CN106892794B - A method of preparing trans-1,3,3,3-tetrafluoropropene - Google Patents

A method of preparing trans-1,3,3,3-tetrafluoropropene Download PDF

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CN106892794B
CN106892794B CN201611239503.XA CN201611239503A CN106892794B CN 106892794 B CN106892794 B CN 106892794B CN 201611239503 A CN201611239503 A CN 201611239503A CN 106892794 B CN106892794 B CN 106892794B
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aqueous solution
tetrafluoropropenes
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pentafluoropropane
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CN106892794A (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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    • 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
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Abstract

Anti-form-1 is prepared the invention discloses a kind of, 3,3, the method of 3- tetrafluoropropene, this method is in the presence of phase transfer catalyst and aromatic solvent, and 1,1,1,3,3- pentafluoropropane and alkaline aqueous solution occur dehydrofluorination and prepare anti-form-1,3,3,3- tetrafluoropropenes, reaction temperature are 30~100 DEG C, reaction time is 10~120min, wherein phase transfer catalyst is crown ether or polyalkylene glycol, and aromatic solvent is chlorobenzene or alkylbenzene, and alkaline aqueous solution is the aqueous solution of sodium hydroxide or the aqueous solution of potassium hydroxide.The present invention constructs the two-phase dehydrofluorination system being made of alkaline aqueous solution and aromatic solvent, in the presence of a phase transfer catalyst, prepares anti-form-1 by 1,1,1,3,3- pentafluoropropane, 3,3,3- tetrafluoropropenes have the advantages that high conversion rate, solvent are reusable.

Description

A method of preparing trans-1,3,3,3-tetrafluoropropene
Technical field
Anti-form-1 is prepared the present invention relates to a kind of, the method for 3,3,3- tetrafluoropropenes, especially one kind is in phase transfer catalysis (PTC) In the presence of agent and aromatic solvent, 1,1,1,3,3- pentafluoropropane and alkaline aqueous solution occur dehydrofluorination and prepare anti-form-1, The method of 3,3,3- tetrafluoropropene.
Background technique
Anti-form-1, the ozone depletion value (ODP) of 3,3,3- tetrafluoropropenes (E-HFO-1234ze) are 0, the latent value of greenhouse effects (GWP) be 6, be known as by international community be the hydrofluorocarbon (HFCs) of high GWP ideal low-carbon environment-friendly substitute, such as foaming Agent substitutes 1,1,3,3,3- pentafluoropropane (HFC-245fa), 1,1,1,2- tetrafluoroethane (HFC-134a) and 1,1- difluoro second Alkane (HFC-152a), as aerosol propellant substitution HFC-134a etc..
Chinese patent CN104177219A, which is reported, to be included the organic matter containing alkyl and aryl nitrile, is containing 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 and alkaline aqueous solution occur Dehydrofluorination obtains HFO-1234ze.Reporting in the embodiment of Chinese patent CN1852880B will be by 91.5% HFC- The raw material of the HFO-1234ze composition of 245fa and 0.0121% is bubbled in the potassium hydroxide solution of 2.0% weight, reaction outlet It include 15.455% HFO-1234ze in mixture.In above-mentioned preparation E-HFO-1234ze technology, HFC-245fa alkali, which takes off method, to be made It is solvent with dimethyl sulfoxide soluble easily in water, tetrahydrofuran and acetonitrile etc., such organic solvent dissolves each other with alkaline aqueous solution, difficult With recycling.
Summary of the invention
It is an object of the invention to overcome deficiency present in background technique, it is repeatable to provide a kind of high conversion rate, solvent The method for preparing trans-1,3,3,3-tetrafluoropropene utilized.
The technical solution of the invention is as follows constructs the two-phase reaction system being made of alkaline aqueous solution and aromatic solvent, In the presence of a phase transfer catalyst, 1,1,1,3,3- pentafluoropropane occurs dehydrofluorination and prepares anti-form-1,3,3,3- tetrafluoros Propylene, reaction temperature are 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 be sodium hydroxide aqueous solution or potassium hydroxide it is water-soluble Liquid.
Preferably, the invention also includes the recycling steps of organic solvent:
Above-mentioned recycling step are as follows: after reaction, inorganic water phase and organic solvent phase AUTOMATIC ZONING pass through simple phase point Operation recycles organic solvent from the inorganic water phase and organic solvent phase of AUTOMATIC ZONING, is used for next secondary response.
The selected phase transfer catalyst of the present invention can be stabilized in high concentration basic aqueous solution, primarily serve by OH in alkaline aqueous solution-Ion brings the effect into aromatic solvent into.Above-mentioned crown ether is selected from 18- crown ether -6 or 15- crown ether - 5, above-mentioned polyalkylene glycol be selected from polyethylene glycol 400, Macrogol 600, cetomacrogol 1000, polyethylene glycol 2000 or its Mixture.
Aromatic solvent of the present invention has the characteristics that hydrophobicity and polarity, wherein the hydrophobicity of solvent make solvent with Alkaline aqueous solution constitutes immiscible two-phase system, and the polarity of solvent makes polar OH-Ion salt can be dissolved in organic In solvent, dehydrofluorination occurs with HFC-245fa.Above-mentioned chlorobenzene is or mixtures thereof chlorobenzene, dichloro-benzenes；Above-mentioned alkane Base benzene is or mixtures thereof dimethylbenzene, ethylbenzene.
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 1 in neutral and alkali aqueous solution of the present invention, the molar ratio of 1,1,3,3- pentafluoropropane are 1.1:1~10:1, alkali Property 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 are as follows: the molar ratio of alkali in alkaline aqueous solution and 1,1,1,3,3- pentafluoropropane be 1.5:1~ The mass ratio of 5:1 alkaline aqueous solution and aromatic solvent is 0.25:1~5:1, phase transfer catalyst and 1,1,1,3,3- pentafluoropropane Mass ratio be 0.01:1~0.1:1.
To reaction pressure, there is no limit can operate the present invention under normal pressure, negative pressure or pressurized conditions.In addition, reaction can It to be carried out continuously, also may be carried out batchwise, reaction itself requires reaction formation without obvious；
The beneficial effects of the present invention are:
1, reaction system of the invention is two-phase system, after reaction, inorganic water phase and organic solvent phase AUTOMATIC ZONING, By the i.e. recyclable organic solvent of simple phase point operation, it to be used for next secondary response, solvent can not return compared to the prior art It receives, this technology is more environmentally protective；
2, it is phase transfer catalyst that the present invention, which selects crown ether or polyalkylene glycol to high concentration basic stabilized aqueous solution, In alkaline aqueous solution and aromatic solvent two-phase system, still there is very high reactivity, under the appropriate reaction conditions, HFC- The reaction conversion ratio of 245fa dehydrofluorination reaches as high as 99% 80% or more.
Specific embodiment
It is following that explanation is described in further detail to the present invention in conjunction with the embodiments, but do not limit the scope of the invention.
Embodiment one
It reacts and is carried out in the 500mL stainless steel autoclave with stirring.Successively put into 200g's 50% into reaction kettle KOH aqueous solution, 200g chlorobenzene, 1.2g polyethylene glycol 2000 and 119g HFC-245fa open stirring, reaction temperature are risen to 70 DEG C, after reacting 60min, reaction temperature is kept, low-boiling reaction mass is slowly drained from reactor gas phase mouth, collects -30 DEG C cold hydrazine in, gas chromatographic analysis is carried out to the material of collection, the results showed 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 overall selectivity that the conversion ratio of 245fa is 20.1%, HFO-1234ze is 99.3%, and wherein the selectivity of E-HFO-1234ze is 75.2%.After comparative example one is the result shows that be added chlorobenzene, the activity of alkaline aqueous solution dehydrofluorination is greatly improved.
Embodiment three
Chlorobenzene solvent unlike embodiment one in the present embodiment is the recycling design of embodiment one, specifically: it will Reaction solution is cooled to room temperature in kettle in embodiment one, is placed in quantizer phase point, is taken lower layer's organic phase, as chlorobenzene solvent.It will return The chlorobenzene of receipts is directly used in the present embodiment reaction, other operations are constant, and reaction result shows that the conversion ratio of HFC-245fa is The overall selectivity of 95.8%, HFO-1234ze are 99.4%, and wherein the selectivity of E-HFO-1234ze is 79.1%, analyze result Show that solvent can directly recycle 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
Figure BDA0001195974970000041
Note: X245faIndicate the conversion ratio of HFC-245fa, S1234zeIt indicates to generate E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeIndicate 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 are as shown in table 2.
Table 2
Figure BDA0001195974970000042
Figure BDA0001195974970000051
Note: X245faIndicate the conversion ratio of HFC-245fa, S1234zeIt indicates to generate E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeIndicate 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 to 50% NaOH aqueous solution.Reaction result shows that the conversion ratio of HFC-245fa is for the overall selectivity of 82.5%, HFO-1234ze The selectivity of 98.5%, E-HFO-1234ze are 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 are as shown in table 3.
Table 3
Figure BDA0001195974970000052
Note: X245faIndicate the conversion ratio of HFC-245fa, S1234zeIt indicates to generate E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeIndicate 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 The results are shown in Table 4.
Table 4
Figure BDA0001195974970000061
Note: X245faIndicate the conversion ratio of HFC-245fa, S1234zeIt indicates to generate E-HFO-1234ze and Z-HFO-1234ze Overall selectivity, SE-1234zeIndicate 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
Figure BDA0001195974970000062
Note: X245faIndicate the conversion ratio of HFC-245fa, S1234zeIt indicates to generate E-HFO-1234ze's and Z-HFO-1234z Overall selectivity, SE-1234zeIndicate the selectivity of generation E-HFO-1234ze.

Claims (8)

1. a kind of prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: in the presence of a phase transfer catalyst, 1, 1,1,3,3- pentafluoropropane occurs dehydrofluorination with alkaline aqueous solution in aromatic solvent and obtains anti-form-1,3,3,3- tetrafluoro Propylene, wherein reaction temperature is 30~100 DEG C, and the reaction time is 10~120min；The phase transfer catalyst is polyalkylene Glycol, the aromatic solvent are chlorobenzene or alkylbenzene, and the alkaline aqueous solution is the aqueous solution or potassium hydroxide of sodium hydroxide Aqueous solution.
2. according to claim 1 prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: further include having The recycling step of solvent:
The recycling step are as follows: after reaction, inorganic water phase and organic solvent phase AUTOMATIC ZONING pass through simple phase point operation Organic solvent is recycled from the inorganic water phase and organic solvent phase of AUTOMATIC ZONING, is used for next secondary response.
3. according to claim 1 or 2 prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: described Polyalkylene glycol is selected from or mixtures thereof polyethylene glycol 400, Macrogol 600, cetomacrogol 1000, polyethylene glycol 2000.
4. according to claim 1 or 2 prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: described Chlorobenzene is or mixtures thereof chlorobenzene, dichloro-benzenes；The alkylbenzene is or mixtures thereof dimethylbenzene, ethylbenzene.
5. according to claim 1 or 2 prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: the alkali Property aqueous solution in alkali mass concentration be 20%~90%.
6. according to claim 1 or 2 prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: the alkali Property aqueous solution in alkali mass concentration be 40%~70%.
7. according to claim 1 or 2 prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: alkaline water Alkali in solution and 1, the molar ratio of 1,1,3,3- pentafluoropropane are 1.1:1~10:1, the matter of alkaline aqueous solution and aromatic solvent Amount is than being 0.1:1~10:1, and phase transfer catalyst and 1, the mass ratio of 1,1,3,3- pentafluoropropane is 0.005:1~0.5:1.
8. according to claim 1 or 2 prepare anti-form-1, the method for 3,3,3- tetrafluoropropenes, it is characterised in that: alkaline water Alkali in solution and 1, the molar ratio of 1,1,3,3- pentafluoropropane are 1.5:1~5:1, the quality of alkaline aqueous solution and aromatic solvent Than for 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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CN1589248A (en) * 2001-09-25 2005-03-02 霍尼韦尔国际公司 Process for producing fluoroolefins
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

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CN1589248A (en) * 2001-09-25 2005-03-02 霍尼韦尔国际公司 Process for producing fluoroolefins
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

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