kind of easily industrial method synthesis hexafluoro-1,3-butadiene
Method.
Background technology
Hexafluoro-1,3-butadiene has the highest industrial value, is a kind of broad-spectrum raw material of industry, and product can be used for downstream
Precise electronic pcb cleaning agent, agricultural chemical insecticide, have in terms of the fluoride-containing PMMA synthesis such as fluorine-containing medicines intermediate simultaneously
There is higher using value.In terms of fluoro containing polymers synthesis, it can prepare poly-hexachlorobutadiene as high polymer monomer, also
Can be with other monomers synthesis fluorine-containing rubber and the excellent resin of electrical property.Test result indicate that at present, hexafluoro-1,3-butadiene exists
The dry etching aspect of ultra-large integrated circuit has huge application potential.
At present, a lot of research worker have carried out correlational study to the preparation method of hexafluoro-1,3-butadiene.
US2894043 report one dichlorodifluoroethylene under fluorine gas dimerization synthesis intermediate product tetrachloro-hexafluoro butane, then,
Under the effect of zinc powder, dechlorination obtains target product hexafluoro-1,3-butadiene.The shortcoming of the method is that fluorination dimerization stage needs are relatively low
Temperature and the gas fluorine gas of use high-risk.Additionally, the reaction yield of this system is only 30-40%.And, this reaction system
By-product is more, and product separates more difficult.
Above-mentioned technique is optimized by US2676193, and under optimum condition, feed stock conversion is 77%, and product yield is 87%.
Its primary operational method is as follows: by dimer under ultra violet lamp, carries out additive reaction with chlorine, the most quantitatively obtains chlordene
Tetrafluoro butane.Chlordene tetrafluoro butane carries out exchange chloride for fluoride subsequently, and a chlorine of end group is replaced by fluorine respectively, obtains tetrachloro six
Fluorine butane.This reaction has four reactions steps, and it is longer that the telomerisation stage expends the time, needs High Temperature High Pressure, and by-product is relatively
Many, purify to product and bring difficulty.Additionally, catalyst SbF3Cl2Costly.
US3046304 reports a kind of process route being Material synthesis hexafluoro-1,3-butadiene with CTFE.Concrete grammar
As follows: first CTFE and lodine chloride reacts in sealing system and obtain dichloro trifluoro iodoethane, after product rectification, yield
It is 97%.Then, in the case of ultra violet lamp, coupling obtains tetrachloro-hexafluoro butane, and yield is 82%.Finally, at zinc
Under the effect of powder, obtaining hexafluoro-1,3-butadiene, yield is 98%.Process avoids the condition of telomerisation High Temperature High Pressure,
But needing stoichiometric hydrargyrum to participate in reaction, an other product is mercuric iodixde, and toxicity is bigger.
JP2001114710 reports a kind of with tetrafluoroethene as raw material, a kind of method of synthesis hexafluoro-1,3-butadiene.It is main
Step is as follows: tetrafluoroethene and bromine addition obtain dibromotetrafluoroethane (molecular formula CF2Br-CF2Br)；Dibromotetrafluoroethane is at Lewis
Reset under acid catalysis, obtain dibromotetrafluoroethane (molecular formula CF3-CFBr2)；This dibromotetrafluoroethane (molecular formula
CF3-CFBr2) under zinc powder effect, obtain bromination trifluoro-ethylene zincon；Bromination trifluoro-ethylene zincon is under catalyst action
Target product hexafluoro-1,3-butadiene is obtained from coupling.This technological reaction mild condition, cost of material is relatively low, but in technique
The synthesis step yield of zincon is on the low side.Additionally, the usage amount of zinc is too big, cause raw material quality unit consumption high.
A kind of method preparing hexafluoro-1,3-butadiene with bromotrifluoroethylene of WO2006026400 patent report.Reaction scheme is such as
Under: tetrafluoroethane (HFC-134a), under zinc chloride and lithium diisopropylamine effect, forms chloro trifluoro ethylene zinc.Then,
Trifluoro-ethylene zinc catalytic coupling obtains hexafluoro-1,3-butadiene.In terms of tetrafluoroethane, total recovery is between 65-70%.This technique is former
Material HFC-134a cost is relatively low, and synthesis step is simple.But, reaction uses much more expensive and that activity is higher diisopropyl
Lithamide., production process is abnormally dangerous, is not suitable for industrialization.
By above it can be seen that when preparing hexachlorobutadiene with tetrachloro perfluorinated butane for raw material, route is long, condition is harsh,
Use this solvent to be eliminated of dichloromethane, expensive iodine, poisonous fluorine gas.Equipment requirements is high, and the three wastes are many, relatively costly.
When preparing hexachlorobutadiene with trifluoro vinyl zinc halide reagent coupling, productivity all ratios are relatively low, or to use the examination of difficult operation
Agent, such as LDA etc..These all limit the industrialized production of hexachlorobutadiene.
Summary of the invention
The present invention seeks to the hexafluoro-1,3-butadiene utilizing simple reaction system and applicable reaction condition to prepare high yield, this
Invention cheaper starting materials, source facility；Product yield is high；Product separating-purifying is simple；Building-up process safety, is suitable for industrialization
Produce.
A kind of method synthesizing hexafluoro-1,3-butadiene, including order below step:
(1) tetrafluoroethane HFC-134a gas phase bromination is used to generate dibromotetrafluoroethane CF3CBr2F；
(2), after dibromotetrafluoroethane and zinc powder react in DMF, it is directly added into Fe3+ reagent and occurs even
Connection reaction generates hexafluoro-1,3-butadiene；
Described bromination reaction condition is: with activated carbon as catalyst, and tetrafluoroethane and bromine are passed through reactor hybrid chamber, in
React in reactor at 100 600 DEG C, described tetrafluoroethane and mol ratio 1:2-1:8 of bromine.
Described tetrafluoroethane HFC-134a gas phase bromination generate dibromotetrafluoroethane reaction time of contact be: 0.1 20s.
It is 400 DEG C-500 DEG C that described tetrafluoroethane HFC-134a gas phase bromination generates dibromotetrafluoroethane reaction temperature.
It is 1:3-1:7 that described tetrafluoroethane HFC-134a gas phase bromination generates dibromotetrafluoroethane reaction mol ratio.
Described catalyst needs activation before use, and described activation step is: activated-carbon catalyst under nitrogen protection, first with
10 DEG C/min is dried at a temperature of rising to 400 DEG C 2 hours, then, rises to 600 DEG C with the speed of 10 DEG C/min and is dried 2 hours i.e.
Can.
Described (2nd) step operation process is: A) the N,N-dimethylformamide solution stirring of zinc powder is mixed and is cooled to
-70 DEG C, then in solution, import dibromotetrafluoroethane CF3CBr2F gas, keeps reaction temperature to be less than 70 DEG C, the response time
1-3 hour, B) at-10 DEG C 10 DEG C, by Fe3+The N,N-dimethylformamide solution of reagent adds A) reactant mixture
In, in 1-3 hour response time, collect gaseous product.
Described dibromotetrafluoroethane: Zn:Fe3+Mol ratio is 1:1:0.5.
Described Fe3+Reagent is anhydrous ferric chloride or anhydrous ferric bromide.
Described zinc powder needs activation before using, described activation method is: Zn powder washs with 10% hydrochloric acid, then washes with acetone
Wash, filter, dry 3 hours for 150 DEG C.
The recycling step of solvent is also included after described step (2).
The application (1st) step uses cheaper starting materials, originate tetrafluoroethane (HFC-134a) easily, utilizes gas phase reaction bromination to obtain
To dibromotetrafluoroethane CF3CBr2F, the gas phase response time is short, and after product separates, raw material can continue reuse.Dibromotetrafluoroethane
CF3CBr2F again with zinc powder, N,N-dimethylformamide, Fe3+Coupling reaction is occurred to obtain product.The application method reactor product
Yield is high, and product separating-purifying is simple, building-up process safety, and catalyst is partially suitable, and solvent can recycle, particularly suitable
In industrialized production.
The total process of synthesis technique of the present invention is:
Beneficial effects of the present invention is as follows:
Cheaper starting materials the most of the present invention, source facility.
2. solvent can recycle.
3. product yield is high, and product separating-purifying is simple.
4. building-up process safety, is suitable for industrialized production
Specific embodiment
Below by way of the description of detailed description of the invention, the invention will be further described, but this is not limitation of the present invention, this
Skilled person is according to the basic thought of the present invention, and various modifications may be made or improves, but without departing from the present invention's
Basic thought, the most within the scope of the present invention.
Embodiment 1
(1) by 20ml activated-carbon catalyst [purpose of activated carbon is to increase reaction contact time, it is also possible to be considered catalyst]
Loading fixed bed reactors, fixed bed reactors open-type pipe heating furnace heats.Catalyst is under 50ml nitrogen is protected, first
It is dried at a temperature of rising to 400 DEG C with 10 DEG C/min 2 hours, then, rises to 600 DEG C with the speed of 10 DEG C/min and be dried 2 hours.
So complete the activation process of catalyst.
Reactor is heated to 450 DEG C, and then, 30ml/min tetrafluoroethane enters hybrid chamber together with 30ml/min bromine and mixes
Close uniformly.Afterwards, by reactor until surge flask, washing bottle, high alkali liquid, cooling collector.After experiment terminates, product
It is mainly distributed in cooling collector.The product collected is carried out GC analysis.GC result shows, collects in product and contains
27% dibromotetrafluoroethane, 18% 1 teflurane.
(2) pour 50g Zn powder into hydrochloric acid that 100ml concentration is 10%, stir rapidly 1-3min.Then, acetone is used
Wash twice.Under 150 DEG C of air conditionses, dry 3 hours.So complete zinc powder activation process.
(3) in 150ml there-necked flask, add 2.0g activated zinc powder, 47.0g DMF, use ethanol
Liquid nitrogen mixture controls reaction temperature and is about-70 DEG C, and the rotating speed of magnetic stirring apparatus is 200r/min.After stirring 2 hours, Xiang Qi
Middle importing 6.4g dibromotetrafluoroethane.Then ethanol nitrogen mixture is removed, use ice-water bath to control the reaction in there-necked flask
Thing temperature is within 70 DEG C.After stirring 2 hours, the DMF of dropping 21.6g anhydrous ferric chloride is molten wherein
Liquid.This solution 5.4g Han anhydrous ferric chloride.In keeping there-necked flask, temperature of charge is in about 0 DEG C.Turning of magnetic stirring apparatus
Speed is 100r/min.Strictly control reactor internal pressure so that it is slowly successively decrease simultaneously, until 100mTorr.Gaseous products
Collect to condensing collector.After stoichiometric number hour, until the weight of condensing collector is not further added by.After reaction terminates, collect altogether
To 1.38g Organic substance.GC analysis result shows, wherein 87.0% is hexafluoro-1,3-butadiene.With dibromotetrafluoroethane, yield
It is 69.0%.
Embodiment 2
(1) 20ml activated-carbon catalyst being loaded fixed bed reactors, fixed bed reactors open-type pipe heating furnace heats.
Catalyst, under 50ml nitrogen is protected, is dried 2 hours at a temperature of first rising to 400 DEG C with 10 DEG C/min, then, with 10 DEG C/min
Speed rise to 600 DEG C be dried 2 hours.So complete the activation process of catalyst.
Reactor is heated to 550 DEG C, and then, 30ml/min tetrafluoroethane enters hybrid chamber together with 30ml/min bromine
Mix homogeneously.Afterwards, by reactor until surge flask, washing bottle, high alkali liquid, cooling collector.After experiment terminates, produce
Thing is mainly distributed in cooling collector.The product collected is carried out GC analysis.GC result shows, collects in product and contains
19% dibromotetrafluoroethane, 15% 1 teflurane.
(2) in 150ml there-necked flask, add 2.0g activated zinc powder, 47.0g DMF, use ethanol
Liquid nitrogen mixture controls reaction temperature and is about-70 DEG C, and the rotating speed of magnetic stirring apparatus is 200r/min.After stirring 2 hours, Xiang Qi
Middle importing 5.8g dibromotetrafluoroethane.Then ethanol nitrogen mixture is removed, use ice-water bath to control the reaction in there-necked flask
Thing temperature is within 70 DEG C.After stirring 2 hours, the dropping 24.8g DMF containing anhydrous ferric bromide wherein
Solution.This solution contains anhydrous ferric bromide 11.2g.In keeping there-necked flask, temperature of charge is in about 0 DEG C.Magnetic stirring apparatus
Rotating speed is 100r/min.Strictly control reactor internal pressure so that it is slowly successively decrease simultaneously, until 100mTorr.Gaseous state produces
Thing is collected to condensing collector.After stoichiometric number hour, until the weight of condensing collector is not further added by.After reaction terminates, receive altogether
Collection is to 1.17g Organic substance.GC analysis result shows, wherein 90.0% is hexafluoro-1,3-butadiene.In terms of dibromotetrafluoroethane,
Yield is 65.0%.
Claims (8)
1. the method synthesizing hexafluoro-1,3-butadiene, including order below step:
(1) tetrafluoroethane HFC-134a gas phase bromination is used to generate dibromotetrafluoroethane CF3CBr2F；
(2), after dibromotetrafluoroethane and zinc powder react in DMF, it is directly added into Fe3+Reagent generation coupling
Reaction generates hexafluoro-1,3-butadiene；
Described bromination reaction condition is: with activated carbon as catalyst, and tetrafluoroethane and bromine are passed through reactor hybrid chamber, in
React in reactor at 100 600 DEG C, described tetrafluoroethane and mol ratio 1:2-1:8 of bromine；
Described (2nd) step operation process is: A) the N,N-dimethylformamide solution stirring of zinc powder is mixed and is cooled to
-70 DEG C, then in solution, import dibromotetrafluoroethane CF3CBr2F gas, keeps reaction temperature to be less than 70 DEG C, the response time
1-3 hour, B) at-10 DEG C 10 DEG C, by Fe3+The N,N-dimethylformamide solution of reagent adds A) reactant mixture
In, in 1-3 hour response time, collect gaseous product, described Fe3+Reagent is anhydrous ferric chloride or anhydrous ferric bromide.
Method the most according to claim 1, it is anti-that described tetrafluoroethane HFC-134a gas phase bromination generates dibromotetrafluoroethane
The time of contact answered is: 0.1 20s.
Method the most according to claim 1, it is anti-that described tetrafluoroethane HFC-134a gas phase bromination generates dibromotetrafluoroethane
Answering temperature is 400 DEG C-500 DEG C.
Method the most according to claim 1, it is anti-that described tetrafluoroethane HFC-134a gas phase bromination generates dibromotetrafluoroethane
Answering mol ratio is 1:3-1:7.
Method the most according to claim 1, described catalyst needs activation before use, and described activation step is: activity
Pd/carbon catalyst under nitrogen protection, is dried 2 hours at a temperature of first rising to 400 DEG C with 10 DEG C/min, then, with 10 DEG C/min
Speed rise to 600 DEG C be dried 2 hours.
Method the most according to claim 1, described dibromotetrafluoroethane: zinc powder: Fe3+Mol ratio is 1:1:0.5.
Method the most according to claim 1, described zinc powder needs activation before using, described activation method is: Zn powder is used
10% hydrochloric acid washs, and then with washing with acetone, filters, and dries 3 hours for 150 DEG C.
Method the most according to claim 1, also includes the recycling step of solvent after described step (2).
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| CN105272818B (en) * | 2015-11-19 | 2017-07-04 | 北京宇极科技发展有限公司 | Prepare the new method of perfluorobutadiene |
| 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 |
| CN109232167A (en) * | 2018-11-06 | 2019-01-18 | 南通宝凯化工有限公司 | A kind of preparation process of perfluorobutadiene |
| CN111187145B (en) * | 2020-01-08 | 2023-01-24 | 广东电网有限责任公司电力科学研究院 | Preparation method of hexafluorobutadiene |
| CN112645794B (en) * | 2020-12-28 | 2022-12-27 | 山东东岳化工有限公司 | Preparation method of hexafluoro-1,3-butadiene |
| CN114478207A (en) * | 2022-03-17 | 2022-05-13 | 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） | Hexafluorobutenyl dimethyl ether and preparation method and application thereof |
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