CN102036938A - High selectivity process to make dihydrofluoroalkenes - Google Patents

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

Highly selective process for the preparation of dihydrofluoroalkenes

Background Information

public domain

The present disclosure generally relates to the synthesis of hydrofluoroolefins.

Description of related fields

The fluorocarbon industry has been working for decades to find alternative refrigerants due to the Montreal Protocol's phase-out of the ozone-depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs). The solution for many applications is the commercialization of hydrofluorocarbon (HFC) compounds for use as refrigerants, solvents, fire suppressants, blowing agents and propellants. These new compounds, such as HFC refrigerants, of which HFC-134a is currently the most widely used, have zero ozone depletion potential and are therefore not affected by their phase-out due to the current provisions of the Montreal Protocol.

In addition to the issue of ozone depletion, global warming is another environmental concern associated with many of these applications. Accordingly, there is a need for compositions that meet low ozone depletion criteria while having low global warming potential. Certain HFOs are believed to meet both goals. Accordingly, there is a need for processes that provide for the preparation of halohydrocarbons and fluoroalkenes that do not contain chlorine while having a low global warming potential.

Contents of the invention

In one embodiment, the method is a method of synthesizing fluorinated alkenes, the method comprising allowing a fluorinated alkyne of formula R ¹ -C≡CR ² in a pressure vessel, wherein R ¹ and R ² are independently selected from CF ₃ , C ₂ F ₅ , C ₃ F ₇ and C ₄ F ₉ , contacted with a Lindler catalyst and essentially at most one molar equivalent (and including one) of hydrogen to produce formula R ^HC with high selectivity = The corresponding cis or trans olefin of CHR ² , wherein the hydrogen is added in portions over a period of time to create an initial pressure in the vessel of no greater than about 100 psi.

In another embodiment, the method is a method of synthesizing fluorinated alkenes, the method comprising: allowing a fluorinated alkyne of formula R ₁ C≡CR ₂ in a pressure vessel, wherein R ₁ and R ₂ are independently selected from From CF ₃ , C ₂ F ₅ , C ₃ F ₇ and C ₄ F ₉ , contact with Lindler's catalyst and essentially one molar equivalent of hydrogen in a solvent to obtain the formula R ¹ HC=CH R ² with high selectivity the corresponding cis-alkene.

In another embodiment, the method is a method for the synthesis of fluorinated alkenes in a continuous process, in the presence of a Lindler catalyst, in the reaction zone, in the gas phase, the fluorinated alkyne of the formula R ¹ C≡C R ² , wherein R ¹ and R ² are independently selected from CF ₃ , C ₂ F ₅ , C ₃ F ₇ , and C ₄ F ₉ , contacted with substantially one equivalent or less of hydrogen.

The foregoing summary, as well as the following detailed description, are presented for purposes of illustration and description only and are not restrictive of the invention, which is defined by the appended claims.

Detailed description of the invention

In one embodiment, the method is a method for the highly selective synthesis of fluorinated alkenes from the corresponding fluorinated alkynes by selective hydrogenation in the presence of a specific catalyst.

A number of aspects and embodiments have been described above by way of illustration only and not limitation. After reading this specification, skilled artisans appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

Other features and benefits of any one or more embodiments will become apparent from a reading of the following detailed description and claims.

Before addressing the details of the embodiments described below, some terms are defined or clarified.

As used herein, the terms "comprises," "including," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to only those elements, but may include other elements not expressly listed or inherent to the process, method, article, or apparatus. Furthermore, unless expressly stated to the contrary, "or" means an inclusive "or", not an exclusive "or". For example, either of the following conditions A or B is satisfied: A is true (or exists) and B is false (or does not exist), A is false (or does not exist) and B is true (or exist), and both A and B are true (or exist).

Likewise, use of "a" or "an" is used to describe elements and components described herein. This is done merely for convenience and to give a general sense of the scope of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns in the Periodic Table of the Elements use the "new symbol" convention found in the "CRC Handbook of Chemistry and Physics" 81st Edition (2000-2001).

As used herein, the reaction zone may be a reaction vessel machined from nickel, iron, titanium, or alloys thereof, as described in US Patent 6,540,933, which is incorporated herein by reference. Reaction vessels (such as metal tubes) of these materials can also be used. When referring to alloys, it is meant that nickel alloys contain from about 1% to about 99.9% by weight nickel, iron alloys contain from about 0.2% to about 99.8% by weight iron, and titanium alloys contain from about 72% to about 99.8% by weight titanium . Of note is the use of tubes packed with Lindler catalysts as described above, made of nickel or nickel alloys, such as those containing from about 40% to about 80% by weight nickel, for example Inconel ^™ 600 nickel alloy, Hastelloy ^TM C617 nickel alloy, or Hastelloy ^TM C276 nickel alloy.

Lindler catalysts are hybrid palladium catalysts on a calcium carbonate support that have been deactivated or bound by lead compounds. The lead compound may be lead acetate, lead oxide or any other suitable lead compound. In one embodiment, the catalyst is prepared by reduction of a palladium salt in the presence of a calcium carbonate slurry, followed by the addition of a lead compound. In one embodiment, the palladium salt is palladium chloride. In another embodiment, the catalyst is deactivated or conditioned with quinoline. The amount of palladium on the support is typically 5% by weight, but can be any catalytically effective amount.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of the invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are hereby incorporated by reference in their entirety, unless a specific passage is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

In one embodiment, by making a fluorinated alkyne of formula R ¹ C≡C R ² , wherein R ¹ and R ² are independently selected from CF ₃ , C ₂ F ₅ , C ₃ F , in the presence of a selected catalyst, ₇ , and C ₄ F ₉ , contact with hydrogen to synthesize fluorinated olefins. Representative fluorinated alkynes include alkynes selected from the group consisting of hexafluoro-2-butyne, octafluoro-2-pentyne, decafluoro-2-hexyne, decafluoro-3-hexyne, dodecafluoro -2-heptyne, dodecafluoro-3-heptyne, tetradecafluoro-3-octyne and tetradecafluoro-4-octyne.

Hexafluoro-2-butyne is readily obtained by dechlorination of 1,1,1,4,4,4-hexafluoro-2,3-dichloro-2-butene (CFC-1316mxx) with zinc. CFC-1316mxx is readily prepared from _CF3CCl3 as disclosed in US Patent No. _5,919,994 , the disclosure of which is incorporated herein by reference. Similarly, _decafluoro -3-hexyne _is readily prepared from _CF3CF2CCl = _CClCF2CF3 by dechlorination with zinc. Similarly _{, CF3CF2CCl} = _{CClCF2CF3 is} prepared _{from CF3CF2CCl3 .} Similarly, decafluoro-2 _- hexyne is readily prepared _from CF ₃ CCl=CClCF ₂ CF _{2 CF 3 which is} readily prepared by reaction with tetra The reaction of vinyl fluoride, made by CFC-1316mxx. Octafluoro-2-pentyne can be prepared from 1,1,1,2,2,3,4,5,5,5-decafluoropentane by double dehydrofluorination in the presence of base or zeolite, as Disclosed in Japanese Patent 2004292329.

In one embodiment, the catalyst of the method is a Lindler catalyst. In one embodiment, the catalyst is used in an amount of about 0.5% to about 4% by weight based on the amount of the fluorinated alkyne. In another embodiment, the catalyst is used in an amount of about 1% to about 3% by weight based on the amount of the fluorinated alkyne. In another embodiment, the catalyst is used in an amount of about 1% to about 2% by weight based on the amount of the fluorinated alkyne.

In some embodiments, the reaction is performed in a solvent. In one such embodiment, the solvent is alcohol. Typical alcoholic solvents include ethanol, isopropanol and n-propanol. In another embodiment, the solvent is a fluorocarbon or hydrofluorocarbon. Common fluorocarbons or hydrofluorocarbons include 1,1,1,2,2,3,4,5,5,5-decafluoropentane and 1,1,2,2,3,3,4-hepta Fluorocyclopentane.

In one embodiment, the method is performed as a batch process.

In another embodiment, the process is carried out in the gas phase as a continuous process.

In one embodiment, the reaction of the fluorinated alkyne with hydrogen in the presence of a catalyst should be carried out by adding hydrogen in portions with an increase in vessel pressure of not more than about 100 psi per addition. In another embodiment, the addition of hydrogen is controlled so that the pressure increase in the vessel does not exceed about 50 psi per addition. In one embodiment, after the hydrogenation reaction has consumed sufficient hydrogen to convert at least 50% of the fluorinated alkyne to an alkene, hydrogen may be added in larger increments to the remainder of the reaction. In another embodiment, after the hydrogenation reaction has consumed sufficient hydrogen to convert at least 60% of the fluorinated alkynes to alkenes, hydrogen may be added in larger increments to the remainder of the reaction. In another embodiment, after the hydrogenation reaction has consumed sufficient hydrogen to convert at least 70% of the fluorinated alkynes to alkenes, hydrogen may be added in larger increments to the remainder of the reaction. In one embodiment, greater hydrogen addition increments may be 300 psi. In another embodiment, greater hydrogen addition increments may be 400 psi.

In one embodiment, hydrogen is added in an amount of about one molar equivalent per mole of fluorinated alkyne. In another embodiment, hydrogen is added in an amount of about 0.9 moles to about 1.3 moles per mole of fluorinated alkyne. In another embodiment, hydrogen is added in an amount of about 0.95 moles to about 1.1 moles per mole of fluorinated alkyne. In another embodiment, hydrogen is added in an amount of about 0.95 moles to about 1.03 moles per mole of fluorinated alkyne.

In one embodiment, the hydrogenation is performed at ambient temperature. In another embodiment, the hydrogenation is carried out at above ambient temperature. In another embodiment, the hydrogenation is performed at subambient temperature. In another embodiment, the hydrogenation reaction is carried out at a temperature below about 0°C.

In one embodiment of the continuous process, a mixture of fluorinated alkyne and hydrogen is passed through a reaction zone comprising a catalyst. In one embodiment, the molar ratio of hydrogen to fluorinated alkyne is about 1:1. In another embodiment of the continuous process, the molar ratio of hydrogen to fluorinated alkyne is less than 1:1. In another embodiment, the molar ratio of hydrogen to fluorinated alkyne is about 0.67:1.0.

In one embodiment of the continuous process, the reaction zone is maintained at ambient temperature. In another embodiment of the continuous process, the reaction zone is maintained at a temperature of 30°C. In another embodiment of the continuous process, the reaction zone is maintained at a temperature of about 40°C.

In one embodiment of the continuous process, the flow of fluorinated alkyne and hydrogen is maintained to provide a residence time in the reaction zone of about 30 seconds. In another embodiment of the continuous process, the flow of fluorinated alkyne and hydrogen is maintained to provide a residence time in the reaction zone of about 15 seconds. In another embodiment of the continuous process, the flow of fluorinated alkyne and hydrogen is maintained to provide a residence time in the reaction zone of about 7 seconds.

It will be appreciated that the contact time in the reaction zone is reduced due to the increased flow of fluorinated alkyne and hydrogen into the reaction zone. This will increase the amount of fluorinated alkyne hydrogenated per unit time as the flow rate is increased. Since hydrogenation is exothermic, depending on the length and diameter of the reaction zone and its ability to dissipate heat, at higher flow rates it may be desirable to provide the reaction zone with an external source of cooling to maintain the desired temperature.

In one embodiment of the continuous process, the amount of supported palladium in the Lindler catalyst is 5% by weight. In another embodiment, the amount of supported palladium in the Lindler catalyst is greater than 5% by weight. In another embodiment, the amount of palladium on the support may be from about 5% to about 1% by weight.

In one embodiment, after completion of the batch or continuous hydrogenation process, the cis-dihydrofluoroolefins can be recovered by any conventional means, including, for example, fractional distillation. In another embodiment, the cis-dihydrofluoroalkene is of sufficient purity after completion of the batch or continuous hydrogenation process that no further purification steps are required.

Example

The concepts described herein will be further described in the following examples, which do not limit the scope of the invention described in the claims.

Example 1

Example 1 shows the selective hydrogenation of hexafluoro-2-butyne.

5 g of Lindler (5% Pd on CaCO3 poisoned with lead) catalyst was added to a 1.3 L shaker cylinder. 480 g (2.96 moles) of hexafluoro-2-butyne were added to the shaker cylinder. The reactor was cooled (-78°C) and evacuated. After shaking the cylinder to room temperature, slowly add _H2 in increments not exceeding Δp = 50 psi. A total of 3 moles of _H2 were added to the reactor. Gas chromatographic analysis of the crude product showed a mixture consisting of _CF3C≡CCF3 (0.236%), the trans isomer _{of CF3CH} = _CHCF3 (0.444% ₎ , _{saturated CF3CH2CH2CF3} (1.9% ₎ ), CF ₂ =CHCl (impurity from raw material butyne, 0.628%), CF ₃ CH=CHCF ₃ cis-isomer (96.748%). Distillation afforded 287 g (59% yield) of 100% pure cis- _CF3CH = _CHCF3 (boiling point 33.3°C). MS: 164[MI], 145[M-19], 95[ _CF3CH =CH], 69[ _CF3 ]. NMR H ¹ : 6.12ppm (multiplet), F ¹⁹ : -60.9ppm (triplet, J=0.86Hz)

Example 2

Example 2 shows the hydrogenation of hexafluoro-2-butyne using 2% by weight of catalyst.

10 g of Lindler's catalyst were added to a 1.3 l Hastelloy reactor. Then 500 g (3.08 moles) of hexafluoro-2-butyne were added to the reactor. Hydrogen was added in small increments of 50-100 psi. A total of 1100 psi of hydrogen (3.08 moles) was added. Hydrogen was consumed at an average rate of 150 psi/hr over a 6.5 hour period. Gas chromatographic analysis of the product indicated that 93.7% _of the hexafluorobutyne was converted to cis- _CF3CH = _CHCF3 , and 4.8% of _{saturated CF3CH2CH2CF3 .}

Example 3

Example 3 shows the hydrogenation of octafluoro-2-pentyne using 1% by weight of catalyst.

10 g of Lindler's catalyst were added to a 1.3 l Hastelloy reactor. Next, 650 g (3.06 moles) of octafluoro-2-pentyne was added to the reactor. Hydrogen was then slowly added in increments not to exceed Δp = 50 psi. A total of 3 moles of _H2 were added to the reactor. Gas chromatographic analysis _of the product indicated that 96.7% of _octafluoro -2-pentyne was converted to cis- _CF3CH = _CHCF2CF3 , and 1.8% _{of saturated CF3CH2CH2CF2CF3 .}

Example 4

Example 4 shows the hydrogenation of hexafluoro-2-butyne using 1% by weight of catalyst.

5 g of Lindler's catalyst were added to a 1.3 l Hastelloy reactor. Then 500 g (3.08 moles) of hexafluoro-2-butyne were added to the reactor. Hydrogen was added in small increments of 30-50 psi. A total of 1414 psi (4.0 moles of hydrogen) was added. Hydrogen was consumed at an average rate of 50 psi/hr over a 28 hour period. Analysis of the resulting product _mixture showed 80.7% cis- _CF3CH = _CHCF3 and 19.3% _{saturated CF3CH2CH2CF3 .}

Example 5

Example 5 shows the hydrogenation of decafluoro-3-hexyne.

8 g of Lindler's catalyst were added to a 1.3 l Hastelloy reactor. Then 800 g (3.05 moles) of decafluoro-3-hexyne were added to the reactor. Hydrogen was then slowly added in increments not to exceed Δp = 50 psi. A total of 3 moles of H2 were added to the reactor. Gas chromatographic analysis of the _product indicated that 96.7% _{of decafluoro} -3 _- hexyne was converted to cis- _CF3CF2CH = _CHCF2CF3 , and _1.8 % _of saturated _{CF3CF2CH2CH2CF2CF 3} .

Example 6

Example 6 shows the sequential hydrogenation of hexafluoro-2-butyne to produce a mixture of cis- and trans-1,1,1,4,4,4-hexafluoro-2-butene.

Into a Hastelloy tubular reactor 10" long and having a 5" OD (outer diameter) and a 0.35" wall thickness, 10 g of Lindler's catalyst was charged. The catalyst was conditioned at 70° C. for 24 hours with a stream of hydrogen. Then at 30 A stream of hexafluoro-2-butyne and hydrogen in a 1:1 molar ratio was passed through the reactor at a flow rate sufficient to provide a contact time of 30 seconds at °C. The product mixture leaving the reactor was collected in a cold trap , and analyzed by gas chromatography. The product mixture was found to contain CF ₃ CH=CHCF ₃ (cis) (72%), CF ₃ CH=CHCF ₃ (trans) (8.8%), CF ₃ CH ₂ CH ₂ CF _{3 (} 7.8%), and _CF3C≡CCF3 (3.3%).

Example 7

Example 7 shows a continuous hydrogenation process of hexafluoro-2-butyne with a contact time of 15 seconds.

The method of Example 6 was followed except that the flow rate was adjusted to provide a contact time of 15 seconds. The reaction was slightly exothermic and the reactor warmed to 35-36°C. Analysis of the product _mixture showed _CF3CH = _CHCF3 (cis ₎ (72%), _CF3CH = _CHCF3 (trans) (9.3%), _CF3CH2CH2CF3 ( _11.3 %), and CF ₃ C≡CCF ₃ (3.9%).

Example 8

Example 8 shows a process for the continuous hydrogenation of hexafluoro-2-butyne with a hydrogen:alkyne molar ratio of 0.67:1.

According to the method of Example 6, the difference is that the molar ratio of hydrogen: hexafluoro-2-butyne added to the reactor is 0.67:1.0. Analysis of _the product _mixture showed _CF3CH = _CHCF3 (cis ₎ (65.3%), _CF3CH = _CHCF3 (trans) (4.4%), _CF3CH2CH2CF3 (3.4%), and _CF3C≡CCF3 ( _23.5 %).

Example 9

Example 9 shows a continuous hydrogenation process of hexafluoro-2-butyne with a contact time of 7 seconds.

The method of Example 6 was followed except that the flow rate was adjusted to provide a contact time of 7 seconds. The reaction was slightly exothermic and the reactor warmed to 42°C. Analysis of the product mixture showed CF ₃ CH=CHCF ₃ (cis) (72.5%), CF ₃ CH=CHCF ₃ (trans) (8.7%), CF ₃ CH ₂ CH ₂ CF ₃ (8.6%), and CF ₃ C≡CCF ₃ (6.9%).

Comparative Example 1

Add 2g of Lindler catalyst and 30g of hexafluoro-2-butyne into a 400ml Hastelloy shaking tube. The shaking tube was pressurized to a maximum of 300 psi with H2. The pressure rose abruptly to 4000 psi, and the temperature of the reactor contents rose to 70°C. A black powder was recovered as product.

Comparative Example 2

10 g of Lindler's catalyst were added to a 1.3 l Hastelloy reactor. Then 500 g (3.08 moles) of hexafluoro-2-butyne were added to the reactor. Hydrogen was added in small increments of 30-50 psi. A total of 2385psi was added. The average rate was 40 psi/hr. Hydrogen was consumed at an average rate of 35 psi/hr during the 60 hours. As a result, 89% of hexafluoro-2-butyne was converted to saturated CF ₃ CH ₂ CH ₂ CF ₃ , and 7.7% of unsaturated cis-CF ₃ CH═CHCF ₃ was detected in the product mixture.

Comparative Example 3

Put 1g of Raney nickel into a 210ml Hastelloy shaker tube. After the reactor had cooled, 25 g (0.154 mol) of hexafluoro-2-butyne were added. The reactor was pressurized to 150 psi (about 0.09 moles) with _H2 at ambient temperature. The reactor was then heated to 50°C. The pressure rose to 299 psi at 52°C and dropped only 14 psi over the ensuing hour. After raising the temperature to 90°C, the pressure dropped to 214 psi and did not change during the next three hours. After carefully releasing the remaining pressure, 20 g of the crude product mixture were recovered. The mixture contained 86% of hexafluoro-2-butyne starting material, 8.375% of saturated CF ₃ CH ₂ CH ₂ CF ₃ , and 5.6% of cis-CF ₃ CH═CHCF ₃ .

Note that not all of the activities described above in the general description or in the examples are required, that a portion of a specific activity may not be required, and that one or more other activities may be performed in addition to those described. Furthermore, the order in which the actions are listed is not necessarily the order in which they are performed.

In the foregoing specification, various concepts have been described with reference to specific embodiments. However, one of ordinary skill in the art recognizes that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. Accordingly, the specification and drawings are to be regarded as illustrative rather than restrictive, and all such modifications are intended to be included within the scope of this invention.

Benefits, other advantages, and solutions to problems have been described above in conjunction with specific embodiments. However, benefits, advantages, solutions to problems, and any feature that may cause any benefit, advantage or solution to be produced or made more pronounced, are not to be construed as critical, required or essential features of any or all claims.

It should be appreciated that, for clarity, certain features that are described herein in the context of different implementations can also be provided in combination in a single implementation. Conversely, various features which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. Further, reference to numerical values stated within ranges includes each and every value within that range.

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.