CN103553869B - The preparation method of bromine fluorine butane - Google Patents
The preparation method of bromine fluorine butane Download PDFInfo
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- CN103553869B CN103553869B CN201310594720.0A CN201310594720A CN103553869B CN 103553869 B CN103553869 B CN 103553869B CN 201310594720 A CN201310594720 A CN 201310594720A CN 103553869 B CN103553869 B CN 103553869B
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Abstract
Disclose a kind of preparation method of bromine fluorine butane; under it is included in fluorine-containing catalyst action; under the reaction pressure of the temperature of reaction of 30-90 DEG C and 0.1-0.3MPa; make 1; 2-dibromotetrafluoroethane and ethene react; the described fluorine catalyst that contains is selected from two Perfluorodipropionyl peroxides, two perfluor butyryl superoxide, two perfluorocyclohexyl acyl groups, di-t-butyl peroxide, peroxidation dimethylbenzoyl or its two or more mixtures formed.The product molar yield of the inventive method is greater than 85%, and easily realizes low-cost industrial production, and whole processing method significantly improves reaction yield, decreases the reaction times, reduces temperature of reaction and reaction pressure.
Description
Technical field
The present invention relates to bromo-3,3,4, the 4-tetrafluoro butane (BrCF of a kind of important brominated fluorine butane compound-Isosorbide-5-Nitrae-two
2cF
2cH
2cH
2br) preparation method, the inventive method has high yield, and the reaction times is short, is suitable for the advantage of suitability for industrialized production.The invention still further relates to and prepare the catalyzer of bromine fluorine butane method for this.
Background technology
Bromo-3,3,4, the 4-tetrafluoro butane of Isosorbide-5-Nitrae-two are a kind of important fluorochemicals intermediates.As the intermediate of multiple fluoride-containing PMMA, can synthesize for fluorine-containing medicines, the synthesis etc. of fluoropolymer monomer.
About Isosorbide-5-Nitrae-two bromo-3,3, the synthetic method of 4,4-tetrafluoro butane, " 1 of organic fluorine industry, the Addition on ethylene repercussion study of 2-dibromotetrafluoroethane " document introduction, adopt and use dibromotetrafluoroethane and ethene under the effect of di-t-butyl peroxide initiator, temperature of reaction 110-140 DEG C, reaction pressure 0.88MPa, reaction times 30h, transformation efficiency reaches 88.0%, and content 67.1%, yield is 59.1%.
The patent of US5254773 mainly studies the product B rCH of the two addition of ethene
2cH
2cF
2cF
2cH
2cH
2the synthetic method of Br, adopts BrCF
2cF
2cH
2cH
2br again with the method for Addition on ethylene, wherein introduce in the synthetic method of bromo-3,3,4, the 4-tetrafluoro butane of Isosorbide-5-Nitrae-two, temperature of reaction reaches 135-140 DEG C, reaction pressure 1.007MPa, and transformation efficiency is 28%, and selectivity is 80%, and yield is 22.4%.
Said synthesis route, the reaction times is very long, and temperature of reaction and pressure are very high, yield is lower, therefore, the manufacture Isosorbide-5-Nitrae-two bromo-3 developing a kind of efficient gentleness is needed, 3, the method of 4,4-tetrafluoro butane, requires that this preparation method not only has the high advantage of reaction yield, but also it is short to have the reaction times, the advantage being easy to suitability for industrialized production of reaction conditions gentleness.
Summary of the invention
Goal of the invention of the present invention is to provide a kind of manufacture method of bromo-3,3,4, the 4-tetrafluoro butane of Isosorbide-5-Nitrae-two efficiently, and it is high that the inventive method has reaction yield, and the reaction times is short, and temperature of reaction pressure is low, and be easy to the advantage of suitability for industrialized production.
Therefore, the invention provides one and prepare bromo-3,3,4, the 4-tetrafluoro butane (BrCF of Isosorbide-5-Nitrae-two
2cF
2cH
2cH
2br) method: under it is included in the existence of fluorine-containing superoxide, under the pressure of the temperature of 30-90 DEG C and 0.1-0.3MPa, makes 1,2-dibromotetrafluoroethane (CF
2brCF
2br) with ethylene reaction 2-5 hour.
The invention still further relates to fluorine-containing superoxide at 1,2-dibromotetrafluoroethane (CF
2brCF
2as the purposes of catalyzer when Br) preparing bromo-3,3,4, the 4-tetrafluoro butane of Isosorbide-5-Nitrae-two with ethylene reaction.
Embodiment
The invention provides a kind of manufacture method of bromo-3,3,4, the 4-tetrafluoro butane of Isosorbide-5-Nitrae-two efficiently, its reaction process route is as shown below:
Under the inventive method is included in fluorine-containing catalyst action, low-temp low-pressure makes 1,2-dibromotetrafluoroethane and ethylene reaction fast, the step obtaining bromo-3,3,4, the 4-tetrafluoro butane of Isosorbide-5-Nitrae-two of high yield.
In the methods of the invention, the consumption of 1,2-dibromotetrafluoroethane and ethene is without particular limitation, can be any conventional amount used known in the art.For making raw material reaction complete, improve reaction yield, the added in molar amounts of 1,2-dibromotetrafluoroethane is better less than or equal to the consumption of ethene.
In an example of the present invention, with the amount of 1,2-dibromotetrafluoroethane for radix, the add-on of ethene is generally 90 ~ 180 % by mole of 1,2-dibromotetrafluoroethane add-on, preferably 95 ~ 110 % by mole.
1, the 2-dibromotetrafluoroethane being applicable to the inventive method is without particular limitation, can be buied by market, and such as, it can purchased from Shanghai three Ai Fu limited-liability company.The purity of 1,2-dibromotetrafluoroethane is preferably greater than 95wt%, but also can prepare target compound lower than 95wt% purity.
The ethene being applicable to the inventive method can from market purchasing, and preferred purity is greater than 99wt%.
The inventive method can be carried out when there is not solvent, also can carry out in the presence of the solvent.Use solvent to be conducive to improving speed of reaction further, but improve the cost of separation.Do not adopt the reaction of solvent more can embody economy, but will strictly control reaction conditions.
The oxygen-free halogenated solvent of general use.The not limiting example of good halogenated solvent has, such as methylene dichloride, trichloromethane, chlorobenzene, 1, and 1,1-Refrigerant R 113,1,1-bis-chloro-1-mono-fluoroethane, 1,1-bis-chloro-2, the mixed solvent of 2,2-Halothane, perflexane or multiple above-mentioned solvent.
In the methods of the invention, the yield that can further improve final product containing fluorous solvent is contained in solvent or 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 normally 1,2-dibromotetrafluoroethane add-on 0 ~ 200 % by weight, be better 10 ~ 120 % by weight, be more preferably 20 ~ 50 % by weight.
Add a small amount of catalyzer in the reaction system of above-mentioned 1,2-dibromotetrafluoroethane known in the art and ethene, have conclusive effect to reaction, to temperature of reaction, pressure, the time, yield all has a significant effect.Such as, as stated in the Background Art, document " 1, the Addition on ethylene repercussion study of 2-dibromotetrafluoroethane " disclose and adopt di-t-butyl peroxide catalyzer under 110-140 DEG C of temperature of reaction and 0.88MPa reaction pressure, make dibromotetrafluoroethane and ethylene reaction 30 hours, result transformation efficiency reaches 88.0%, content 67.1%, yield is 59.1%.
Existing catalyzer is more, such as: alkyl peroxide, as di-t-butyl peroxide (DTBP), peroxidation two tertiary amyl (DTAP); Peroxide lipid, as peroxide acetic acid butyl ester, the peroxidation trimethylacetic acid tert-butyl ester etc.; Peroxycarbonates class, as peroxy dicarbonate diethyl ester, di-isopropyl peroxydicarbonate (IPP) etc.; Azo, as azobisisobutyronitrile initiator and azo two eyeball initiator in different heptan; Peroxidation two acyl class: peroxidation dimethylbenzoyl etc.But it is slow to find to adopt the reaction of described catalyzer to there is speed of response, and long reaction time, reaction pressure is high, the shortcoming such as reaction yield and poor selectivity.
The present inventor finds, if adopt fluorine-containing superoxide as catalyzer, then the speed of response that can overcome the existence of existing reaction method is slow, and long reaction time, reaction pressure is high, the shortcoming such as reaction yield and poor selectivity.The present invention completes on the basis of this discovery.
Therefore; the present invention adopts fluorine-containing superoxide as catalyzer, and described catalyzer is selected from two perfluor acetyl pexoxides, two Perfluorodipropionyl peroxides, two perfluor butyryl superoxide, two perfluor hexanoyl superoxide, two perfluors (2-n-propyl propionyl) superoxide, two perfluorocyclohexyl acyl peroxides, two perfluor ether superoxide or its two or more mixtures formed.
The consumption of the fluorine-containing peroxide catalyst of the present invention is without particular limitation, can be conventional amount used known in the art.Such as, it can account for 0.1 ~ 10 % by weight of 1,2-dibromotetrafluoroethane add-on, is better 0.5 ~ 5 % by weight, is more preferably 0.8 ~ 3 % by weight.
In a better example of the present invention, catalyzer adopts two Perfluorodipropionyl peroxides, and its add-on accounts for 0.1 ~ 10 % by weight of 1,2-dibromotetrafluoroethane add-on usually, is better 0.5 ~ 5 % by weight, is more preferably 0.8 ~ 3 % by weight.
In the methods of the invention, because the present invention is containing the cause of fluorine catalyst, bearing reaction temperature greatly declines.Temperature of reaction is generally 20 DEG C ~ 120 DEG C, 30 DEG C more fortunately ~ 90 DEG C, more preferably 40 DEG C ~ 70 DEG C.
In the methods of the invention, reaction pressure declines obviously, can react, under being better placed in the pressure of 0.1 ~ 0.8MPa, under being preferably placed in the pressure of 0.1 ~ 0.3MPa under the pressure of 0 to 1.5MPa.Reaction pressure adds speed and controlling reaction temperature generally by ethene.The pressure of reaction is higher, and speed of reaction is faster, but easily produces by product.
In the methods of the invention, the reaction times of described reaction greatly reduces, and controls at 2-12 hour, preferably 2-7 hour, more preferably 2-5 hour.
The product molar yield of the inventive method is greater than 85%, and easily realizes low-cost industrial production, and whole processing method significantly improves reaction yield, decreases the reaction times, reduces temperature of reaction and reaction pressure.
After the completion of reaction, the product that the inventive method also comprises collecting carries out conventional rectification, obtains the product that purity is greater than 99%.
The following example further illustrates objects and advantages of the present invention, but the concrete material in these embodiments and consumption thereof, and other condition and details all should not be considered as limitation of the present invention, as do not added explanation, the purity of the compound of use is analytical pure.
embodiment 1
1, the 2-dibromotetrafluoroethane of 5.2kg is added, 50g bis-Perfluorodipropionyl peroxides in 10L reactor, be heated to 40 DEG C, pass into ethene 580g, amount to reaction 3 hours, reaction pressure is 0.2MPa, after reaction terminates, is isolated to product 1,4-bis-bromo-3,3,4,4-tetrafluoro butane is 5.18kg altogether, be 98.5% through its purity of GC stratographic analysis, molar yield is 88.5%.
embodiment 2
1, the 2-dibromotetrafluoroethane of 5.2kg is added, 80g bis-perfluor butyryl superoxide in 10L reactor, be heated to 60 DEG C, pass into ethene 620g, amount to reaction 3.5 hours, reaction pressure is 0.3MPa, after reaction terminates, is isolated to product 1,4-bis-bromo-3,3,4,4-tetrafluoro butane is 4.99kg altogether, be 99.2% through its purity of GC stratographic analysis, molar yield is 86.7%.
embodiment 3
1, the 2-dibromotetrafluoroethane of 5.2kg is added, 100g bis-perfluor hexanoyl superoxide in 10L reactor, be heated to 80 DEG C, pass into ethene 640g, amount to reaction 4 hours, reaction pressure is 0.4MPa, after reaction terminates, is isolated to product 1,4-bis-bromo-3,3,4,4-tetrafluoro butane is 4.91kg altogether, be 97.8% through its purity of GC stratographic analysis, molar yield is 83.4%.
embodiment 4
1, the 2-dibromotetrafluoroethane of 5.2kg is added, 30g bis-Perfluorodipropionyl peroxides and 50g bis-perfluorocyclohexyl acyl group in 10L reactor; be heated to 70 DEG C, pass into ethene 640g, amount to reaction 4 hours; reaction pressure is 0.35MPa, after reaction terminates, is isolated to product 1; 4-bis-bromo-3; 3,4,4-tetrafluoro butane is 5.02kg altogether; be 98.4% through its purity of GC stratographic analysis, molar yield is 85.7%.
embodiment 5
1, the 2-dibromotetrafluoroethane of 5.2kg is added, 30g bis-Perfluorodipropionyl peroxides and 40g di-t-butyl peroxide in 10L reactor, be heated to 90 DEG C, pass into ethene 660g, amount to reaction 6 hours, reaction pressure is 0.8MPa, after reaction terminates, is isolated to product 1,4-bis-bromo-3,3,4,4-tetrafluoro butane is 3.89kg altogether, be 96.7% through its purity of GC stratographic analysis, molar yield is 65.3%.
comparative example 1
1, the 2-dibromotetrafluoroethane of 5.2kg is added, 80g40g di-t-butyl peroxide in 10L reactor, be heated to 110 DEG C, pass into ethene 680g, amount to reaction 24 hours, reaction pressure is 1.0MPa, after reaction terminates, is isolated to product 1,4-bis-bromo-3,3,4,4-tetrafluoro butane is 3.33kg altogether, be 97.5% through its purity of GC stratographic analysis, molar yield is 56.4%.
comparative example 2
1, the 2-dibromotetrafluoroethane of 5.2kg is added, 80g peroxidation dimethylbenzoyl in 10L reactor, be heated to 120 DEG C, pass into ethene 660g, amount to reaction 24 hours, reaction pressure is 1.2MPa, after reaction terminates, is isolated to product 1,4-bis-bromo-3,3,4,4-tetrafluoro butane is 2.13kg altogether, be 96.5% through its purity of GC stratographic analysis, molar yield is 35.7%.
Claims (6)
1. prepare the method for bromo-3,3,4, the 4-tetrafluoro butane of Isosorbide-5-Nitrae-two for one kind, it comprises:
Under fluorine-containing catalyst action, under the reaction pressure of the temperature of reaction of 30-90 DEG C and 0.1-0.3MPa, make 1,2-dibromotetrafluoroethane and ethylene reaction 2-5 hour,
The described fluorine catalyst that contains is selected from two Perfluorodipropionyl peroxides, two perfluor butyryl superoxide, two perfluorocyclohexyl acyl peroxides, two perfluor hexanoyl superoxide or its two or more mixtures formed;
The add-on of described catalyzer is the 0.1-10 % by weight of 1,2-dibromotetrafluoroethane add-on.
2. the method for claim 1, is characterized in that described temperature of reaction is 40 DEG C-70 DEG C.
3. the method for claim 1, is characterized in that the add-on of described catalyzer is the 0.5-5 % by weight of 1,2-dibromotetrafluoroethane add-on.
4. method as claimed in claim 3, is characterized in that the add-on of described catalyzer is the 0.8-3 % by weight of 1,2-dibromotetrafluoroethane add-on.
5. the method according to any one of claim 1-4, is characterized in that it also containing the second catalyzer being selected from di-t-butyl peroxide, peroxidation two tertiary amyl, peroxide acetic acid butyl ester, the peroxidation trimethylacetic acid tert-butyl ester, peroxy dicarbonate diethyl ester, di-isopropyl peroxydicarbonate, Diisopropyl azodicarboxylate initiator, 2,2'-Azobis(2,4-dimethylvaleronitrile) and peroxidation dimethylbenzoyl.
6. fluorochemicals makes 1; 2-dibromotetrafluoroethane and ethylene reaction prepare 1; 4-bis-bromo-3; 3; 4; as the purposes of catalyzer in the method for 4-tetrafluoro butane, described fluorochemicals is selected from two Perfluorodipropionyl peroxides, two perfluor butyryl superoxide, two perfluorocyclohexyl acyl peroxides, two perfluor hexanoyl superoxide or its two or more mixtures formed.
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