CN102875324A - Preparation method of fluorobromoethylene - Google Patents
Preparation method of fluorobromoethylene Download PDFInfo
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Abstract
The invention provides a method for a novel process route of 1-bromo-2,2-difluoroethylene. The method comprises the following steps of (i) preparing 1,2-dibromo-1,1-difluoroethane (CF2Br-CH2Br) with high selectivity by employing a catalytic addition reaction of 1,1-difluoroethylene (CF2=CH2); and (ii) adding 100-350 mol% of an alkaline water solution according to a molar weight of 1,2-dibromo-1,1-difluoroethane, performing selective dehydrobromination reaction on the 1,2-dibromo-1,1-difluoroethane and the alkaline water solution at a temperature of 30-150 DEG C by using a professionally designed reaction refinery system to obtain 1-bromo-2,2-difluoroethylene.
Description
Technical field
The present invention relates to a kind of important brominated vinyl fluoride compound--1-bromo-2,2-difluoroethylene (CF
2=CHBr) preparation method, the reaction process route of the inventive method can obtain high yield, is a kind of processing method of green, is suitable for suitability for industrialized production.
Background technology
1-bromo-2,2-difluoroethylene are a kind of important fluorochemicals intermediate and fluoropolymer the 3rd monomer, can be used as the intermediate of multiple fluorine-containing fine chemicals, and it is synthetic to be used for fluorine-containing medicines; Can be used as fluoropolymer the 3rd monomer, improve vulcanization process and the use properties of fluoroelastomer, improve the melt-processable of fluoropolymer and produce property.
Prior art has proposed many preparation 1-bromo-2, the method for 2-difluoroethylene.For example, the people such as the Davis of Dow Chemical have described a kind of 1-of preparation bromo-2, the method for 2-difluoroethylene in US Patent No. P in 1970 3,505,416.It adopts the tetrabromo C2H4F2 C2H4F2 as the synthetic 1-bromo-2 of raw material debrominate, the 2-difluoroethylene, according to an one example, this reacts in the there-necked flask of 1L, adds the 4.14mol zinc powder, 200ml ethanol, and then slowly add the mixed solution of 1.53mol tetrabromo C2H4F2 C2H4F2 and 280ml ethanol, and refluxing 2 hours, the dry ice condensation is collected and is obtained 1-bromo-2,2-difluoroethylene, yield are 82%.
Although the method can make with about 82% higher yields 1-bromo-2, the 2-difluoroethylene, there is following defective in the method:
(i) raw material that adopts is difficult the acquisition, and cost is higher;
(ii) it can produce a large amount of zinc bromide trade wastes, is difficult to industrially scalable and implements.
Therefore, need the 1-bromo-2 of a kind of efficient environmental protection of exploitation, the manufacture method of 2-difluoroethylene requires this preparation method not only to have the high advantage of reaction yield, but also has low cost, the advantage that is easy to suitability for industrialized production of low waste.
Summary of the invention
Goal of the invention of the present invention provides a kind of new 1-bromo-2, and the manufacture method of 2-difluoroethylene, the inventive method not only have the high advantage of reaction yield of new technology route, but also has low-cost and environmental protection and be easy to the advantage of suitability for industrialized production.
Therefore, the invention provides a kind of 1-of preparation bromo-2,2-difluoroethylene (CF
2=CHBr) method, it may further comprise the steps:
(i) adopt vinylidene fluoride (CF
2=CH
2) catalytic addition reaction, make 1,2-, two bromo-1,1-C2H4F2 C2H4F2 (CF
2Br-CH
2Br);
(ii) by described 1,2-two bromo-1, the molar weight meter of 1-C2H4F2 C2H4F2, add the aqueous solution of 100-350 % by mole alkali, reactive distillation under 30-150 ℃ temperature makes described 1,2-two bromo-1,1-C2H4F2 C2H4F2 and alkali aqueous solution carry out optionally dehydrobromination reaction, obtain 1-bromo-2, the 2-difluoroethylene.
Embodiment
The invention provides a kind of efficient 1-bromo-2, the manufacture method of 2-difluoroethylene, the inventive method comprise provides 1,2-, two bromo-1, and then the 1-C2H4F2 C2H4F2 removes hydrogen bromide under debrominate agent effect and collection obtains 1-bromo-2, the step of 2-difluoroethylene.
1.
Provide 1,2-, two bromo-1, the 1-C2H4F2 C2H4F2
The inventive method comprises provides 1,2-, two bromo-1, the step of 1-C2H4F2 C2H4F2.Described 1,2-two bromo-1,1-C2H4F2 C2H4F2 can adopt the known any conventional steps of the present invention to make.In a better example of the present invention, described 1,2-two bromo-1, the 1-C2H4F2 C2H4F2 is by 1,1-difluoroethylene and bromine reaction make, because this reaction is easy to produce the compound of adding into of the polymer of vinylidene and bromine, therefore needs to adopt specific reaction conditions and catalyzer to obtain high yield and selectivity.
Vinylidene fluoride and bromine reaction generate 1,2-, two bromo-1, and side reaction equation common during the 1-C2H4F2 C2H4F2 is as follows:
In the present invention, term " bromine " refers to the pure bromine simple substance of liquid, can be buied by market, and its content dilutes or do not dilute and can react bromine greater than 99%, requires molar weight to reach and gets final product.
The vinylidene fluoride that is applicable to the inventive method is without particular limitation, can be buied by market, and its preferred purity is greater than 95%, but being lower than 95% purity also can prepare target compound.
In the methods of the invention, 1,2-, two bromo-1, in the building-up process of 1-C2H4F2 C2H4F2, calculate with molar weight, the add-on of vinylidene fluoride is generally equal to or is higher than the consumption of bromine, because excessive bromine may cause 1, the 1-difluoroethylene generates by product, and namely reaction product is the product of 3 to 4 bromines of addition, for example tribromo C2H4F2 C2H4F2, tetrabromo C2H4F2 C2H4F2s etc. reduce reaction yield.Excessive vinylidene fluoride can reclaim re-using.
In an example of the present invention, to calculate with the amount of pure bromine, the add-on of bromine is generally 80～120 % by mole of vinylidene fluoride add-on, preferably 95～100 % by mole.
The inventive method can be carried out in the presence of solvent, perhaps also can carry out in the situation that does not have solvent.Use solvent to be conducive to further improve speed of reaction, but for subsequent reactions, improved the cost that separates.Do not adopt the reaction of solvent more can embody Atom economy, but will strictly control reaction conditions.
The oxygen-free halogenated solvent of normal operation.In the present invention, term " halogenated solvent " has referred to the C of solvent action
1-8Halogenated alkane better is C
1-6Halogenated alkane is more preferably C
1-4Halogenated alkane.
The indefiniteness example of halogenated solvent has preferably, for example methylene dichloride, trichloromethane, chlorobenzene, 1,1,1-Refrigerant R 113,1,1-two chloro-1-one fluoroethane, 1,1-two chloro-2, the mixed solvent of 2,2-Halothane, perflexane or multiple above-mentioned solvent.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and/or iodine; Better be fluorine and/or chlorine.
Generate 1,2-, two bromo-1 at vinylidene fluoride of the present invention and bromine reaction, in the reaction of 1-C2H4F2 C2H4F2, contain the yield that fluorous solvent can further improve final product in solvent or the solvent mixture.The add-on of solvent is without particular limitation, can be the consumption of any routine known in the art.In a better example of the present invention, solvent is 0～500 % by weight of bromine add-on normally, better is 10～350 % by weight, is more preferably 20～150 % by weight.
Generate 1,2-, two bromo-1 at vinylidene fluoride of the present invention and bromine reaction, in the reaction of 1-C2H4F2 C2H4F2, the contriver finds that this reaction interpolation catalyzer can further improve the selectivity of reaction.The indefiniteness example of applicable catalyzer has, aminated compounds for example, and such as triethylamine, Tributylamine, Tetramethyl Ethylene Diamine, six first class tetramines; With the Polyenes catalyzer, firpene for example, terpenes and limonene etc.The existence of catalyzer mainly is the polymerization that can remove the oxygen initiator of polyreaction or stop free radical, can suppress vinylidene autohemagglutination or poly, stops the reaction of adding into of bromine.
In a better example of the present invention, by the add-on of bromine, the consumption of catalyzer is 0～0.5 % by weight normally, better is 0.01～0.2 % by weight, is more preferably 0.02～0.05 % by weight.
In the present invention 1,1-difluoroethylene and bromine reaction generate 1,2-two bromo-1, in the reaction of 1-C2H4F2 C2H4F2, the contriver finds that temperature has larger impact to yield and the speed of reaction, reaction can further obviously increase the yield of reaction product under suitable temperature, improves speed of response, and temperature of reaction is crossed the higher position and produced easily by product.Temperature of reaction is generally-20 ℃～120 ℃, and 10 ℃ more fortunately～80 ℃, more preferably 40 ℃～70 ℃.
In the present invention 1,1-difluoroethylene and bromine reaction generate 1,2-two bromo-1, in the reaction of 1-C2H4F2 C2H4F2, the reaction pressure of described reactions steps is obvious on speed of reaction and selectivity impact, can to the pressure of 1.5MPa, react in vacuum, better place under the pressure of 0～0.8MPa, preferably place under the pressure of 0.1～0.5MPa.Reaction pressure is generally by adding speed and the controlling reaction temperature of reactant.The pressure of reaction is higher, and speed of reaction is faster, but produces by product easily.
Generate 1,2-, two bromo-1 at the vinylidene fluoride of the present invention that adopts above-mentioned reaction conditions and bromine reaction, in the reaction of 1-C2H4F2 C2H4F2,1,2-, two bromo-1, the synthesis yield of 1-C2H4F2 C2H4F2 is greater than 98%.
2.
The dehydrobromination reaction
The inventive method also comprises uses 1,2-, two bromo-1, and 1-C2H4F2 C2H4F2 and alkali aqueous solution react in the reactive distillation equipment of controlled condition, i.e. dehydrobromination reaction obtains 1-bromo-2 efficiently, 2-difluoroethylene, and the step of recovery byproduct Bromide.
In the prior art, the dehydrobromination reaction is generally adopted than the debrominate agent reaction of low reaction temperatures and the method for blank pipe Pintsch process, but the reaction yield of two kinds of methods is not high:
Adopt in the reaction of debrominate agent, the debrominate agent can be adopted the oxyhydroxide of metal powder (such as calcium, magnesium, aluminium, copper, nickel, iron, zinc etc.), basic metal and/or alkaline-earth metal.Reaction generally needs a large amount of organic solvents to promote reaction, and in order to improve yield, the metal powder add-on of reaction is generally all excessive a lot, produces the more organic liquid waste that contains solid, and environmental pollution is larger;
Adopt in the method for blank pipe Pintsch process, the method is not easy to control the per pass conversion of reaction, and the more by product of the easy generation of cracking, needs a large amount of alkali liquor absorptions to process.
The reaction equation that dehydrobromination reacts possible is as follows:
BrF
2C-CH
2Br→F
2C＝CHBr+F
2C＝CH
2+F
2C＝CBr
2
The alkali aqueous solution debrominate method that dehydrobromination method of the present invention adopts, selectivity is very high, and byproduct of reaction only has Bromide and water, and Bromide can be sold or resynthesis bromine and alkali through refining, reaches the Atom economy that each atom obtains utilizing in the technique.
In a better example of the present invention, the aqueous solution of described alkali is the aqueous solution of alkali metal compound, the aqueous solution of potassium hydroxide, sodium hydroxide, lithium hydroxide for example, by 1,2-two bromo-1, the add-on meter of 1-C2H4F2 C2H4F2, the add-on of alkali metal compound is generally 100～350 % by mole, preferably 102～180 % by mole, be preferably 105-120 % by mole.
In dehydrobromination reaction of the present invention, be preferably in the water and react, also can add a small amount of organic solvent and promote reaction, preferred solvent mainly contains one or more organic solvents of the oxygenatedchemicalss such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, dme, diethyl ether, acetone, methyl ethyl ketone, metacetone, tetrahydrofuran (THF), the mass ratio of better solvent and water is 0.05-10:1 in the mixture, preferred 0.1-0.5:1.The mass ratio of solvent or water and alkali is 0.1-8:1 more fortunately, preferred 0.3-4:1.
Existing dehydrobromination reaction is carried out under conventional temperature usually.But the contriver finds the temperature of reaction of dehydrobromination reaction the yield that reacts is had obvious impact, reaction yield is higher under suitable temperature, and preferred temperature of reaction is 30 ℃～150 ℃, 40 ℃ more fortunately～120 ℃, and better 60 ℃～100 ℃.
The reactor that dehydrobromination reaction of the present invention is used can be conventional reactor, the enamel class of preferred alkaline-resisting liquid and bromine compounds or surface treated stainless steel cauldron.In order to prevent that product that reaction process produces and the alkali of high reaction activity from further reacting, form by product, thereby lowered reaction yield, in a better example of the present invention, use the reactor with the rectifying tower section, i.e. the system of stirring tank reactive distillation, make the low 1-bromo-2 that boils of reaction gained, the 2-difluoroethylene can be deviate from from reaction system rapidly, and the condensation collection, avoids it further to be reacted into impurity in reactor.For the reactive distillation system, can select suitable reactor volume and collection process body of the tower height according to amount and the reaction adding speed of reaction, preferred reaction tower number of theoretical plate is 5-80, preferably 10-40.
In dehydrobromination method of the present invention, the method reaction pressure of described dehydrobromination reactions steps is less on the impact of speed of reaction and selectivity, and reaction pressure generally can be lower than normal atmosphere, normal pressure or be higher than normal atmosphere.In general, just lower to the conversion unit requirement preferably near atmospheric pressure, be easy to suitability for industrialized production.
Adopt method of the present invention, can make 1-bromo-2, the synthesis yield of 2-difluoroethylene can reach greater than 97%, calculates total reaction yield greater than 95% from vinylidene, and is suitable for the industrialization low cost production.
In the methods of the invention, the reaction times of described reaction is not crucial, the temperature in the reaction process, and the add-on of pressure and material has determined the reaction times, and the adding speed of material should be at the uniform velocity usually, and the control temperature and pressure changes less.After having read content disclosed by the invention, those of ordinary skill in the art is non-just can easily to determine the suitable reaction times through creative work.
In an example of the present invention, the reaction times of described reaction is controlled at 2-12 hour, and preferably 4-10 hour, more preferably 5-7 hour.
The total amount that feeds intake of the present invention is not crucial to the inventive method, and it only has relation with the reactive system size that adopts.
After reaction finished, the product of collection was through conventional rectification, can obtain purity greater than 99% product.
The present invention can be used for the synthetic 1-bromo-2 of industry, 2-difluoroethylene.
In a better example of the present invention, adopt following reaction process route to prepare 1-bromo-2 of the present invention, the 2-difluoroethylene:
Wherein M is alkali-metal lithium, sodium, potassium, rubidium, caesium etc.; Described catalyzer is selected from triethylamine, Tributylamine, Tetramethyl Ethylene Diamine, six first class tetramines, firpene, terpenes and limonene etc.
The total molar yield of product of this new reaction process method of the present invention is greater than 95%, and realize easily cheaply continuous or repetition suitability for industrialized production intermittently, whole processing method is the processing method with very high Atom economy of environmental protection, use the raw material vinylidene, bromine and alkali lye obtain 1-bromo-2,2-difluoroethylene product and Bromide, Bromide can be sold or resynthesis bromine and alkali through refining, reaches the Atom economy that each atom obtains utilizing in the technique.
The following example further specifies objects and advantages of the present invention, but concrete material and consumption thereof among these embodiment, and other condition and details all should not be considered as limitation of the present invention, as do not add explanation, the purity of the compound that uses is analytical pure.
Embodiment 1
1. prepare 1,2-, two bromo-1, the 1-C2H4F2 C2H4F2
In the 10L reactor, add the 10kg bromine, be heated to 40 ℃, slowly pass into vinylidene 4.3kg, reacted altogether 6 hours, reaction pressure is 0.3MPa, and after reaction finished, excessive vinylidene found time to be collected into accumulator tank, can recycle through separating, reactor obtains product 1,2-two bromo-1, and the 1-C2H4F2 C2H4F2 is 14.09kg altogether, be 85.2% through its purity of GC stratographic analysis, molar yield is 85.8%.
After tested, the boiling point of products therefrom: 92.1 ℃/760mmHg; Mass spectrum MS molecular weight=223.8; Nuclear magnetic resonance nmr H
1, chemical shift δ 4.1; NMR F
19, chemical shift δ-50.2.
2. prepare 1-bromo-2,2-difluoroethylene
0.5m at-35 ℃ of salt solution of band
2Add 2kg potassium hydroxide in the 10L reactor of the condenser of condensation area, 3kg water, be heated to 60 ℃, slowly pass into make above 1,2-two bromo-1,1-C2H4F2 C2H4F2 5.5kg, reacted altogether 5 hours, collect product 3.25kg in the reaction process, GC stratographic analysis purity is 89%, and molar yield is 85.0%.
After tested, the boiling point of products therefrom: 6.7 ℃/760mmHg; Mass spectrum MS molecular weight=142.9; Nuclear magnetic resonance nmr H
1, chemical shift δ 5.16; NMR F
19, chemical shift δ-83.2 and-84.1.
Embodiment 2
1. prepare 1,2-, two bromo-1, the 1-C2H4F2 C2H4F2
In the 10L reactor, add the 10kg bromine, be heated to 70 ℃, slowly pass into vinylidene 4.2kg, reacted altogether 3 hours, reaction pressure is 0.2MPa, and after reaction finished, excessive vinylidene found time to be collected into accumulator tank, can recycle through separating, reactor obtains product 1,2-two bromo-1, and the 1-C2H4F2 C2H4F2 is 14.02kg altogether, its purity is 86.5% by analysis, and molar yield is 86.6%.
2. prepare 1-bromo-2,2-difluoroethylene
0.5m at-35 ℃ of salt solution of band
2The 10L reactor of the condenser of condensation area, be that theoretical plate number is 20 packing tower pipeline at rising steam to the pipeline modification of condenser, reactor adds 2kg potassium hydroxide, 4kg water, be heated to 60 ℃, slowly pass into 1 of above-mentioned 96.5% purity, 2-two bromo-1,1-C2H4F2 C2H4F2 5.5kg, reacted altogether 5 hours, collect product 3.42kg in the reaction process, purity is 92.7%, and molar yield is 93.2%.Potassium Bromide in the aqueous solution can be made with extra care purifying through unified the collection.
Embodiment 3
1. prepare 1,2-, two bromo-1, the 1-C2H4F2 C2H4F2
In the 10L reactor, add the 10kg bromine, be heated to 60 ℃, slowly pass into vinylidene 4.3kg, reacted altogether 4 hours, reaction pressure is 0.4MPa, and after reaction finished, excessive vinylidene found time to be collected into accumulator tank, can recycle through separating, reactor obtains product 1,2-two bromo-1, and the 1-C2H4F2 C2H4F2 is 14.03kg altogether, its purity is 87.3% by analysis, and molar yield is 87.5%.
2. prepare 1-bromo-2,2-difluoroethylene
0.5m at-35 ℃ of salt solution of band
2The 10L reactor of the condenser of condensation area is that theoretical plate number is 20 packing tower pipeline at rising steam to the pipeline modification of condenser, and reactor adds 2kg potassium hydroxide, 3kg water, 0.5kg ethanol is heated to 60 ℃, slowly passes into 1 of 97% purity, 2-two bromo-1,1-C2H4F2 C2H4F2 5.5kg reacted 4 hours altogether, collected product 3.37kg in the reaction process, purity is 96.0%, and molar yield is 95.0%.
Embodiment 4
1. prepare 1,2-, two bromo-1, the 1-C2H4F2 C2H4F2
Add the 10kg bromine in the 10L reactor, the 100g triethylamine is heated to 50 ℃, slowly pass into vinylidene 4.25kg, reacted altogether 4 hours, reaction pressure is 0.2MPa, after reaction finishes, excessive vinylidene finds time to be collected into accumulator tank, can recycle through separating, and reactor obtains product 1,2-two bromo-1, the 1-C2H4F2 C2H4F2 is 13.79kg altogether, and purity is 99.7% by analysis, and molar yield is 98.2%.
2. prepare 1-bromo-2,2-difluoroethylene
0.5m at-35 ℃ of salt solution of band
2The 10L reactor of the condenser of condensation area is that theoretical plate number is 30 packing tower pipeline at rising steam to the pipeline modification of condenser, and reactor adds 2kg potassium hydroxide, 3kg water, 0.5kg ethylene glycol is heated to 80 ℃, slowly passes into 1 of 97% purity, 2-two bromo-1,1-C2H4F2 C2H4F2 5.5kg reacted 3 hours altogether, collected product 3.41kg in the reaction process, purity is 98.2%, and molar yield is 98.3%.
Embodiment 5
1. prepare 1,2-, two bromo-1, the 1-C2H4F2 C2H4F2
Add the 10kg bromine in the 10L reactor, the 80g terpenes is heated to 50 ℃, slowly pass into vinylidene 4.25kg, reacted altogether 4 hours, reaction pressure is 0.2MPa, after reaction finishes, excessive vinylidene finds time to be collected into accumulator tank, can recycle through separating, and reactor obtains product 1,2-two bromo-1, the 1-C2H4F2 C2H4F2 is 13.88kg altogether, and purity is 99.5% by analysis, and molar yield is 98.6%.
2. prepare 1-bromo-2,2-difluoroethylene
0.5m at-35 ℃ of salt solution of band
2The 10L reactor of the condenser of condensation area, be that theoretical plate number is 20 packing tower pipeline at rising steam to the pipeline modification of condenser, reactor adds 1.43kg sodium hydroxide, 3kg water, be heated to 70 ℃, slowly pass into 1 of 97% purity, 2-two bromo-1,1-C2H4F2 C2H4F2 5.5kg, reacted altogether 3 hours, collect product 3.3kg in the reaction process, purity is 96.6%, and molar yield is 93.5%.
It is different 1 that Comparative Examples 1(adopts, 2-two bromo-1,1-C2H4F2 C2H4F2 preparation method)
In the 10L reactor, add the 10kg bromine, the room temperature synthesis under normal pressure slowly passes into vinylidene 4.3kg, reacts altogether 24 hours, after reaction finishes, excessive vinylidene finds time to be collected into accumulator tank, can recycle through separating, and reactor obtains product 1,2-two bromo-1, the 1-C2H4F2 C2H4F2 is 13.2kg altogether, is 83.2% through its purity of GC stratographic analysis, and molar yield is 78.4%.
Comparative Examples 2
1. prepare 1,2-, two bromo-1,1-C2H4F2 C2H4F2 (with embodiment 1)
In the 10L reactor, add the 10kg bromine, be heated to 40 ℃, slowly pass into vinylidene 4.3kg, reacted altogether 6 hours, reaction pressure is 0.3MPa, and after reaction finished, excessive vinylidene found time to be collected into accumulator tank, can recycle through separating, reactor obtains product 1,2-two bromo-1, and the 1-C2H4F2 C2H4F2 is 14.09kg altogether, be 85.2% through its purity of GC stratographic analysis, molar yield is 85.8%.
After tested, the boiling point of products therefrom: 92.1 ℃/760mmHg; Mass spectrum MS molecular weight=223.8; Nuclear magnetic resonance nmr H
1, chemical shift δ 4.1; NMR F
19, chemical shift δ-50.2.
2. prepare 1-bromo-2,2-difluoroethylene
0.5m at-35 ℃ of salt solution of band
2Add the 1.8kg zinc powder in the 10L reactor of the condenser of condensation area, 3kg ethanol, be heated to 70 ℃, slowly pass into 1 of 97% purity, 2-two bromo-1,1-C2H4F2 C2H4F2 5.5kg, mix 2kg ethanol and add together, reacted altogether 5 hours, collect product 3.62kg in the reaction process, purity is 77.7%, and molar yield is 72.6%.Produce a large amount of unreacted zinc powders and zinc bromide mixed solvent ethanol, more difficult.
Comparative Examples 3
1. prepare 1,2-, two bromo-1,1-C2H4F2 C2H4F2 (with embodiment 4)
Add the 10kg bromine in the 10L reactor, the 100g triethylamine is heated to 50 ℃, slowly pass into vinylidene 4.25kg, reacted altogether 4 hours, reaction pressure is 0.2MPa, after reaction finishes, excessive vinylidene finds time to be collected into accumulator tank, can recycle through separating, and reactor obtains product 1,2-two bromo-1, the 1-C2H4F2 C2H4F2 is 13.79kg altogether, and purity is 99.7% by analysis, and molar yield is 98.2%.
2. prepare 1-bromo-2,2-difluoroethylene
0.5m at-35 ℃ of salt solution of band
2The 10L reactor of the condenser of condensation area is that theoretical plate number is 20 packing tower pipeline at rising steam to the pipeline modification of condenser, and reactor adds the 1.7kg zinc powder, 3kg ethanol, be heated to 80 ℃, slowly pass into 1 of 97% purity, 2-two bromo-1,1-C2H4F2 C2H4F2 5.5kg, mix 2kg ethanol and add together, reacted altogether 4 hours, collect product 3.47kg in the reaction process, purity is 86.2%, and molar yield is 77.8%.
Comparative Examples 4
1. prepare 1,2-, two bromo-1,1-C2H4F2 C2H4F2 (with embodiment 4)
Add the 10kg bromine in the 10L reactor, the 100g triethylamine is heated to 50 ℃, slowly pass into vinylidene 4.25kg, reacted altogether 4 hours, reaction pressure is 0.2MPa, after reaction finishes, excessive vinylidene finds time to be collected into accumulator tank, can recycle through separating, and reactor obtains product 1,2-two bromo-1, the 1-C2H4F2 C2H4F2 is 13.79kg altogether, and purity is 99.7% by analysis, and molar yield is 98.2%.
2. prepare 1-bromo-2,2-difluoroethylene
At diameter 20mm, long in the stainless steel reaction pipe of 80cm, the Stainless Steel Cloth filler of adding 1.5*1.5mm, described reaction tubes is heated to 570 ℃, pass into 1 of 97% purity, 2-two bromo-1,1-C2H4F2 C2H4F2 3.46kg(15mol), the residence time is 4.2 seconds, reacted altogether 2 hours, reaction is collected and is passed through first a 20L washing kettle, 10% of adding 12L potassium hydroxide aqueous solution in this still, and the 0.5m that adopts-35 ℃ of salt solution is collected in reaction
2The condenser of condensation area is collected product 1.88kg in the reaction process, purity is 86.5%, and molar yield is 75.8%.
Claims (10)
1. one kind prepares 1-bromo-2, the method for 2-difluoroethylene, and it may further comprise the steps:
(i) adopt vinylidene fluoride and bromine catalytic addition reaction, make 1,2-, two bromo-1, the 1-C2H4F2 C2H4F2;
(ii) by described 1,2-two bromo-1, the molar weight meter of 1-C2H4F2 C2H4F2, the aqueous solution that adds 100-350 % by mole alkali, under 30-150 ℃ temperature, make described 1,2-two bromo-1,1-C2H4F2 C2H4F2 and alkali aqueous solution carry out optionally dehydrobromination reaction, obtain 1-bromo-2, the 2-difluoroethylene.
2. the method for claim 1 is characterized in that described preparation 1,2-two bromo-1, and 1-C2H4F2 C2H4F2 step (i) comprises bromine and the reaction of 1,1-C2H4F2 C2H4F2, temperature of reaction is 10 ℃～80 ℃, more preferably 40 ℃～70 ℃.
3. method as claimed in claim 2 is characterized in that the reaction of described bromine and 1,1-C2H4F2 C2H4F2 carries out under the pressure of 0.1～0.5MPa.
4. such as each described method among the claim 1-3, it is characterized in that the reaction of described bromine and 1,1-C2H4F2 C2H4F2 is being selected from triethylamine, Tributylamine, Tetramethyl Ethylene Diamine, six first class tetramines, firpene carries out under the existence of the catalyzer of terpenes and limonene.
5. method as claimed in claim 4 is characterized in that the amount by bromine, and the add-on of catalyzer is 0.01～0.5 % by weight, better is 0.02～0.2 % by weight, is more preferably 0.03～0.05 % by weight.
6. the method for claim 1, the alkali that it is characterized in that step (ii) is alkali-metal compound, its add-on is 1,2-, two bromo-1,100～350 % by mole of 1-C2H4F2 C2H4F2 add-on.
7. method as claimed in claim 6 is characterized in that described alkali-metal compound is selected from potassium hydroxide, sodium hydroxide, and its add-on is 1,2-, two bromo-1, and 102～180 % by mole of 1-C2H4F2 C2H4F2 add-on are preferably 105-120 % by mole.
8. method as claimed in claim 6 is characterized in that the reaction of described step (ii) is carried out in the blending agent of water and organic solvent formation, and the amount of described organic solvent accounts for the 5-30 volume % of the amount of water.
9. such as claim 6 or 7 described methods, the temperature of reaction that it is characterized in that the reaction of described step (ii) is 40 ℃～120 ℃.
10. such as the described method of claim 6-9, the reactor design that it is characterized in that the reaction of described step (ii) is the system of reactive distillation, and the vapor riser road of reactor is packing tower, and preferred packing tower number of theoretical plate is 5-80, preferably 10-40.
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| CN103242196A (en) * | 2013-05-15 | 2013-08-14 | 联保作物科技有限公司 | Cyclopropane carboxylic ester type compound, and preparation and application of same |
| CN105152852A (en) * | 2015-09-16 | 2015-12-16 | 湖南城市学院 | Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene |
| CN105820031A (en) * | 2016-04-26 | 2016-08-03 | 南通宝凯化工有限公司 | Synthesis technology of 1-bromine 2,2-polyvinylidene floride |
| CN109369323A (en) * | 2018-12-07 | 2019-02-22 | 湖南有色郴州氟化学有限公司 | A kind of preparation method of the bromo- 1,1- difluoroethylene of 2- |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242196A (en) * | 2013-05-15 | 2013-08-14 | 联保作物科技有限公司 | Cyclopropane carboxylic ester type compound, and preparation and application of same |
| CN103242196B (en) * | 2013-05-15 | 2016-01-27 | 联保作物科技有限公司 | Cyclopropane carboxylic ester compound, its preparation method and application thereof |
| CN105152852A (en) * | 2015-09-16 | 2015-12-16 | 湖南城市学院 | Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene |
| CN105152852B (en) * | 2015-09-16 | 2017-05-10 | 湖南城市学院 | Preparation method of 1-bromo-1-chloro-2,2-difluoroethylene |
| CN105820031A (en) * | 2016-04-26 | 2016-08-03 | 南通宝凯化工有限公司 | Synthesis technology of 1-bromine 2,2-polyvinylidene floride |
| CN109369323A (en) * | 2018-12-07 | 2019-02-22 | 湖南有色郴州氟化学有限公司 | A kind of preparation method of the bromo- 1,1- difluoroethylene of 2- |
| CN109369323B (en) * | 2018-12-07 | 2021-01-12 | 湖南有色郴州氟化学有限公司 | Preparation method of 2-bromo-1, 1-difluoroethylene |
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