CN102036938A - High selectivity process to make dihydrofluoroalkenes - Google Patents

High selectivity process to make dihydrofluoroalkenes Download PDF

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CN102036938A
CN102036938A CN2008801293981A CN200880129398A CN102036938A CN 102036938 A CN102036938 A CN 102036938A CN 2008801293981 A CN2008801293981 A CN 2008801293981A CN 200880129398 A CN200880129398 A CN 200880129398A CN 102036938 A CN102036938 A CN 102036938A
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weight
alkynes
hydrogen
fluoro
cis
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E·N·斯维林根
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/354—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by hydrogenation

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Abstract

Disclosed is a method for the synthesis of fluorinated alkenes comprising contacting a fluorinated alkyne of the formula R1 CC R2, wherein R1 and R2 are independently selected from CF3, C2F5, C3F7, and C4F9, in a pressure vessel, with a Lindlar catalyst, with substantially one molar equivalent of hydrogen, to make the corresponding cis-alkene of formula R1 CC R2 with high selectivity, wherein said hydrogen is added in portions over a period of time, so as to produce an initial pressure in the pressure in the vessel of no more than about 100 psi.

Description

The high selective method for preparing two HF hydrocarbons
Background information
Open field
The disclosure relates generally to the synthetic of HF hydrocarbon.
Association area is described
Because the Montreal Protocol regulation is progressively stopped using the Chlorofluorocarbons (CFCs) (CFC) and the Hydrochlorofluorocarbons (HCFC) of loss ozonosphere, therefore in the past in decades, the fluorocarbon industry is devoted to seek substitute refrigerant always.The solution of many application is to be used as refrigerant, solvent, fire-fighting medium, bubbling agent and propelling agent with the commercialization of hydrogen fluorohydrocarbon (HFC) compound.These novel cpds, HFC refrigerant for example, wherein HFC-134a is most widely used at present, and has zero ozone depletion potentiality, therefore can not be subjected to since the present regulation of Montreal Protocol with its influence of eliminating gradually.
Except the ozone depletion problem, Global warming is another relevant environmental problems of numerous therewith application.Therefore, need not only satisfy the low-ozone loss standard but also have the composition of low Global warming potentiality.It is believed that some HF hydrocarbon meets this two targets.Therefore, need to provide the preparation method of halohydrocarbon and fluoroolefins, described halohydrocarbon and fluoroolefins do not comprise chlorine, have low Global warming potentiality simultaneously.
Summary of the invention
In one embodiment, described method is the method for synthetic fluorinated olefin, and described method is included in and makes formula R in the pressurized vessel 1-C ≡ C-R 2Fluoridize alkynes, wherein R 1And R 2Be independently selected from CF 3, C 2F 5, C 3F 7And C 4F 9, with lindlar catalyst and basically at the most the hydrogen of a molar equivalent (and comprising a molar equivalent) contact so that highly selective makes formula R 1HC=CHR 2Corresponding cis or trans olefins, wherein said hydrogen added in for some time in batches, so that produce the original pressure that is not more than about 100psi in described container.
In another embodiment, described method is the method for synthetic fluorinated olefin, and described method comprises: make formula R in pressurized vessel 1C ≡ CR 2Fluoridize alkynes, wherein R 1And R 2Be independently selected from CF 3, C 2F 5, C 3F 7And C 4F 9, in solvent with lindlar catalyst and basically the hydrogen of a molar equivalent contact so that highly selective makes formula R 1HC=CH R 2Corresponding cis-form olefin.
In another embodiment, described method is with the method for the synthetic fluorinated olefin of successive processes, in the presence of lindlar catalyst, in reaction zone, in gas phase, makes formula R 1C ≡ C R 2Fluoridize alkynes, wherein R 1And R 2Be independently selected from CF 3, C 2F 5, C 3F 7, and C 4F 9, with equivalent or hydrogen still less contact basically.
Above only property and illustrative purpose presented for purpose of illustration of summary and following detailed Description Of The Invention, rather than limit the invention, the present invention is limited by the appended claims.
Detailed Description Of The Invention
In one embodiment, described method is for passing through selective hydration in the presence of special catalyst, by the method for fluoridizing the synthetic fluorinated olefin of alkynes highly selective accordingly.
Many aspects and embodiment are described in the above, and only are exemplary and nonrestrictive.After running through this specification sheets, the technician it should be understood that without departing from the present invention other aspects and embodiment also are possible.
By reading following detailed Description Of The Invention and claim, the further feature and the beneficial effect of any one or a plurality of embodiments will become apparent.
Before proposing following embodiment details, define or illustrate some terms earlier.
As used herein, term " comprises ", " comprising ", " having " or their any other modification all are intended to contain comprising of nonexcludability.For example, comprise that technology, method, goods or the equipment of key element tabulation needn't only limit to those key elements, but can comprise clearly do not list or this technology, method, goods or equipment institute other key elements of inherent.In addition, unless opposite offering some clarification on arranged, " or " be meant inclusive " or ", rather than refer to exclusiveness " or ".For example, below all satisfy condition A or B:A of any situation be that real (or existence) and B are false (or non-existent), A is that false (or non-existent) and B are real (or existence), and A and B are real (or existence).
Equally, use " one " or " a kind of " to describe key element described herein and component.Doing so only is for convenience, and provides general meaning to scope of the present invention.This description should be understood to include one or at least one, and this odd number also comprises plural number, anticipates unless clearly refer to him in addition.
With the corresponding family in hurdle number employing " new symbol " agreement, be found in " CRC Handbook of Chemistry and Physics " the 81st edition (2000-2001) in the periodic table of elements.
As used herein, reaction zone can be the reaction vessel that is processed by nickel, iron, titanium or their alloy, as United States Patent (USP) 6,540, described in 933, incorporates described document into this paper with way of reference.Also can use the reaction vessel (as metal tube) of these materials.When relating to alloy, it means that nickelalloy comprises about 1% nickel to about 99.9% weight, and iron alloy comprises about 0.2% iron to about 99.8% weight, and titanium alloy comprises about 72% titanium to about 99.8% weight.The noticeable tubing that is to use aforesaid filling lindlar catalyst, it is made by nickel or nickelalloy, as comprises about 40 weight % to those of about 80 weight % nickel, for example Inconel TM600 nickelalloys, Hastelloy TMC617 nickelalloy or Hastelloy TMThe C276 nickelalloy.
Lindlar catalyst is the hydridization palladium catalyst on calcium carbonate carrier, by lead compound deactivation or restriction.Described lead compound can be lead acetate, plumbous oxide or any other suitable lead compound.In one embodiment, catalyzer is by reduction palladium salt in the presence of calcium carbonate serosity, and next the adding by lead compound prepares.In one embodiment, described palladium salt is Palladous chloride.In another embodiment, described catalyzer quinoline deactivation or restriction.The amount of palladium is generally 5% by weight on carrier, but can be any catalytically effective amount.
Unless otherwise defined, otherwise the implication of all scientific and technical terminologies used herein and those skilled in the art's common sense the same.Although also can be used for hereinafter having described suitable method and material in the enforcement or test of embodiment of the present invention with method described herein and materials similar or the method that is equal to and material.Remove the non-quoted physical segment and fall, otherwise all publications that this paper mentions, patent application, patent and other reference all in full way of reference incorporate this paper into.As conflict, then be as the criterion with the included definition of this specification sheets.In addition, material, method and embodiment only are exemplary, are not intended to limit.
In one embodiment, by in the presence of selected catalyzer, make formula R 1C ≡ C R 2Fluoridize alkynes, wherein R 1And R 2Be independently selected from CF 3, C 2F 5, C 3F 7, and C 4F 9, contact synthetic fluorinated olefin with hydrogen.The representational alkynes of fluoridizing comprises and is selected from following alkynes: hexafluoro-2-butyne, octafluoro-valerylene, ten fluoro-2-hexins, ten fluoro-3-hexins, 12 fluoro-2-heptyne, 12 fluoro-3-heptyne, ten tetrafluoros-3-octyne and ten tetrafluoros-4-octyne.
Hexafluoro-2-butyne is easy to by 1,1,1,4,4,4-hexafluoro-2, and 3-two chloro-2-butylene (CFC-1316mxx) obtain with the dechlorination reaction of zinc.CFC-1316mxx is easy to by CF 3CCl 3Make, as U.S. Patent Publication 5,919, disclosed in 994, its disclosure is incorporated this paper into way of reference.Similarly, ten fluoro-3-hexins be easy to by with the dechlorination reaction of zinc, by CF 3CF 2CCl=CClCF 2CF 3Make.Similarly, CF 3CF 2CCl=CClCF 2CF 3By CF 3CF 2CCl 3Make.Similarly, ten fluoro-2-hexins are easy to by CF 3CCl=CClCF 2CF 2CF 3Make described CF 3CCl=CClCF 2CF 2CF 3Be easy to by in the presence of the chlorofluorination Al catalysts with the reaction of tetrafluoroethylene, make by CFC-1316mxx.Octafluoro-valerylene can be by twice dehydrofluorination in the presence of alkali or zeolite, and by 1,1,1,2,2,3,4,5,5, the 5-Decafluoropentane makes, as disclosed in the Japanese Patent 2004292329.
In one embodiment, the catalyzer of described method is a lindlar catalyst.In one embodiment, described catalyst consumption is counted about 0.5 weight % to about 4 weight % by described amount of fluoridizing alkynes.In another embodiment, described catalyst consumption is counted about 1 weight % to about 3 weight % by described amount of fluoridizing alkynes.In another embodiment, described catalyst consumption is counted about 1 weight % to about 2 weight % by described amount of fluoridizing alkynes.
In some embodiments, described being reflected in the solvent carried out.In such embodiment, described solvent is an alcohol.General alcoholic solvent comprises ethanol, Virahol and n-propyl alcohol.In another embodiment, described solvent is fluorocarbon or hydrogen fluorohydrocarbon.General fluorocarbon or hydrogen fluorohydrocarbon comprise 1,1,1,2,2,3,4,5,5,5-Decafluoropentane and 1,1,2,2,3,3,4-seven fluorine pentamethylene.
In one embodiment, described method is carried out with batch processes.
In another embodiment, described method is carried out in gas phase with continuation method.
In one embodiment, fluoridize alkynes and the reaction of hydrogen in the presence of catalyzer and should carry out, add fashionable container pressure increment at every turn and be no more than about 100psi in the mode that adds hydrogen in batches.In another embodiment, the adding of control hydrogen is so that the pressure increase that adds in the container is no more than about 50psi at every turn.In one embodiment, consumed capacity hydrogen at hydrogenation, thus will at least 50% fluoridize alkynes and change into alkene after, hydrogen can join in the remaining reaction by bigger increment.In another embodiment, consumed capacity hydrogen at hydrogenation, thus will at least 60% fluoridize alkynes and change into alkene after, hydrogen can join in the remaining reaction by bigger increment.In another embodiment, consumed capacity hydrogen at hydrogenation, thus will at least 70% fluoridize alkynes and change into alkene after, hydrogen can join in the remaining reaction by bigger increment.In one embodiment, bigger hydrogen adds to increase progressively and can be 300psi.In another embodiment, bigger hydrogen adds to increase progressively and can be 400psi.
In one embodiment, the add-on of hydrogen is that an about molar equivalent is fluoridized alkynes for every mole.In another embodiment, the add-on of hydrogen is about 0.9 mole to about 1.3 moles every mole and fluoridizes alkynes.In another embodiment, the add-on of hydrogen is about 0.95 mole to about 1.1 moles every mole and fluoridizes alkynes.In another embodiment, the add-on of hydrogen is about 0.95 mole to about 1.03 moles every mole and fluoridizes alkynes.
In one embodiment, hydrogenation is carried out at ambient temperature.In another embodiment, hydrogenation is carried out being higher than under the envrionment temperature.In another embodiment, hydrogenation is carried out being lower than under the envrionment temperature.In another embodiment, hydrogenation carries out being lower than under about 0 ℃ temperature.
In an embodiment of continuation method, make the mixture of fluoridizing alkynes and hydrogen by comprising the reaction zone of catalyzer.In one embodiment, hydrogen is about 1: 1 with the mol ratio of fluoridizing alkynes.In another embodiment of continuation method, hydrogen with fluoridize the mol ratio of alkynes less than 1: 1.In another embodiment, hydrogen is about 0.67: 1.0 with the mol ratio of fluoridizing alkynes.
In an embodiment of continuation method, reaction zone keeps envrionment temperature.In another embodiment of continuation method, reaction zone keeps 30 ℃ temperature.In another embodiment of continuation method, reaction zone keeps about 40 ℃ temperature.
In an embodiment of continuation method, keep fluoridizing the flow of alkynes and hydrogen, in reaction zone so that about 30 seconds residence time to be provided.In another embodiment of continuation method, keep fluoridizing the flow of alkynes and hydrogen, in reaction zone so that about 15 seconds residence time to be provided.In another embodiment of continuation method, keep fluoridizing the flow of alkynes and hydrogen, in reaction zone so that about 7 seconds residence time to be provided.
Should be appreciated that reduce because of the raising of fluoridizing alkynes and hydrogen flowing quantity that enters into reaction zone the duration of contact in the reaction zone.Along with the raising of flow, this will increase and fluoridize the amount that alkynes is hydrogenated in the time per unit.Because hydrogenation is heat release, depend on the length of reaction zone and diameter with and heat-sinking capability, under high flow rate more, expectation provides the exterior cooling source to keep required temperature to reaction zone.
In an embodiment of continuation method, the amount of palladium is 5% by weight on the carrier in lindlar catalyst.In another embodiment, in lindlar catalyst on the carrier amount of palladium by weight greater than 5%.In another embodiment, the amount of palladium can be about 5% to about 1% by weight on carrier.
In one embodiment, after method for hydrogenation was finished in batches or continuously, cis-two HF hydrocarbon can reclaim by the method for any routine, comprises for example fractionation.In another embodiment, after method for hydrogenation was finished in batches or continuously, cis-two HF hydrocarbon had enough purity, thereby did not need other purification step.
Embodiment
Notion described herein will further describe in the following example, and described embodiment is not limited in the scope of describing in the claim of the present invention.
Embodiment 1
Embodiment 1 shows the selective hydration of hexafluoro-2-butyne.
5g Lin Dele (with the Pd of the CaCO3 of lead poisoningization last 5%) catalyzer is joined in the 1.3L vibration bomb.480g (2.96 moles) hexafluoro-2-butyne is joined in the described vibration bomb.With reactor cooling (78 ℃) and emptying.After the vibration bomb rises to room temperature, slowly add H with the increment that is no more than Δ p=50psi 2Totally 3 moles of H 2Join in the reactor.The gas chromatographic analysis of crude product shows that mixture is by CF 3C ≡ CCF 3(0.236%), CF 3CH=CHCF 3Trans-isomer(ide) (0.444%), saturated CF 3CH 2CH 2CF 3(1.9%), CF 2=CHCl (from the impurity of raw material butine, 0.628%), CF 3CH=CHCF 3Cis-isomeride (96.748%) form.Distillation obtains the pure cis-CF of 287g (59% yield) 100% 3CH=CHCF 3(33.3 ℃ of boiling points).MS：164[MI]，145[M-19]，95[CF 3CH＝CH]，69[CF 3]。NMR H 1: 6.12ppm (multiplet), F 19:-60.9ppm (triplet, J=0.86Hz)
Embodiment 2
Embodiment 2 shows the hydrogenation of the hexafluoro-2-butyne that uses 2 weight % catalyzer.
In 1.3l Hastelloy reactor, add the 10g lindlar catalyst.Then 500g (3.08 moles) hexafluoro-2-butyne is joined in the reactor.Little increment with 50-100psi adds hydrogen.The hydrogen (3.08 moles) that adds 1100psi altogether.During 6.5 hours, hydrogen on average is consumed with the speed of 150psi/hr.The gas chromatographic analysis of product shows that 93.7% hexafluoro butine is converted to cis-CF 3CH=CHCF 3, and 4.8% saturated CF 3CH 2CH 2CF 3
Embodiment 3
Embodiment 3 shows the hydrogenation of the octafluoro-valerylene that uses 1 weight % catalyzer.
In 1.3l Hastelloy reactor, add the 10g lindlar catalyst.Then, 650g (3.06 moles) octafluoro-valerylene is joined in the reactor.Slowly add hydrogen with the increment that is no more than Δ p=50psi then.To amount to 3 moles of H 2Join in the reactor.The gas chromatographic analysis of product shows that octafluoro-valerylene of 96.7% is converted to cis-CF 3CH=CHCF 2CF 3, and 1.8% saturated CF 3CH 2CH 2CF 2CF 3
Embodiment 4
Embodiment 4 shows the hydrogenation of the hexafluoro-2-butyne that uses 1 weight % catalyzer.
In 1.3l Hastelloy reactor, add the 5g lindlar catalyst.Then 500g (3.08 moles) hexafluoro-2-butyne is joined in the reactor.Little increment with 30-50psi adds hydrogen.Add 1414psi (4.0 mol of hydrogen) altogether.During 28 hours, hydrogen on average is consumed with the speed of 50psi/hr.The analysis of products therefrom mixture demonstrates cis-CF of 80.7% 3CH=CHCF 3With 19.3% saturated CF 3CH 2CH 2CF 3
Embodiment 5
Embodiment 5 shows the hydrogenation of ten fluoro-3-hexins.
In 1.3l Hastelloy reactor, add the 8g lindlar catalyst.Then 800g (3.05 moles) ten fluoro-3-hexins are joined in the reactor.Slowly add hydrogen with the increment that is no more than Δ p=50psi then.To amount to 3 moles of H2 joins in the reactor.The gas chromatographic analysis of product shows that 96.7% ten fluoro-3-hexins are converted to cis-CF 3CF 2CH=CHCF 2CF 3, and 1.8% saturated CF 3CF 2CH 2CH 2CF 2CF 3
Embodiment 6
Embodiment 6 shows the continuous hydrogenation method of hexafluoro-2-butyne, to make cis-and anti-form-1,1,1,4,4, the mixture of 4-hexafluoro-2-butylene.
To long by 10 " and have 5 " O.D. (external diameter) and 0.35 " in the Hastelloy tubular reactor of wall thickness, filling 10g lindlar catalyst.With hydrogen stream described catalyzer is regulated 24 hours down at 70 ℃.Under 30 ℃,, make the hexafluoro-2-butyne stream and the hydrogen stream of 1: 1 mol ratio pass through described reactor then to be enough to provide the flow of 30 second duration of contact.The product mixtures that leaves behind the reactor is collected in the cold-trap, and uses gc analysis.Find that product mixtures comprises CF 3CH=CHCF 3(cis) (72%), CF 3CH=CHCF 3(trans) (8.8%), CF 3CH 2CH 2CF 3(7.8%) and CF 3C ≡ CCF 3(3.3%).
Embodiment 7
Embodiment 7 shows the continuous hydrogenation method of the hexafluoro-2-butyne with 15 second duration of contact.
According to the method for embodiment 6, different is, regulates flow so that duration of contact of 15 seconds to be provided.Described reaction heat release slightly, reactor are warming up to 35-36 ℃.The product mixtures analysis illustrates CF 3CH=CHCF 3(cis) (72%), CF 3CH=CHCF 3(trans) (9.3%), CF 3CH 2CH 2CF 3(11.3%) and CF 3C ≡ CCF 3(3.9%).
Embodiment 8
Embodiment 8 illustrates hydrogen: the alkynes mol ratio is the continuous hydrogenation method of hexafluoro-2-butyne of 0.67: 1.
According to the method for embodiment 6, different is the hydrogen that joins in the reactor: the mol ratio of hexafluoro-2-butyne is 0.67: 1.0.The analysis of product mixtures illustrates CF 3CH=CHCF 3(cis) (65.3%), CF 3CH=CHCF 3(trans) (4.4%), CF 3CH 2CH 2CF 3(3.4%) and CF 3C ≡ CCF 3(23.5%).
Embodiment 9
Embodiment 9 shows the continuous hydrogenation method of the hexafluoro-2-butyne with 7 second duration of contact.
According to the method for embodiment 6, different is, regulates flow so that duration of contact of 7 seconds to be provided.Described reaction heat release slightly, reactor are warming up to 42 ℃.The product mixtures analysis illustrates CF 3CH=CHCF 3(cis) (72.5%), CF 3CH=CHCF 3(trans) (8.7%), CF 3CH 2CH 2CF 3(8.6%) and CF 3C ≡ CCF 3(6.9%).
Comparing embodiment 1
In 400ml Hastelloy oscillator tube, add 2g lindlar catalyst, 30g hexafluoro-2-butyne.With H2 described oscillator tube is forced into maximum 300psi.Pressure suddenly rises to 4000psi, and the reactor content temperature rises to 70 ℃.Reclaim black powder as product.
Comparing embodiment 2
In 1.3l Hastelloy reactor, add the 10g lindlar catalyst.Then 500g (3.08 moles) hexafluoro-2-butyne is joined in the reactor.Little increment with 30-50psi adds hydrogen.Add 2385psi altogether.Mean rate is 40psi/hr.During 60 hours, hydrogen on average is consumed with the speed of 35psi/hr.As a result, hexafluoro-2-butyne of 89% is converted to saturated CF 3CH 2CH 2CF 3, in product mixtures, detect unsaturated cis-CF of 7.7% 3CH=CHCF 3
Comparing embodiment 3
The 1g Raney's nickel is put in the 210ml Hastelloy oscillator tube.After reactor cooling, add 25g (0.154 mole) hexafluoro-2-butyne.At ambient temperature, use H 2Reactor is forced into 150psi (about 0.09 mole).Reactor is heated to 50 ℃ then.52 ℃ of overdraft rise to 299psi, and the 14psi that only descends in subsequently one hour.After temperature was risen to 90 ℃, pressure was reduced to 214psi, and did not change during three hours subsequently.After discharging remaining pressure carefully, be recovered to the 20g crude mixture.Described mixture comprises hexafluoro-2-butyne raw material of 86%, 8.375% saturated CF 3CH 2CH 2CF 3And cis-CF of 5.6% 3CH=CHCF 3
Notice, above general describe or embodiment described in behavior not all is necessary, a part of concrete behavior is optional, and those, also can implement one or more other behaviors except described.In addition, the order of listed behavior needs not to be the order of implementing them.
In above-mentioned specification sheets, with reference to specific embodiment different concepts has been described.Yet those of ordinary skill in the art recognizes, under the situation that does not break away from the scope of the invention as hereinafter described in the claims, can carry out various modifications and variations.Therefore, specification sheets and accompanying drawing are considered to illustrative and nonrestrictive, and all these type of modifications all are intended to be included in the category of the present invention.
The solution of beneficial effect, other advantages and problem has above been described in conjunction with specific embodiment.Yet, the solution of beneficial effect, advantage, problem and can cause any beneficial effect, advantage or solution produces or the more significant any feature that becomes may not be interpreted as the key of any or all claim, essential or essential characteristic.
Will be appreciated that for clarity sake, some characteristic described in the context of this paper different embodiments also can provide with array mode in single embodiment.Otherwise for simplicity, a plurality of characteristics described in single embodiment context also can provide respectively, or provide in the mode of any sub-portfolio.In addition, the correlation values of describing in the scope comprises each value in the described scope.

Claims (38)

1. synthesize the method for fluorinated olefin, described method comprises:
In pressurized vessel, make formula R 1C ≡ C R 2Fluoridize alkynes, wherein R 1And R 2Be independently selected from CF 3, C 2F 5, C 3F 7And C 4F 9, with lindlar catalyst and basically the hydrogen of a molar equivalent contact so that highly selective makes formula R 1CH=CH R 2Corresponding cis-alkene, wherein said hydrogen added in for some time in batches, so that produce the original pressure that is not more than about 100psi in described container.
2. the process of claim 1 wherein that described method implements in solvent.
3. the method for claim 2, wherein said solvent are alcohol, and described alcohol is selected from ethanol, n-propyl alcohol or Virahol.
4. the method for claim 2, wherein said solvent is fluorohydrocarbon or hydrogen fluorohydrocarbon.
5. the method for claim 4, wherein said hydrogen fluorohydrocarbon is selected from 1,1,1,2,2,3,4,5,5,5-Decafluoropentane and 1,1,2,2,3,3,4-seven fluorine pentamethylene.
6. the process of claim 1 wherein that incremental ground adds hydrogen and produce the initial supercharging that is no more than about 50psi in described container.
7. the process of claim 1 wherein that the amount of described catalyzer is that the described about 0.5 weight % of alkynes that fluoridizes is to about 4 weight %.
8. the process of claim 1 wherein that the amount of described catalyzer is that the described about 1 weight % of alkynes that fluoridizes is to about 3 weight %.
9. the process of claim 1 wherein that the amount of described catalyzer is that the described about 1 weight % of alkynes that fluoridizes is to about 2 weight %.
10. the process of claim 1 wherein that the selection rate of described cis-olefin product is at least 95%.
11. the process of claim 1 wherein that the selection rate of described cis-olefin product is at least 97%.
12. the process of claim 1 wherein that the described alkynes of fluoridizing is selected from hexafluoro-2-butyne, octafluoro-valerylene, ten fluoro-2-hexins, ten fluoro-3-hexins, 12 fluoro-2-heptyne, 12 fluoro-3-heptyne, ten tetrafluoros-3-octyne and ten tetrafluoros-4-octyne.
13. also comprising by fractionation, the method for claim 1, described method reclaim described cis-alkene.
14. the process of claim 1 wherein at least 50% described fluoridize alkynes reaction after, join the hydrogen share in the described pressurized vessel.
15. the process of claim 1 wherein at least 60% described fluoridize alkynes reaction after, join the hydrogen share in the described pressurized vessel.
16. the method for synthetic fluorinated olefin, described method comprises: make formula R in pressurized vessel 1C ≡ C R 2Fluoridize alkynes, wherein R 1And R 2Be independently selected from CF 3, C 2F 5, C 3F 7And C 4F 9, in solvent with lindlar catalyst and basically the hydrogen of a molar equivalent contact so that highly selective makes formula R 1CH=CH R 2Corresponding cis-alkene.
17. the method for claim 16, wherein said hydrogen added in for some time, so that produce the original pressure that is not more than about 100psi in described container in batches.
18. the method for claim 16, wherein said solvent are alcohol, described alcohol is selected from ethanol, n-propyl alcohol or Virahol.
19. the method for claim 16, wherein said solvent are fluorohydrocarbon or hydrogen fluorohydrocarbon.
20. the method for claim 19, wherein said hydrogen fluorohydrocarbon is selected from 1,1,1,2,2,3,4,5,5,5-Decafluoropentane and 1,1,2,2,3,3,4-seven fluorine pentamethylene.
21. the method for claim 16, the amount of wherein said catalyzer are that the described about 0.5 weight % of alkynes that fluoridizes is to about 4 weight %.
22. the method for claim 16, the amount of wherein said catalyzer are that the described about 1 weight % of alkynes that fluoridizes is to about 3 weight %.
23. the method for claim 16, the amount of wherein said catalyzer are that the described about 1 weight % of alkynes that fluoridizes is to about 2 weight %.
24. the method for claim 16, the selection rate of wherein said cis-olefin product is at least 95%.
25. the method for claim 16, the selection rate of wherein said cis-olefin product is at least 97%.
26. the method for claim 16, the wherein said alkynes of fluoridizing is selected from hexafluoro-2-butyne, octafluoro-valerylene, ten fluoro-2-hexins, ten fluoro-3-hexins, 12 fluoro-2-heptyne, 12 fluoro-3-heptyne, ten tetrafluoros-3-octyne and ten tetrafluoros-4-octyne.
27. also comprising by fractionation, the method for claim 16, described method reclaim described cis-olefin product.
28. method for hydrogenation, described method comprises: in the presence of lindlar catalyst, in reaction zone, in gas phase, make formula R 1C ≡ C R 2Fluoridize alkynes, wherein R 1And R 2Be independently selected from CF 3, C 2F 5, C 3F 7And C 4F 9, contact with equivalent or hydrogen still less basically, to make formula R 1CH=CH R 2Fluorinated olefin.
29. the method for claim 28, the wherein said alkynes of fluoridizing is selected from hexafluoro-2-butyne, octafluoro-valerylene, ten fluoro-2-hexins, ten fluoro-3-hexins, 12 fluoro-2-heptyne, 12 fluoro-3-heptyne, ten tetrafluoros-3-octyne and ten tetrafluoros-4-octyne.
30. the method for claim 28, wherein hydrogen is about 0.67: 1 to about 1: 1 with the ratio of fluoridizing alkynes.
31. the method for claim 28, wherein the weight percent of the palladium catalyst on the calcium carbonate carrier is that about 1 weight % is to about 10 weight %.
32. the method for claim 28, wherein the weight percent of the palladium catalyst on the calcium carbonate carrier is that about 1 weight % is to about 5 weight %.
33. the method for claim 28, the described alkynes of fluoridizing that wherein joins in the reaction zone also comprises inert carrier gas.
34. the method for claim 33, wherein said inert carrier gas is selected from nitrogen, helium or argon gas.
Reclaim product mixtures 35. the method for claim 28, described method also comprise by fractionation, described product mixtures comprises formula R 1CH=CH R 2The described cis-isomer of described fluorinated olefin.
36. the method for claim 28, its Chinese style R 1CH=CH R 2Described fluorinated olefin product comprise cis-and trans-isomer.
37. the method for claim 36, the trans-isomer of wherein said fluorinated olefin product are at least 5 weight % of described fluorinated olefin product.
38. the method for claim 36, the trans-isomer of wherein said fluorinated olefin product are at least 10 weight % of described fluorinated olefin product.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106008147A (en) * 2016-05-23 2016-10-12 北京宇极科技发展有限公司 Preparation method of Z-1,1,1,4,4,4-hexafluoro-2-butene
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Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8524955B2 (en) * 2010-05-21 2013-09-03 Honeywell International Inc. Process for the preparation of hexafluoro-2-butyne
US8901360B2 (en) * 2010-05-21 2014-12-02 Honeywell International Inc. Process for cis 1,1,1,4,4,4-hexafluoro-2-butene
US8530709B2 (en) * 2010-05-21 2013-09-10 Honeywell International Inc. Process for the production of fluorinated alkenes
JP5598910B2 (en) * 2010-06-14 2014-10-01 独立行政法人産業技術総合研究所 Method for producing fluorine compound
JP6413848B2 (en) * 2015-03-03 2018-10-31 Ａｇｃ株式会社 Method for producing fluorine-containing symmetric olefin
KR102664130B1 (en) * 2015-08-07 2024-05-10 더 케무어스 컴퍼니 에프씨, 엘엘씨 Catalytic isomerization of Z-1,1,1,4,4,4-hexafluoro-2-butene to E-1,1,1,4,4,4-hexafluoro-2-butene
CN107262092B (en) * 2017-06-16 2021-03-09 巨化集团技术中心 Catalyst for synthesizing cis-1, 1,1,4,4, 4-hexafluoro-2-butene and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB810913A (en) * 1956-07-17 1959-03-25 Hoffmann La Roche Improvements in or relating to the hydrogenation of acetylenic carbinols
JPS56133230A (en) * 1980-03-21 1981-10-19 Otsuka Pharmaceut Co Ltd Preparation of cis-olefin
DE4305163A1 (en) * 1993-02-19 1994-08-25 Bayer Ag Process for the preparation of hexafluorobutene
US8618339B2 (en) * 2007-04-26 2013-12-31 E I Du Pont De Nemours And Company High selectivity process to make dihydrofluoroalkenes
CN101903313A (en) * 2007-12-17 2010-12-01 纳幕尔杜邦公司 Processes for the synthesis of 3-chloroperfluoro-2-pentene, octafluoro-2-pentyne, and 1,1,1,4,4,5,5,5-octafluoro-2-pentene
US8143462B2 (en) * 2007-12-17 2012-03-27 E.I. Du Pont De Nemours And Company Processes for the synthesis of 2-chloro-1,1,1,3,3,4,4,4-heptafluoro-2-butene and hexafluoro-2-butyne
CN102112420A (en) * 2008-07-31 2011-06-29 霍尼韦尔国际公司 Process for the preparation of perfluorinated cis-alkene

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107879890A (en) * 2013-03-15 2018-04-06 得凯莫斯公司弗罗里达有限公司 The method for reducing the alkyne impurities in fluoroolefins
CN107879890B (en) * 2013-03-15 2022-01-18 得凯莫斯公司弗罗里达有限公司 Process for reducing alkyne impurities in fluoroolefins
CN106008147A (en) * 2016-05-23 2016-10-12 北京宇极科技发展有限公司 Preparation method of Z-1,1,1,4,4,4-hexafluoro-2-butene
CN106008147B (en) * 2016-05-23 2018-11-02 北京宇极科技发展有限公司 Z-1,1, Isosorbide-5-Nitrae, the preparation method of 4,4- hexafluoro -2- butylene
CN106349007A (en) * 2016-08-22 2017-01-25 巨化集团技术中心 Preparation method of Z-HFO-1336
CN106349007B (en) * 2016-08-22 2019-06-11 巨化集团技术中心 A kind of preparation method of Z-HFO-1336

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