CN106892794A - A kind of method for preparing trans 1,3,3,3 tetrafluoropropene - Google Patents

A kind of method for preparing trans 1,3,3,3 tetrafluoropropene Download PDF

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CN106892794A
CN106892794A CN201611239503.XA CN201611239503A CN106892794A CN 106892794 A CN106892794 A CN 106892794A CN 201611239503 A CN201611239503 A CN 201611239503A CN 106892794 A CN106892794 A CN 106892794A
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aqueous solution
tetrafluoropropenes
phase
solvent
transfer catalyst
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CN106892794B (en
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张伟
李宝太
曾纪珺
马家琪
韩升
焦锋刚
唐晓博
聂剑飞
吕剑
尹双良
孟庆宇
武海涛
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SHAANXI YANCHANG PETROLEUM GROUP FLUOROSILICONE CHEMICAL CO Ltd
Xian Modern Chemistry Research Institute
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SHAANXI YANCHANG PETROLEUM GROUP FLUOROSILICONE CHEMICAL CO Ltd
Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Trans 1 is prepared the invention discloses one kind, 3,3, the method of 3 tetrafluoropropenes, the method in the presence of phase transfer catalyst and aromatic solvent, 1,1, trans 1 prepared and dehydrofluorination with alkaline aqueous solution in 1,3,3 pentafluoropropane there is, 3,3,3 tetrafluoropropenes, reaction temperature is 30~100 DEG C, reaction time is 10~120min, wherein phase transfer catalyst is crown ether or PAG, and aromatic solvent is chlorobenzene or alkylbenzene, and alkaline aqueous solution is the aqueous solution of NaOH or the aqueous solution of potassium hydroxide.The present invention constructs the two-phase dehydrofluorination system being made up of alkaline aqueous solution and aromatic solvent, and in the presence of a phase transfer catalyst, by 1,1,1,3,3 pentafluoropropane prepares trans 1, and 3,3,3 tetrafluoropropenes have the advantages that high conversion rate, solvent are repeated and utilize.

Description

A kind of method for preparing trans-1,3,3,3-tetrafluoropropene
Technical field
Anti-form-1 is prepared the present invention relates to one kind, the method for 3,3,3- tetrafluoropropenes is particularly a kind of in phase transfer catalysis (PTC) In the presence of agent and aromatic solvent, there is dehydrofluorination and prepare anti-form-1 in 1,1,1,3,3- pentafluoropropane with alkaline aqueous solution, The method of 3,3,3- tetrafluoropropenes.
Background technology
Anti-form-1, the ozone depletion value (ODP) of 3,3,3- tetrafluoropropenes (E-HFO-1234ze) is 0, the latent value of greenhouse effects (GWP) be 6, be known as by international community be the HFC (HFCs) of GWP high preferable low-carbon environment-friendly substitute, such as foam Agent substitutes 1,1,3,3,3- pentafluoropropanes (HFC-245fa), 1,1,1,2- HFC-134as (HFC-134a) and 1,1- difluoro second Alkane (HFC-152a), HFC-134a etc. is substituted as aerosol propellant.
Chinese patent CN104177219A report including the organic matter containing alkyl and aryl nitrile, contain alkyl and virtue In the presence of the organic matter of base ether, the organic matter containing sulfoxide and its mixture equal solvent, HFC-245fa occurs with alkaline aqueous solution Dehydrofluorination obtains HFO-1234ze.Reported by 91.5% HFC- in the embodiment of Chinese patent CN1852880B The raw material of the HFO-1234ze compositions of 245fa and 0.0121% bubbling in the potassium hydroxide solution of 2.0% weight, reaction outlet Comprising 15.455% HFO-1234ze in mixture.In above-mentioned preparation E-HFO-1234ze technologies, the de- method of HFC-245fa alkali makes It is solvent with dimethyl sulfoxide (DMSO) soluble in water, tetrahydrofuran and acetonitrile etc., such organic solvent dissolves each other with alkaline aqueous solution, it is difficult To reclaim.
The content of the invention
It is not enough present in background technology it is an object of the invention to overcome, there is provided a kind of high conversion rate, solvent are repeated The method for preparing trans-1,3,3,3-tetrafluoropropene for utilizing.
Technical solution of the invention is to construct the two-phase reaction system being made up of alkaline aqueous solution and aromatic solvent, In the presence of a phase transfer catalyst, 1, there is dehydrofluorination and prepare anti-form-1,3,3,3- tetrafluoros in 1,1,3,3- pentafluoropropane Propylene, reaction temperature is 30~100 DEG C, and the reaction time is 10~120min, and above-mentioned phase transfer catalyst is crown ether or poly- alkylene Base glycol, aromatic solvent be chlorobenzene or alkylbenzene, alkaline aqueous solution for NaOH the aqueous solution or potassium hydroxide it is water-soluble Liquid.
Preferably, present invention additionally comprises the recycling step of organic solvent：
Above-mentioned recycling step is：After reaction terminates, inorganic water phase and organic solvent phase AUTOMATIC ZONING, by simple phase point Operation reclaims organic solvent from the inorganic water phase and organic solvent phase of AUTOMATIC ZONING, for next secondary response.
The selected phase transfer catalyst of the present invention can in the high concentration basic aqueous solution stable existence, primarily serve by OH in alkaline aqueous solution-The effect that ion is brought into aromatic solvent.Above-mentioned crown ether be selected from 18- crown ethers -6 or 15- crown ethers - 5, above-mentioned PAG be selected from PEG400, Macrogol 600, cetomacrogol 1000, polyethylene glycol 2000 or its Mixture.
The hydrophobicity of the characteristics of aromatic solvent of the present invention has hydrophobicity and polarity, wherein solvent cause solvent with Alkaline aqueous solution constitutes immiscible two-phase system, and the polarity of solvent causes the OH of polarity-Ion salt can be dissolved in organic In solvent, there is dehydrofluorination with HFC-245fa.Above-mentioned chlorobenzene is chlorobenzene, dichloro-benzenes or its mixture；Above-mentioned alkane Base benzene is dimethylbenzene, ethylbenzene or its mixture.
The mass concentration of alkali is 20%~90% in alkaline aqueous solution of the present invention, and the mass concentration of preferred alkali is 40%~70%.
Alkali and the mol ratio of 1,1,1,3,3- pentafluoropropanes in the neutral and alkali aqueous solution of the present invention are 1.1:1~10:1, alkali Property the aqueous solution and aromatic solvent mass ratio be 0.1:1~10:1, phase transfer catalyst and 1, the matter of 1,1,3,3- pentafluoropropane Amount is than being 0.005:1~0.5:1.
Preferred material ratio is：Alkali and the mol ratio of 1,1,1,3,3- pentafluoropropanes in alkaline aqueous solution are 1.5:1~ 5:1 alkaline aqueous solution is 0.25 with the mass ratio of aromatic solvent:1~5:1, phase transfer catalyst and 1,1,1,3,3- pentafluoropropane Mass ratio be 0.01:1~0.1:1.
The present invention is not limited reaction pressure, can be operated under normal pressure, negative pressure or pressurized conditions.Additionally, reaction can To be carried out continuously, it is also possible to intermittently carry out, reaction is in itself to reaction formation without substantially requirement；
The beneficial effects of the invention are as follows：
1st, reaction system of the invention is two-phase system, after reaction terminates, inorganic water phase and organic solvent phase AUTOMATIC ZONING, It is recyclable organic solvent by point operation of simple phase, for next secondary response, middle solvent can not be returned compared to existing technology Receive, this technology more environmental protection；
2nd, present invention selection is phase transfer catalyst to the crown ether or PAG of high concentration basic stabilized aqueous solution, In alkaline aqueous solution and aromatic solvent two-phase system, still with reactivity very high, under the appropriate reaction conditions, HFC- The reaction conversion ratio of 245fa dehydrofluorinations reaches as high as 99% more than 80%.
Specific embodiment
It is following to be described in further detail explanation to the present invention in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment one
React is carried out in the 500mL stainless steel autoclaves of band stirring.To putting into 200g's 50% in reactor successively The KOH aqueous solution, 200g chlorobenzenes, 1.2g polyethylene glycol 2000s and 119g HFC-245fa, open stirring, and reaction temperature is risen into 70 DEG C, after reaction 60min, reaction temperature is kept, lower boiling reaction mass is slowly drained from reactor gas phase mouth, collect -30 DEG C cold hydrazine in, the material to collecting carries out gas chromatographic analysis, as a result shows that the conversion ratio of HFC-245fa is 95.9%, The overall selectivity of HFO-1234ze is 99.5%, and wherein the selectivity of E-HFO-1234ze is 78.4%.
Embodiment two
Embodiment two is similar to embodiment one, except that being added without aromatic solvent chlorobenzene, reaction result shows HFC- The conversion ratio of 245fa is 99.3% for the overall selectivity of 20.1%, HFO-1234ze, and the wherein selectivity of E-HFO-1234ze is 75.2%.After the result of comparative example one shows to add chlorobenzene, the activity of alkaline aqueous solution dehydrofluorination is greatly improved.
Embodiment three
It is the recycling design of embodiment one from the chlorobenzene solvent in the present embodiment unlike embodiment one, specially：Will After reaction solution is down to room temperature in kettle in embodiment one, quantizer phase point is placed in, removes a layer organic phase, as chlorobenzene solvent.To return The chlorobenzene of receipts is directly used in the present embodiment reaction, and other operations are constant, and reaction result shows that the conversion ratio of HFC-245fa is The overall selectivity of 95.8%, HFO-1234ze is 99.4%, and wherein the selectivity of E-HFO-1234ze is 79.1%, analysis result Show that solvent can be reclaimed directly to use.
Example IV~six
The operating process of example IV~six is similar to embodiment one, except that changing solvent, reaction result such as table 1 It is shown.
Table 1
Note：X245faRepresent the conversion ratio of HFC-245fa, S1234zeRepresent generation E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeRepresent the selectivity of generation E-HFO-1234ze.
Embodiment seven~11
The operating process of embodiment seven~11 is similar to embodiment one, except that changing the kind of phase transfer catalyst Class, reaction result is as shown in table 2.
Table 2
Note：X245faRepresent the conversion ratio of HFC-245fa, S1234zeRepresent generation E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeRepresent the selectivity of generation E-HFO-1234ze.
Embodiment 12
The operating process of embodiment 12 is similar to embodiment one, except that alkaline aqueous solution is changed into 50% The NaOH aqueous solution.Reaction result shows the conversion ratio of HFC-245fa for the overall selectivity of 82.5%, HFO-1234ze is The selectivity of 98.5%, E-HFO-1234ze is 79.3%.
Embodiment 13~16
The operating process of embodiment 13~16 is similar to embodiment one, except that changing reaction temperature and reaction Time, reaction result is as shown in table 3.
Table 3
Note：X245faRepresent the conversion ratio of HFC-245fa, S1234zeRepresent generation E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeRepresent the selectivity of generation E-HFO-1234ze.
Embodiment 17~20
The operating process of embodiment 17~20 is similar to embodiment one, except that change concentration of lye, reaction Result is as shown in table 4.
Table 4
Note：X245faRepresent the conversion ratio of HFC-245fa, S1234zeRepresent generation E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeRepresent the selectivity of generation E-HFO-1234ze.
Embodiment 21~25
The operating process of embodiment 21~25 is similar to embodiment one, except that change material proportion, Reaction result is as shown in table 5.
Table 5
Note：X245faRepresent the conversion ratio of HFC-245fa, S1234zeRepresent generation E-HFO-1234ze's and Z-HFO-1234z Overall selectivity, SE-1234zeRepresent the selectivity of generation E-HFO-1234ze.

Claims (8)

1. one kind prepares anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：In the presence of a phase transfer catalyst, 1, Anti-form-1,3,3,3- tetrafluoros obtained and dehydrofluorination with alkaline aqueous solution in aromatic solvent in 1,1,3,3- pentafluoropropanes there is Propylene, wherein reaction temperature are 30~100 DEG C, and the reaction time is 10~120min；The phase transfer catalyst is crown ether or poly- Aklylene glycol, the aromatic solvent is chlorobenzene or alkylbenzene, and the alkaline aqueous solution is the aqueous solution or hydrogen of NaOH The aqueous solution of potassium oxide.
It is 2. according to claim 1 to prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：Also include The recycling step of machine solvent：
The recycling step is：After reaction terminates, inorganic water phase and organic solvent phase AUTOMATIC ZONING, by simple phase point operation Organic solvent is reclaimed from the inorganic water phase and organic solvent phase of AUTOMATIC ZONING, for next secondary response.
It is 3. according to claim 1 and 2 to prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：Described Crown ether is selected from 18- crown ethers -6 or 15- crown ethers -5；Described PAG is selected from PEG400, Macrogol 600, gathers Ethylene glycol 1000, polyethylene glycol 2000 or its mixture.
It is 4. according to claim 1 and 2 to prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：Described Chlorobenzene is chlorobenzene, dichloro-benzenes or its mixture；The alkylbenzene is dimethylbenzene, ethylbenzene or its mixture.
It is 5. according to claim 1 and 2 to prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：The alkali Property the aqueous solution in alkali mass concentration be 20%~90%.
It is 6. according to claim 1 and 2 to prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：The alkali Property the aqueous solution in alkali mass concentration be 40%~70%.
It is 7. according to claim 1 and 2 to prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：Alkaline water Alkali and the mol ratio of 1,1,1,3,3- pentafluoropropanes in solution are 1.1:1~10:1, the matter of alkaline aqueous solution and aromatic solvent Amount is than being 0.1:1~10:1, phase transfer catalyst and 1, the mass ratio of 1,1,3,3- pentafluoropropane is 0.005:1~0.5:1.
It is 8. according to claim 1 and 2 to prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that：Alkaline water Alkali and the mol ratio of 1,1,1,3,3- pentafluoropropanes in solution are 1.5:1~5:1, the quality of alkaline aqueous solution and aromatic solvent Than being 0.25:1~5:1, phase transfer catalyst and 1, the mass ratio of 1,1,3,3- pentafluoropropane is 0.01:1~0.1:1.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452089A (en) * 2019-08-01 2019-11-15 顾小星 The synthetic method of p-chloromethyl styrene
CN111712480A (en) * 2018-03-14 2020-09-25 株式会社吴羽 Process for producing chain olefin

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1589248A (en) * 2001-09-25 2005-03-02 霍尼韦尔国际公司 Process for producing fluoroolefins
WO2005108332A1 (en) * 2004-04-29 2005-11-17 Honeywell International, Inc. Processes for synthesis of 1,3,3,3-tetrafluoropropene
CN102947256A (en) * 2010-04-29 2013-02-27 霍尼韦尔国际公司 Method for producing tetrafluoropropenes
CN103274895A (en) * 2005-11-03 2013-09-04 霍尼韦尔国际公司 Method for producing fluorinated organic compounds

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1589248A (en) * 2001-09-25 2005-03-02 霍尼韦尔国际公司 Process for producing fluoroolefins
WO2005108332A1 (en) * 2004-04-29 2005-11-17 Honeywell International, Inc. Processes for synthesis of 1,3,3,3-tetrafluoropropene
CN103274895A (en) * 2005-11-03 2013-09-04 霍尼韦尔国际公司 Method for producing fluorinated organic compounds
CN102947256A (en) * 2010-04-29 2013-02-27 霍尼韦尔国际公司 Method for producing tetrafluoropropenes

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111712480A (en) * 2018-03-14 2020-09-25 株式会社吴羽 Process for producing chain olefin
CN110452089A (en) * 2019-08-01 2019-11-15 顾小星 The synthetic method of p-chloromethyl styrene

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