CN101851145A - Method for preparing 1,2,3,4-tetrachloro-hexafluoro butane - Google Patents
Method for preparing 1,2,3,4-tetrachloro-hexafluoro butane Download PDFInfo
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Abstract
The invention discloses a method for preparing 1,2,3,4-tetrachloro-hexafluoro butane. In the presence of an oxygen-containing organic compound catalyst, 1-iodine-1,2,2-trifluoro-1,2-dichloroethane and zinc particles react to prepare 1,2,3,4-tetrachloro-hexafluoro butane, wherein the oxygen-containing organic compound catalyst is one or a combination of more of alcohol, ketone, ester, ether and amide; the added quantity of the oxygen-containing organic compound catalyst accounts for 5 to 50 weight percent of that of the 1-iodine-1,2,2-trifluoro-1,2-dichloroethane; the particle size of the zinc particles is of between 3 and 6 mm; and the added quantity of the zinc particles accounts for 10 to 50 weight percent of that of the 1-iodine-1,2,2-trifluoro-1,2-dichloroethane. The invention also provides a method for preparing hexachlorobutadiene from the 1,2,3,4-tetrachloro-hexafluoro butane. The hexachlorobutadiene can be used as a polymer monomer, an etching gas or the like.
Description
Technical field
The present invention relates to a kind of 1,2,3, the preparation method of 4-tetrachloro-hexafluoro butane, particularly with 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride and zinc are that raw material prepares 1,2,3 under the oxygen-containing organic compound effect, the method for 4-tetrachloro-hexafluoro butane.
Background technology
Hexachlorobutadiene is to be not only a kind of good polymerization single polymerization monomer, and is a kind of dry etching gas of excellence, can have highly selective and accuracy to carrying out dry etching less than 100nm even narrower width.The GWP of hexachlorobutadiene 290 (CO only in addition
2100 years=1), the atmospheric lifetime phase was a kind of environmentally friendly etching reagent less than 2 days, and the preparation route of exploitation hexachlorobutadiene has far-reaching environment protection significance and economic benefit.1,2,3, the 4-tetrachloro-hexafluoro butane is a kind of very important intermediate of synthetic hexachlorobutadiene, and its preparation route has following several.
U.S. Pat 3046304 and document J.Chem.Soc.1952, P442 and J.Chem.Soc.1952, P4423 have reported with the trifluorochloroethylene to be feedstock production 1,2,3, the synthetic route of 4-tetrachloro-hexafluoro butane.1,2,3 of this method preparation, 4-tetrachloro-hexafluoro butane yield is higher, but reaction needed uses mercury as catalyzer, and toxicity is bigger, unfavorablely uses with industrialization.
English Patent GB798407 and U.S. Pat 2777004 have reported that with 1 2-difluoro Ethylene Dichloride is raw material three-step approach preparation 1,2,3, the synthetic route of 4-tetrachloro-hexafluoro butane.The required temperature of reaction of this method is higher, and need carry out photochemical reaction, and conversion unit is had relatively high expectations.
In the International Patent Application WO 2005023734 of Japan AGC company application, disclose with 1,4-two chloro-2-butylene are feedstock production 1,2,3, the operational path of 4-tetrachloro-hexafluoro butane.This circuit need use the fluorine gas of severe toxicity to carry out fluoridation, has limited industrial applications.
Russ P RU2246477 has reported with 1-iodo-1,2,2-three fluoro-1, and the 2-ethylene dichloride is a starting raw material, in the presence of solvent and halohydrocarbon such as methylene dichloride medium, with zinc powder prepared in reaction 1,2,3, the 4-tetrachloro-hexafluoro butane.In the process of reaction, need to add oxygen containing organic chelate such as Virahol continuously, ether, tetrahydrofuran (THF), ethyl acetate etc., 1,2,3, the yield of 4-tetrachloro-hexafluoro butane is a little more than 70%.
Russ P RU2246478 has reported that with 1-iodo-1, the 2-dichlorotrifluoroethane is a raw material, and with 1-iodo-1,2-dichlorotrifluoroethane and methylene dichloride, zinc powder are mixed with 1,2,3 in organic solvent medium, the 4-tetrachloro-hexafluoro butane.Need equally in the reaction process to add polar organic solvent such as ethyl formate continuously, ethyl acetate and acetone are waited until reaction mixture, 1,2,3, and the yield of 4-tetrachloro-hexafluoro butane is 70-85%.
1 of Russ P RU2294917 report, 2,3,4-tetrachloro-hexafluoro butane preparation technology, under 0-30 ℃,, make 1,2 in the mixture of 2-dichlorotrifluoroethane and methylene dichloride by polar organic solvent such as acetone, ethyl formate and ethyl acetate etc. are added to 1-iodo-1 simultaneously with zinc powder, 3, the 4-tetrachloro-hexafluoro butane.Product yield 94%.
Above-mentioned three Russ P product yields are low, and raw material methylene dichloride toxicity is bigger, needs to drip continuously organic solvent in the reaction, complicated operation, owing to use zinc powder to react violent when just having begun, than difficult control, and side reaction is more simultaneously.
It is that to take off iodine composition be catalyzer for catalysis that the zinc of 3-6mm is formed that Russ P RU2248844 has reported granular size with the ethyl acetate of 0.95%wt and 8-50%wt, with 1-iodo-1, the 2-dichlorotrifluoroethane is a starting raw material, reacted 20-40 hour down at 20-25 ℃, resultant is washed under normal pressure and is promptly got 1 then, 2,3, the preparation method of 4-tetrachloro-hexafluoro butane.Though 1,2,3 of this method preparation, the yield of 4-tetrachloro-hexafluoro butane is higher, about 90-98%, and this speed of response is slow, and long reaction time has also produced a large amount of white solids in the reaction process, i.e. Lewis acid, by product increases, to the seriously corroded of reactor.
Summary of the invention
The object of the present invention is to provide a kind of 1,2,3, the preparation method of 4-tetrachloro-hexafluoro butane, raw material 1-iodo-1,2,2-three fluoro-1, the transformation efficiency height of 2-ethylene dichloride, 1,2,3, the selectivity of 4-tetrachloro-hexafluoro butane and yield height, speed of response is fast, and the reaction times is short, and side reaction is few, and range of reaction temperature is wide, no matter all can operate in winter or summer.
For achieving the above object, the invention provides following technical scheme:
Adopt 1-iodo-1,2,2-three fluoro-1, the 2-ethylene dichloride is a raw material, under the oxygen-containing organic compound catalyst action, makes 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride and zinc granule prepared in reaction 1,2,3, the 4-tetrachloro-hexafluoro butane, oxygen-containing organic compound is for being selected from alcohol, ketone, ester, the combination of one or more in ether and the acid amides, its add-on are 1-iodo-1,2,2-three fluoro-1,5～50% (weight) of 2-ethylene dichloride add-on, the particle diameter of used zinc granule is about 3～6mm, add-on is a 1-iodo-1,2,2-three fluoro-1,10～50% (weight) of 2-ethylene dichloride add-on.
The add-on of oxygen-containing organic compound is crossed the low catalytic efficiency that can make and is reduced, and speed of response slows down, thereby makes the reaction times prolong, and makes that simultaneously side reaction increases.So the add-on of oxygen-containing organic compound is preferably 1-iodo-1,2,2-three fluoro-1,5～50% (weight) of 2-ethylene dichloride add-on, more preferably 10～20% (weight).
There is influence in the kind of oxygen-containing organic compound equally to catalytic effect of the present invention, oxygen-containing organic compound is preferably: alcohol is preferably methyl alcohol and/or ethanol, ketone is preferably acetone and/or butanone, ester is preferably and is methyl-formiate and/or ethyl acetate, ether is preferably 1, the 4-dioxane, acid amides is preferably N, dinethylformamide (DMF).Especially preferred oxygen-containing organic compound is an ethyl acetate.
Zinc is as another reaction raw materials, and its form and consumption are also influential to reaction.If when using pulverous zinc, exothermic heat of reaction is violent, the by product of reaction side reaction and generation is more, wayward, so zinc preferably adopts particulate state, size is about 3～6mm, its add-on is preferably 1-iodo-1,2,2-three fluoro-1,10～50% (weight) of 2-ethylene dichloride add-on, more preferably the 1-iodo-1,2,2-three fluoro-1,20～30% (weight) of 2-ethylene dichloride add-on.
Of the present invention 1,2,3, the preparation method of 4-tetrachloro-hexafluoro butane all can operate in wide temperature range, and preferred temperature of reaction is 0～45 ℃, and more preferably 5～30 ℃, preferred especially 15～25 ℃.
Among the present invention by 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the reaction times of 4-tetrachloro-hexafluoro butane is shorter, can finish just can finish in the reaction, particularly 5～10h more abundant in common 3～20h.Obviously short than the reaction times in the prior art report.
It is a kind of by 1-iodo-1,2 that the present invention also provides, 2-three fluoro-1, and 2-ethylene dichloride preparation 1,2,3, the processing method of 4-tetrachloro-hexafluoro butane comprises the steps:
(1) in reactor, adds 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride and oxygen-containing organic compound, described oxygen-containing organic compound are selected from ethyl acetate, ethanol and the acetone one or more combination, and its add-on is a 1-iodo-1,2,2-three fluoro-1,5～50% (weight) of 2-ethylene dichloride add-on, and fully stir;
(2) add zinc granule toward reactor in 0.2～3h, size is 3～6mm in batches, and add-on is a 1-iodo-1,2,2-three fluoro-1,10～50% (weight) of 2-ethylene dichloride add-on;
(3) reactor temperature is controlled under 0～45 ℃, makes 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride and zinc granule reaction 5～10h;
(4) after reaction finishes the solution in the reactor being inclined washing, isolates lower floor's organic phase and promptly gets 1,2,3, the 4-tetrachloro-hexafluoro butane.
For avoiding producing in the reaction process salt of zinc halide, this processing method preferably adds entry in above-mentioned processing step (1), with the zinc halide salts that produces in the solubilizing reaction process, avoid its adhering on zinc granule, thereby the increase reaction raw materials contacts with zinc granule, help successful reaction and carry out, and avoid the generation of side reaction simultaneously.The present invention is not particularly limited the kind of water, as long as can the dissolvingization zinc salt, but deionized water preferably, for making the amount that when improving reaction efficiency, reduces the three wastes, the consumption of preferred water is a 1-iodo-1,2,2-three fluoro-1,5～40% (weight) of 2-ethylene dichloride, further preferred 10～25% (weight).
The joining day of zinc granule and adding mode are also influential to reaction, be preferably in to add 1-iodo-1,2, and 2-three fluoro-1, behind 2-ethylene dichloride and the oxygen-containing organic compound, 0.2～3h adds in batches, especially adds better in 0.5～1.5h while stirring in batches.
It is a kind of by above-mentioned 1,2,3 that the present invention also provides, and the 4-tetrachloro-hexafluoro butane prepares the method for hexachlorobutadiene, comprises the steps:
(1) in reactor, adds organic solvent and zinc powder, reactor heating;
(2) when reactor temperature reaches 50～80 ℃, in reactor, add 1,2,3, the 4-tetrachloro-hexafluoro butane, and remain on continuation reaction 2～6h in this temperature range;
The consumption of organic solvent and 1,2,3, the weight ratio of the add-on of 4-tetrachloro-hexafluoro butane is 0.5: 1～5: 1, the consumption of zinc powder and 1,2,3, the weight ratio of the add-on of 4-tetrachloro-hexafluoro butane is 0.3: 1～3.5: 1, collects the hexachlorobutadiene gas that generates with gas holder in the reaction process, and cooling makes hexachlorobutadiene gas become liquid state.
Above-mentioned organic solvent is preferably ethanol, 1, the combination of one or more in 4-dioxane, propyl alcohol and the tetrahydrofuran (THF), special preferred alcohol.The consumption of organic solvent and 1,2,3, the weight ratio of the add-on of 4-tetrachloro-hexafluoro butane be preferably 1.0: 1～and 2.5: 1, the consumption of zinc powder and 1,2,3, the weight ratio of the add-on of 4-tetrachloro-hexafluoro butane is preferably 0.3: 1～and 1.6: 1.
Above-mentioned temperature of reaction is preferably 60～70 ℃, and the reaction times is preferably 4～5h.
Embodiment
Below by embodiment the present invention is specifically described.Following examples only are used for the present invention is further specified, and can not be interpreted as limiting the scope of the invention.
Embodiment 11, and 2,3, the preparation of 4-tetrachloro-hexafluoro butane
In the 100ml there-necked flask, add ethyl acetate 1g, water 1g and 1-iodo-1,2-dichlorotrifluoroethane 7g fully stirs, control reaction temperature adds zinc granule 2g (3-6mm) at 20-25 ℃ in batches in 1h, the about 12h of reaction under 25 ℃ of temperature of reaction is after reaction finishes, reaction solution inclined washing, isolates lower floor, obtains 1,2,3, the 4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 99.1%, 1,2,3,4-tetrachloro-hexafluoro butane yield 92.9%.
Embodiment 21, and 2,3, the preparation of 4-tetrachloro-hexafluoro butane
In the 100ml there-necked flask, add ethyl acetate 1g and 1-iodo-1,2-dichlorotrifluoroethane 7g fully stirs, control reaction temperature adds zinc granule 2g (3-6mm) at 20-25 ℃ in batches in 1h, the about 6h of reaction under 25 ℃ of temperature of reaction is after reaction finishes, reaction solution inclined washing, isolates lower floor, obtains 1,2,3, the 4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 99.0%, 1,2,3,4-tetrachloro-hexafluoro butane yield 87.3%.
Embodiment 31, and 2,3, the preparation of 4-tetrachloro-hexafluoro butane
In the 100ml there-necked flask, add dehydrated alcohol 1g and 1-iodo-1,2-dichlorotrifluoroethane 7g fully stirs, control reaction temperature adds zinc granule 2g (3-6mm) at 20-25 ℃ in batches in 1.5h, the about 6h of reaction under 25 ℃ of temperature of reaction is after reaction finishes, reaction solution inclined washing, isolates lower floor, obtains 1,2,3, the 4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 97.3%, 1,2,3,4-tetrachloro-hexafluoro butane yield 84.5%.
Embodiment 41, and 2,3, the preparation of 4-tetrachloro-hexafluoro butane
In the 100ml there-necked flask, add ethyl acetate 2.4g, water 2.8g, 1-iodo-1,2-dichlorotrifluoroethane 28g fully stirs, and control reaction temperature is at 18-30 ℃, add zinc granule 7g (3-6mm) in 1h, the about 11h of reaction under 20 ℃ of temperature of reaction is after reaction finishes in batches, reaction solution inclined washing, isolates lower floor, obtains 1,2,3, the 4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 97.3%, yield 88%.
Embodiment 51, and 2,3, the preparation of 4-tetrachloro-hexafluoro butane
In the 100ml there-necked flask, add ethyl acetate 0.35g, water 0.35g and 1-iodo-1,2-dichlorotrifluoroethane 7g fully stirs, control reaction temperature adds zinc granule 0.7g (3-6mm) at 20-25 ℃ in batches in 1.5h, the about 12h of reaction under 15 ℃ of temperature of reaction is after reaction finishes, reaction solution inclined washing, isolates lower floor, obtains 1,2,3, the 4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 70.5%, 1,2,3,4-tetrachloro-hexafluoro butane yield 62.3%.
Embodiment 61, and 2,3, the preparation of 4-tetrachloro-hexafluoro butane
In the 100ml there-necked flask, add ethyl acetate 1.4g, water 1.75g and 1-iodo-1,2-dichlorotrifluoroethane 7g fully stirs, control reaction temperature adds zinc granule 2.1g (3-6mm) at 20-25 ℃ in batches in 0.5h, the about 10h of reaction under 25 ℃ of temperature of reaction is after reaction finishes, reaction solution inclined washing, isolates lower floor, obtains 1,2,3, the 4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 99.0%, 1,2,3,4-tetrachloro-hexafluoro butane yield 91.8%.
Embodiment 71, and 2,3, the preparation of 4-tetrachloro-hexafluoro butane
In the 100ml there-necked flask, add ethyl acetate 3.5g, water 2.8g and 1-iodo-1,2-dichlorotrifluoroethane 7g fully stirs, control reaction temperature adds zinc granule 3.5g (3-6mm) at 20-25 ℃ in batches in 1.5h, the about 6h of reaction under 30 ℃ of temperature of reaction is after reaction finishes, reaction solution inclined washing, isolates lower floor, obtains 1,2,3, the 4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 98.1%, 1,2,3,4-tetrachloro-hexafluoro butane yield 88.0%.
Simultaneous test
In the 100ml there-necked flask, add ethyl acetate 0.2g and 1-iodo-1,2-dichlorotrifluoroethane 7g fully stirs, control reaction temperature adds zinc granule 2g (3-6mm) at 20-25 ℃ in batches in 1h, the about 6h of reaction under 25 ℃ of temperature of reaction is after reaction finishes, reaction solution inclined washing, isolates lower floor, obtains 1,2,3,4-tetrachloro-hexafluoro butane, 1-iodo-1,2-dichlorotrifluoroethane transformation efficiency 7.1%, 1,2,3,4-tetrachloro-hexafluoro butane selectivity 20.3%, its yield is 1.4%.
The preparation of embodiment 8 hexachlorobutadienes
In the 250mL there-necked flask, add dehydrated alcohol 40g, zinc powder 16.3g, heating when temperature of reaction is 65 ℃, drips 1,2,3,4-tetrachloro perfluorinated butane 30.4g, drip the back and continue reaction 4.5h, 1,2,3,4-tetrachloro perfluorinated butane transformation efficiency is 100%, and the yield of hexachlorobutadiene is 98.2%, the hexachlorobutadiene selectivity is 98.2%, and its purity is 98.2%.
The preparation of embodiment 9 hexachlorobutadienes
In the 250mL there-necked flask, add dehydrated alcohol 15.2g, zinc powder 9.1g, heating when temperature of reaction is 50 ℃, drips 1,2,3,4-tetrachloro perfluorinated butane 30.4g, drip the back and continue reaction 6h, 1,2,3,4-tetrachloro perfluorinated butane transformation efficiency is 99.9%, and the yield of hexachlorobutadiene is 97.8%, the hexachlorobutadiene selectivity is 98.0%, and its purity is 98.0%.
The preparation of embodiment 10 hexachlorobutadienes
In the 250mL there-necked flask, add 1,4-dioxane 30.4g, zinc powder 48.6g, heating is when temperature of reaction is 80 ℃, drip 1,2,3,4-tetrachloro perfluorinated butane 30.4g drips the back and continues reaction 5h, 1,2,3,4-tetrachloro perfluorinated butane transformation efficiency is 100%, the yield of hexachlorobutadiene is 97.8%, and the hexachlorobutadiene selectivity is 97.8%, and its purity is 97.8%.
The preparation of embodiment 11 hexachlorobutadienes
In the 250mL there-necked flask, add anhydrous propyl alcohol 76g, zinc powder 106.4g, heating when temperature of reaction is 70 ℃, drips 1,2,3,4-tetrachloro perfluorinated butane 30.4g, drip the back and continue reaction 5h, 1,2,3,4-tetrachloro perfluorinated butane transformation efficiency is 99.8%, and the yield of hexachlorobutadiene is 97.8%, the hexachlorobutadiene selectivity is 98.0%, and its purity is 98.0%.
The preparation of embodiment 12 hexachlorobutadienes
In the 250mL there-necked flask, add anhydrous tetrahydro furan 152g, zinc powder 30.4g, heating when temperature of reaction is 60 ℃, drips 1,2,3,4-tetrachloro perfluorinated butane 30.4g, drip the back and continue reaction 5.5h, 1,2,3,4-tetrachloro perfluorinated butane transformation efficiency is 99.0%, and the yield of hexachlorobutadiene is 96.5%, the hexachlorobutadiene selectivity is 97.5%, and its purity is 97.5%.
From the foregoing description as can be seen, 1 of the present invention's preparation, 2,3,4-tetrachloro-hexafluoro butane method compared to existing technology, obvious feed stock conversion, selectivity of product and yield height, and speed of response is fast, and the reaction times is short, and side reaction is few, simultaneously range of reaction temperature is wide, in winter or all can operate summer.
The present invention simultaneously prepares the method for hexachlorobutadiene, and not only operating process is simple, and feed stock conversion, product yield, selectivity and purity are all very high.
Claims (15)
1. one kind by 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method of 4-tetrachloro-hexafluoro butane is characterized in that making 1-iodo-1 in the presence of the oxygen-containing organic compound catalyzer, 2,2-three fluoro-1,2-ethylene dichloride and zinc granule prepared in reaction 1,2,3, the 4-tetrachloro-hexafluoro butane, described oxygen-containing organic compound is selected from alcohol, ketone, ester, the combination of one or more in ether and the acid amides, its add-on is a 1-iodo-1,2,2-three fluoro-1,5～50% (weight) of 2-ethylene dichloride add-on, described zinc granule particle diameter is 3～6mm, and add-on is a 1-iodo-1,2,2-three fluoro-1,10～50% (weight) of 2-ethylene dichloride add-on.
2. described by 1-iodo-1,2 according to claim 1,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane, the add-on that it is characterized in that described oxygen-containing organic compound is a 1-iodo-1,2,2-three fluoro-1,10～20% (weight) of 2-ethylene dichloride add-on.
3. described by 1-iodo-1,2 according to claim 1,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane, the add-on that it is characterized in that described zinc granule is a 1-iodo-1,2,2-three fluoro-1,20～30% (weight) of 2-ethylene dichloride add-on.
4. described by 1-iodo-1,2 according to claim 1,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method of 4-tetrachloro-hexafluoro butane, it is characterized in that described alcohol is methyl alcohol and/or ethanol, described ketone is acetone and/or butanone, and described ester is methyl-formiate and/or ethyl acetate, described ether is 1,4-dioxane, described acid amides are N, dinethylformamide (DMF).
5. described by 1-iodo-1,2 according to claim 1,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane is characterized in that temperature of reaction is 0～45 ℃.
6. described by 1-iodo-1,2 according to claim 5,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane is characterized in that temperature of reaction is 5～30 ℃.
7. described by 1-iodo-1,2 according to claim 6,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane is characterized in that temperature of reaction is 15～25 ℃.
8. one kind by 1-iodo-1,2,2-three fluoro-1, and 2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane is characterized in that comprising following step:
(1) in reactor, adds 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride and oxygen-containing organic compound, described oxygen-containing organic compound are selected from ethyl acetate, ethanol and the acetone one or more combination, and its add-on is a 1-iodo-1,2,2-three fluoro-1,5～50% (weight) of 2-ethylene dichloride add-on, and fully stir;
(2) add zinc granule toward reactor in 0.2～3h, size is 3～6mm in batches, and add-on is a 1-iodo-1,2,2-three fluoro-1,10～50% (weight) of 2-ethylene dichloride add-on;
(3) reactor temperature is controlled under 0～45 ℃, makes 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride and zinc granule reaction 5～10h;
(4) after reaction finishes the solution in the reactor being inclined washing, isolates lower floor's organic phase and promptly gets 1,2,3, the 4-tetrachloro-hexafluoro butane.
9. described by 1-iodo-1,2 according to claim 8,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane is characterized in that adding entry in described step (1).
10. described by 1-iodo-1,2 according to claim 9,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane, the add-on that it is characterized in that water is a 1-iodo-1,2,2-three fluoro-1,5～40% (weight) of 2-ethylene dichloride.
11. described according to claim 10 by 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane, the add-on that it is characterized in that water is a 1-iodo-1,2,2-three fluoro-1,10～25% (weight) of 2-ethylene dichloride.
12. described according to claim 8 by 1-iodo-1,2,2-three fluoro-1,2-ethylene dichloride preparation 1,2,3, the method for 4-tetrachloro-hexafluoro butane is characterized in that adding zinc granule while stirring toward reactor in 0.5～1.5h in described step (2) in batches.
13. one kind by claim 1 or 8 described 1,2,3, the 4-tetrachloro-hexafluoro butane prepares the method for hexachlorobutadiene, it is characterized in that comprising following step:
(1) in reactor, adds organic solvent and zinc powder, reactor heating;
(2) when reactor temperature reaches 50～80 ℃, in reactor, add 1,2,3, the 4-tetrachloro-hexafluoro butane, and remain on continuation reaction 2～6h in this temperature range;
The consumption of described organic solvent and 1,2,3, the weight ratio of the add-on of 4-tetrachloro-hexafluoro butane is 0.5: 1～5: 1, the consumption of described zinc powder and 1,2,3, the weight ratio of the add-on of 4-tetrachloro-hexafluoro butane is 0.3: 1～3.5: 1, collects the hexachlorobutadiene gas that generates with gas holder in the reaction process, and cooling makes hexachlorobutadiene gas become liquid state.
14. described by claim 1 or 8 described 1,2,3 according to claim 13, the 4-tetrachloro-hexafluoro butane prepares the method for hexachlorobutadiene, it is characterized in that temperature of reaction is 60～70 ℃ in the described step (2), continues reaction 4～5h.
15. it is described by claim 1 or 8 described 1,2,3 according to claim 13, the 4-tetrachloro-hexafluoro butane prepares the method for hexachlorobutadiene, it is characterized in that described organic solvent is selected from ethanol, 1, the combination of one or more in 4-dioxane, propyl alcohol and the tetrahydrofuran (THF), the consumption of organic solvent and 1,2,3, the weight ratio of 4-tetrachloro-hexafluoro butane is 1.0: 1～2.5: 1, described zinc powder and 1,2,3, the weight ratio of 4-tetrachloro-hexafluoro butane is 0.3: 1～1.6: 1.
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Cited By (7)
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| CN106336342A (en) * | 2016-07-19 | 2017-01-18 | 浙江博瑞电子科技有限公司 | Method for preparing hexafluorobutadiene from iodine and chlorine |
| CN108083972A (en) * | 2017-12-28 | 2018-05-29 | 浙江博瑞电子科技有限公司 | A kind of method of reactive distillation synthesis hexachlorobutadiene |
| CN109651074A (en) * | 2018-11-20 | 2019-04-19 | 西安近代化学研究所 | A kind of preparation method of 1,2,3,4- tetrachloro-hexafluoro butane |
| CN110092704A (en) * | 2018-01-31 | 2019-08-06 | 上海汇友精密化学品有限公司 | The preparation method of one kind 1,1,1- trichorotrifluoroethane |
| KR20210008518A (en) * | 2018-06-22 | 2021-01-22 | 쇼와 덴코 가부시키가이샤 | Method for producing hexafluoro-1,3-butadiene |
| CN112250541A (en) * | 2020-09-30 | 2021-01-22 | 中国船舶重工集团公司第七一八研究所 | Preparation method of hexafluorobutadiene |
| CN113004118A (en) * | 2021-02-07 | 2021-06-22 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing hexafluorobutadiene by using high-boiling point strong-polarity solvent |
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| CN106336342A (en) * | 2016-07-19 | 2017-01-18 | 浙江博瑞电子科技有限公司 | Method for preparing hexafluorobutadiene from iodine and chlorine |
| CN108083972A (en) * | 2017-12-28 | 2018-05-29 | 浙江博瑞电子科技有限公司 | A kind of method of reactive distillation synthesis hexachlorobutadiene |
| CN110092704A (en) * | 2018-01-31 | 2019-08-06 | 上海汇友精密化学品有限公司 | The preparation method of one kind 1,1,1- trichorotrifluoroethane |
| CN110092704B (en) * | 2018-01-31 | 2021-08-27 | 上海汇友精密化学品有限公司 | Preparation method of 1, 1, 1-trichlorotrifluoroethane |
| KR20210008518A (en) * | 2018-06-22 | 2021-01-22 | 쇼와 덴코 가부시키가이샤 | Method for producing hexafluoro-1,3-butadiene |
| KR102644481B1 (en) | 2018-06-22 | 2024-03-07 | 가부시끼가이샤 레조낙 | Method for producing hexafluoro-1,3-butadiene |
| CN109651074A (en) * | 2018-11-20 | 2019-04-19 | 西安近代化学研究所 | A kind of preparation method of 1,2,3,4- tetrachloro-hexafluoro butane |
| CN112250541A (en) * | 2020-09-30 | 2021-01-22 | 中国船舶重工集团公司第七一八研究所 | Preparation method of hexafluorobutadiene |
| CN113004118A (en) * | 2021-02-07 | 2021-06-22 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing hexafluorobutadiene by using high-boiling point strong-polarity solvent |
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