CN102675033A - Synthesis method of brominated fluoroalkane - Google Patents
Synthesis method of brominated fluoroalkane Download PDFInfo
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- CN102675033A CN102675033A CN2012101211250A CN201210121125A CN102675033A CN 102675033 A CN102675033 A CN 102675033A CN 2012101211250 A CN2012101211250 A CN 2012101211250A CN 201210121125 A CN201210121125 A CN 201210121125A CN 102675033 A CN102675033 A CN 102675033A
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- bromine
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- fluoric ether
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Abstract
The invention discloses a synthesis method of brominated fluoroalkane, which comprises the following steps: carrying out gas-phase reaction on perfluoro-olefin and bromine at 20-200 DEG C under lighting conditions, washing and distilling to obtain the high-purity brominated fluoroalkane, wherein the mol ratio of the perfluoro-olefin to the bromine is (0.8-5):1, and the contact time of the perfluoro-olefin and the bromine is 1-60 seconds. The invention can obtain high-purity brominated fluoroalkane at high yield, has the advantages of high safety, high economic efficiency and the like, and can implement continuous production.
Description
Technical field
The present invention relates to a kind of compound method of brominated fluoric ether, relate in particular to the compound method for preparing brominated fluoric ether by tetrafluoroethylene or R 1216.
Background technology
Brominated fluoric ether is one type of important fluoro-containing intermediate, can be used for the synthetic of novel fluorine medicine, agricultural chemicals and tensio-active agent etc.As 1,2-dibromo HFC-236fa can be as the raw material of preparation organic synthesis building block 2-bromine HFC-227, and 2-bromine HFC-227 can be used for substituting 2-iodine HFC-227 synthesizing efficient agricultural chemicals.1, the 2-dibromotetrafluoroethane can be used for synthetic 4-bromo-3,3,4,4-tetrafluoro butylene etc., and 4-bromo-3,3,4, and 4-tetrafluoro butylene is a kind of compound that can be used as a friendization monomer component of multiple fluoroelastomer preferably.
Patent HU 40599A2 has reported that a kind of tetrafluoroethylene that produces with useless Teflon Pintsch process is a raw material, and the tetrafluoroethylene that cracking is produced is passed in the dichloroethane solution of bromine, reacts down at 40～50 ℃ to obtain 1,2-dibromotetrafluoroethane, yield 65%.This method is reacted in liquid phase, needs solvent, increases the separating step of solvent, and yield is also lower.
Patent DE102005005774 has reported that R 1216 and elemental bromine are reacted and has obtained 1,2-dibromo HFC-236fa in liquid phase.Therefore a large amount of bromine because elemental bromine severe toxicity, liquid phase reaction need prestore in reaction member exists bigger potential safety hazard.
Patent CN1498881A discloses a kind of technology of reacting in the liquid element bromine that R 1216 is passed into.This patent is not mentioned light source, yet under same condition, R 1216 and elemental bromine are not having under the situation of light source, and speed of response is extremely slow, does not in fact have observable reaction.
Summary of the invention
There is poor stability to prior art, is difficult for the quantity-produced shortcoming, the purpose of this invention is to provide a kind of compound method of brominated fluoric ether.Through the method that the present invention adopts, elemental bromine and Fluorine containing olefine can react apace, and reaction preference is high; The total amount of bromine is few in reaction member simultaneously; Reactor drum itself need not to bear self static pressure of elemental bromine in the liquid phase reaction, greatly reduces DESIGN OF REACTOR and requires and manufacture difficulty, is easy to amplify; Security is good, is convenient to advantages such as serialization production.
For realizing above-mentioned purpose, the present invention provides following scheme.
The invention provides a kind of preparation method of brominated fluoric ether.It is perfluoro alkene and bromine; Under 20 ℃～200 ℃, illumination condition, carry out gas-phase reaction; Obtain highly purified brominated fluoric ether through washing, distillation again, perfluoro alkene is 0.8～5: 1 with the molar equivalent ratio of bromine, and be 1s～60s the duration of contact of perfluoro alkene and bromine.
When elemental bromine and perfluoro alkene carried out addition reaction, high temperature helps reaction to carry out, but temperature of reaction is too high, can make reaction wayward, increases the difficulty that reactor design is made simultaneously.Therefore temperature of reaction is 20 ℃～200 ℃, is preferably 40 ℃～100 ℃.
Elemental bromine can get into reactor drum through heating vaporization back, also can in the liquid bromine, feed fluorinated olefin, carries out bubbling, elemental bromine is brought in the reactor drum reacts.
The mol ratio of fluorinated olefin and elemental bromine influences reaction effect, and fluorinated olefin and bromine mol ratio are little, and bromine is difficult for reacting completely; Increase post-processing difficulty, fluorinated olefin and bromine mol ratio are big, and fluorinated olefin is excessive greatly; Bromine reaction is complete; But increase the fluorinated olefin internal circulating load, increase machine utilization, reduced the device processes amount.Therefore the mol ratio of fluorinated olefin and elemental bromine is 0.8～5: 1, is preferably 1～1.5: 1.
Light has katalysis to reaction, is not having light and is not having under other catalyzer condition, and elemental bromine is extremely slow with the perfluoro olefine reaction that the present invention relates to, but reaction can be carried out fast under the irradiation of light.Light wavelength is chosen as the arbitrary wavelength between 200nm～600nm, from security consideration, and the visible light of preferred 400～600nm scope.The selection of light source, main wave band get final product in 400～600nm scope, and from the aspect consideration that is easy to get, incandescent light, floodlight, tungsten-iodine lamp are better as light source, also can utilize sunshine as light source.Light source can be placed on outside the reactor drum, also can be placed in the reactor drum.
The duration of contact of perfluoro alkene and bromine is also more important, and duration of contact is short, and elemental bromine, perfluoro olefine reaction are incomplete, increase post-processing difficulty; Duration of contact is long, and elemental bromine, perfluoro olefine reaction are complete, but plant factor reduces, thus the residence time be 1s～60s, be preferably 5s～20s.
The reaction of perfluoro alkene and bromine can be carried out under decompression, normal pressure and pressurized conditions, considers from aspect such as easy to operate, is preferably normal pressure.
Embodiment
Embodiment 1
In the silica tube of internal diameter 27mm, long 400mm; The irradiation of floodlight that external main wavelength is a visible light is that the speed of 15s feeds R 1216 and bromine vapor with the R 1216 residence time, and the mol ratio of R 1216 and bromine is 1.2: 1; The silica tube temperature is controlled at 100 ℃; The transformation efficiency of bromine is 99.8%, 1, and the selectivity of 2-dibromo HFC-236fa is 99.6%.Reaction back gas is through condensation, can obtain purity after washing, the distillation and be 99.8% 1,2-dibromo HFC-236fa.
Embodiment 2
In the silica tube of internal diameter 32mm, long 600mm; The irradiation of built-in tungsten-iodine lamp is that the speed of 60s feeds R 1216 and bromine vapor with the R 1216 residence time, and the mol ratio of R 1216 and bromine is 5: 1; The silica tube temperature is controlled at 20 ℃; The transformation efficiency of bromine is 99.5%, 1, and the selectivity of 2-dibromo HFC-236fa is 99.8%.
Embodiment 3
In the silica tube of internal diameter 27mm, long 400mm; As light source, is that the speed of 1s feed R 1216 and bromine vapor with the R 1216 residence time with sunshine, and the mol ratio of R 1216 and bromine is 5: 1; The silica tube temperature is controlled at 200 ℃; The transformation efficiency of bromine is 95.5%, 1, and the selectivity of 2-dibromo HFC-236fa is 99.8%.
Embodiment 4
In the silica tube of internal diameter 27mm, long 400mm; The irradiation of external incandescent light is that the speed of 30s feeds tetrafluoroethylene and bromine vapor with the tetrafluoroethylene residence time, and the mol ratio of tetrafluoroethylene and bromine is 1.5: 1; The silica tube temperature is controlled at 60 ℃; The transformation efficiency of bromine is 99.9%, 1, and the selectivity of 2-dibromotetrafluoroethane is 99.8%.
Embodiment 5
In the silica tube of internal diameter 27mm, long 400mm; The irradiation of external tungsten-iodine lamp is that the speed of 20s feeds R 1216 and bromine vapor with the R 1216 residence time, and the mol ratio of R 1216 and bromine is 0.8: 1; The silica tube temperature is controlled at 80 ℃; The transformation efficiency of R 1216 is 99.8%, 1, and the selectivity of 2-dibromo HFC-236fa is 99.5%.
Claims (8)
1. the invention discloses a kind of compound method of brominated fluoric ether; To be perfluoro alkene and bromine carry out gas-phase reaction under 20 ℃～200 ℃, illumination condition for it; Obtain highly purified brominated fluoric ether through washing, distillation again; The mol ratio of perfluoro alkene and bromine is 0.8～5: 1, and be 1s～60s the duration of contact of perfluoro alkene and bromine.
2. the compound method of a kind of brominated fluoric ether according to claim 1 is characterized in that described brominated fluoric ether is 1,2-dibromotetrafluoroethane or 1,2-dibromo HFC-236fa.
3. the compound method of a kind of brominated fluoric ether according to claim 1 is characterized in that described perfluoro alkene is tetrafluoroethylene or R 1216.
4. the compound method of a kind of brominated fluoric ether according to claim 1 is characterized in that described temperature of reaction is 40 ℃～100 ℃.
5. the compound method of a kind of brominated fluoric ether according to claim 1 is characterized in that described illumination condition is a visible light.
6. the compound method of a kind of brominated fluoric ether according to claim 1 is characterized in that being reflected in the gas phase of perfluoro alkene and bromine carry out.
7. the compound method of a kind of brominated fluoric ether according to claim 1, the mol ratio that it is characterized in that perfluoro alkene and bromine is 1.0～1.5: 1.
8. the compound method of a kind of brominated fluoric ether according to claim 1, be 5s～20s the duration of contact that it is characterized in that perfluoro alkene.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101211250A CN102675033A (en) | 2012-04-11 | 2012-04-11 | Synthesis method of brominated fluoroalkane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101211250A CN102675033A (en) | 2012-04-11 | 2012-04-11 | Synthesis method of brominated fluoroalkane |
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| CN102675033A true CN102675033A (en) | 2012-09-19 |
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| CN2012101211250A Pending CN102675033A (en) | 2012-04-11 | 2012-04-11 | Synthesis method of brominated fluoroalkane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058928A (en) * | 2014-06-19 | 2014-09-24 | 巨化集团技术中心 | Method for increasing production capacity of device in bromine-containing hydrofluoroalkane synthesis |
| CN104591957A (en) * | 2015-02-15 | 2015-05-06 | 浙江环新氟材料股份有限公司 | Method for preparing 1,2-dibromohexafluoropropane |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1315785A (en) * | 1970-08-31 | 1973-05-02 | Kali Chemie Ag | Method of producing tetrafluorodibromoethane |
| JP2000169404A (en) * | 1998-12-11 | 2000-06-20 | Tosoh Corp | Method for brominating fluorine-containing olefins |
| CN1320109A (en) * | 1999-08-23 | 2001-10-31 | 旭硝子株式会社 | Method of treating 1,1:1,3-pentafluoropropane |
| CN1498882A (en) * | 2002-11-11 | 2004-05-26 | Prepn. of polyhalid alkane | |
| CN101979364A (en) * | 2010-09-30 | 2011-02-23 | 浙江环新氟材料股份有限公司 | The preparation method of 2,3,3,3-tetrafluoropropene |
-
2012
- 2012-04-11 CN CN2012101211250A patent/CN102675033A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1315785A (en) * | 1970-08-31 | 1973-05-02 | Kali Chemie Ag | Method of producing tetrafluorodibromoethane |
| JP2000169404A (en) * | 1998-12-11 | 2000-06-20 | Tosoh Corp | Method for brominating fluorine-containing olefins |
| CN1320109A (en) * | 1999-08-23 | 2001-10-31 | 旭硝子株式会社 | Method of treating 1,1:1,3-pentafluoropropane |
| CN1498882A (en) * | 2002-11-11 | 2004-05-26 | Prepn. of polyhalid alkane | |
| CN101979364A (en) * | 2010-09-30 | 2011-02-23 | 浙江环新氟材料股份有限公司 | The preparation method of 2,3,3,3-tetrafluoropropene |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058928A (en) * | 2014-06-19 | 2014-09-24 | 巨化集团技术中心 | Method for increasing production capacity of device in bromine-containing hydrofluoroalkane synthesis |
| CN104058928B (en) * | 2014-06-19 | 2017-11-21 | 巨化集团技术中心 | A kind of method that plant capacity is improved in brominated fluoric ether synthesis |
| CN104591957A (en) * | 2015-02-15 | 2015-05-06 | 浙江环新氟材料股份有限公司 | Method for preparing 1,2-dibromohexafluoropropane |
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Application publication date: 20120919 |