CN104370690B - A kind of anti-form-1, the synthetic method of 1,1,4,4,4-hexafluoro-2-butylene - Google Patents

A kind of anti-form-1, the synthetic method of 1,1,4,4,4-hexafluoro-2-butylene Download PDF

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CN104370690B
CN104370690B CN201410667275.0A CN201410667275A CN104370690B CN 104370690 B CN104370690 B CN 104370690B CN 201410667275 A CN201410667275 A CN 201410667275A CN 104370690 B CN104370690 B CN 104370690B
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chclch
hexafluoro
butylene
nitrae
isosorbide
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CN104370690A (en
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吕剑
赵波
毛伟
王博
曾纪珺
张伟
郝志军
唐晓博
马辉
李凤仙
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Xian Modern Chemistry Research Institute
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    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
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    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine

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Abstract

The present invention provides a kind of with 1,1,1 trifluoro 2,2 dichloroethanes and chloroethylenes CH2=CX2For raw material, point three step synthesis of trans 1,1, Isosorbide-5-Nitrae, the method for 4,4 hexafluoro 2 butylene: in the presence of (a) telomerizes catalyst and catalyst aid, 1,1,1 trifluoro 2,2 dichloroethanes and CH2=CX2It is synthesized and obtains CF3CHClCH2CClX2；(b) Light chlorimation CF3CHClCH2CClX2Synthesis obtains CF3CHClCH2CCl3；In the presence of (c) fluorination catalyst, gas phase fluorination CF3CHClCH2CCl3Synthesis obtains trans 1,1,1,4,4,4 hexafluoro 2 butylene.Wherein CH2=CX2For ethene, vinyl chloride, 1,1 dichloroethylene, it is high that the present invention has trans selective, the feature of cheaper starting materials.

Description

A kind of anti-form-1, the synthetic method of 1,1,4,4,4-hexafluoro-2-butylene
Technical field
The present invention relates to the synthetic method of a kind of HF hydrocarbon, particularly relate to anti-form-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-fourths The synthetic method of alkene.
Background technology
Owing to first and second generation foaming agent (fluoro trichloromethane CFC-11, a fluorine dichloroethanes HCFC-141b etc.) destroys smelly Oxygen layer, has been prohibited from using, and third generation blowing agents (1,1,1,3,3-pentafluoropropane HFC-245fa etc.) can produce stronger Greenhouse effects.Along with earth ecology influence is increasingly sharpened by global warming, in the urgent need to finding the foaming agent of environmental protection.
As HF hydrocarbon (HFO) class material, cis-1,1, Isosorbide-5-Nitrae, the ozone of 4,4-hexafluoros-2-butylene (HFO-1336) disappears The latent value (ODP) of consumption is zero, and the latent value (GWP) of greenhouse effects is extremely low, and effect on environment is the least, because of its performance and earlier generations foaming agent phase Closely, it is counted as new generation of green environment-friendly foaming agent, with the trans-HFO-1336 cis-HFO-1336 of synthesis transition, there is route short, green The feature such as pollution-free.
Existing synthesis trans-1,1, Isosorbide-5-Nitrae, the method for 4,4-hexafluoro-2-butylene, some cost of material are higher, the trans choosing having Selecting property is relatively low.Such as: WO 2009117458 reports the copper powder with chemical quantity and HFO-1336 is synthesized with HCFC-123, produce In thing cis with trans ratios close to 1:1, not only the lowest but also pollute bigger.
WO 2011119370 reports catalyst telomerization trifluoro propene and synthesizes tetrachloro trifluorobutane with carbon tetrachloride, is catalyzed fluorine It is combined to product 1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene, use raw material trifluoro propene not yet to mass produce, expensive, produce In thing, cis HFO-1336 and trans HFO-1336 selectivity sum are 93%.
Summary of the invention
For defect or the deficiency of prior art, it is an object of the invention to provide a kind of trans selective high, raw material is honest and clean The anti-form-1 that valency is easy to get, the synthetic method of 1,1,4,4,4-hexafluoro-2-butylene.
For solving the problems referred to above, the present invention provides a kind of anti-form-1, and 1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, Anti-form-1, shown in the structural formula such as formula (I) of 1,1,4,4,4-hexafluoro-2-butylene:
Comprise the following steps:
The fluoro-2,2-dichloroethanes of (a) raw material 1,1,1-tri-and CH2=CX2Mol ratio 1～10:1, is telomerizing catalyst and is urging In the presence of changing auxiliary agent, in polar solvent, reaction temperature 80～180 DEG C, under reaction pressure 0.8～5.0MPa, react 1～48h, To CF3CHClCH2CClX2, wherein, X is Cl or H, telomerizes catalyst and uses 0 valency, 1 valency or the mantoquita of divalent；
(b) chlorine and CF3CHClCH2CClX2Mol ratio 1～3:1, under light illumination, temperature-40～80 DEG C, reaction 5～ 48h, obtains CF3CHClCH2CCl3；
C (), in the presence of fluorination catalyst, controls HF and CF3CHClCH2CCl3Mol ratio is 1:3～20, passes through shell and tube Fixed bed reactors, reaction temperature 100～500 DEG C, time of contact 0.1～10s, synthesis obtains anti-form-1, and 1, Isosorbide-5-Nitrae, 4,4-six Fluoro-2-butylene.Step (a): CF3CHCl2+CX2=CH2→CF3CHClCH2CClX2
Raw material CH2=CX2For CH2=CH2、CH2=CHCl or CH2=CCl2, CF3CHClCH2CClX2For CF3CHClCH2CH2Cl、CF3CHClCH2CHCl2Or CF3CHClCH2CCl3。
Telomerize catalyst and use 0 valency, 1 valency or the mantoquita of divalent, Cupric salicylate cuprous including elemental copper, halo copper, halo, Cupric oxalate or acetylacetone copper, preferably stannous chloride or copper chloride.
Catalyst aid is organic amine, many pyridine compounds and theirs, adds catalyst aid and can improve the dissolving telomerizing catalyst Property, reduce redox potential, although reaction is added without catalyst aid and also is able to carry out, but for reach higher conversion ratio and choosing Selecting property, preferred catalytic auxiliary agent 2,2-bipyridyl, pentamethyl-diethylenetriamine, three (2-pyridylmethyl) amine or three (2-diformazan ammonia Base ethyl) amine.
Solvent is polar solvent, including: alcohols, ketone, nitrile, amide-type, sulfone class, reaction is added without solvent, reaction Also being able to carry out, add polar solvent and can be effectively improved reaction rate and selectivity of product, therefore preferred solvent is acetonitrile, first Alcohol, acetone, dimethylformamide or dimethyl sulfoxide (DMSO).
Reaction condition is: catalyst amount be 1,1,1-tri-fluoro-2,2-dichloroethanes molar percentage be 0.01%～ 50%, preferably molar percentage is 0.5%～20%, and more preferably molar percentage is 1%～5%；Telomerize mol ratio be 1～ 10:1, preferably 2～5:1；Reaction temperature is 80～180 DEG C, and preferable temperature is 100～130 DEG C；Reaction time 1～48h, preferably 5 ～24h；Reaction pressure 0.8～5.0MPa, preferably pressure are 1.2～2.0MPa, and after reaction, product carries out pure in moving to rectifying column Change.
Step (b): CF3CHClCH2CClX2+Cl2→CF3CHClCH2CCl3
Reaction all can be carried out in gas phase, liquid phase, but for reaching more excellent selectivity, selecting response low temperature liquid phase is carried out.
Reaction need to be carried out under the ultraviolet irradiation condition of 250nm～400nm, and light source is mercury lamp or Halogen lamp LED, and reactor selects Select the material of certain light transmittance, to ensure that light is transmissive to CF3CHClCH2CClX2, when being passed through chlorine reaction one section Between, it is possible to make CF3CHClCH2CClX2At least partly it is converted into product CF3CHClCH2CCl3。
Reaction can add solvent without active H atom to improve the selectivity of product, the preferred carbon tetrachloride of solvent, 1,1, 2-trichorotrifluoroethane, chlorobenzene or fluorobenzene.
Reaction condition is: chlorine and CF3CHClCH2CClX2Mol ratio 1～3:1, preferably 1.2～1.4:1；Reaction temperature- 40～80 DEG C ,-10～40 DEG C；Reaction time is 5～48h, 12～36h.
Step (c): CF3CHClCH2CCl3+HF→CF3CH=CHCF3
React and all can obtain product in liquid phase, gas phase, but for reaching more excellent conversion ratio, selecting response is higher in temperature Gas phase is carried out, and due to Cr base catalyst, there is the problems such as bio-toxicity, environmental pollution, the problems such as use temperature is relatively low, this step In employ toxicity, less pollution, use temperature higher Fe base catalysts for gas phase fluorination.
Fe base catalysts for gas phase fluorination by the compound containing ferro element, compound containing thulium, containing element A Compound forms, and its rare earth elements is La or Ce, and element A one in Ca, Al, Mg and Ti, three kinds of element ratios are Ferro element 10～50%, element A 48～89.5%, rare earth element 0.5～2%.
Chrome-free catalysts for gas phase fluorination will be prepared after fired for described presoma, fluorination treatment.Infusion process, coprecipitated can be used Shallow lake method or the various Fe base catalysts for gas phase fluorination of the blending method synthesis present invention, the Fe base catalysts for gas phase fluorination after high-temperature roasting After precursor processes with 400 DEG C of hydrogen fluoride, for gas phase fluorination.
The type of reactor of fluorination reaction preferably has the material such as nickel and alloy thereof of anti-hydrogen fluoride corrosion effect and (includes Hastelloy, Inconel, Incoloy and Monel) calandria type fixed bed reactor made.During reaction, HF gas persistently leads to Enter catalytic fixed bed.After a period of time, start to be passed through CF continuously3CHClCH2CCl3, control CF3CHClCH2CCl3/ HF mol ratio For 1:3～20, preferably 1:6～10.CF3CHClCH2CCl3It is 100～500 DEG C with HF reaction temperature, preferably 300～400 DEG C, instead Should be time of contact 0.1～10s, preferably 3～8s, obtain anti-form-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene.
The invention have the advantages that
(1) present invention uses synthesis trans-1,1, Isosorbide-5-Nitrae, and 4,4-hexafluoro-2-butylene trans selective are not less than 95%, contrast File is suitable, trans product selectivity and be 93%.(2) present invention uses the 1,1,1-tri-fluoro-2,2-dichloroethanes with vinyl chloride to be Raw material, wherein 1,1,1-tri-fluoro-2,2-dichloroethanes be synthesis cold-producing medium HFC-125 raw material sources extensively, cheap, vinyl chloride Also being that chemical industry commonly uses raw material, therefore cost of material is low, and the method employing trifluoro propene of documents report with carbon tetrachloride is Raw material, wherein trifluoro propene not yet mass produces, and expensive is not easy to obtain.
Detailed description of the invention
Embodiment 1
A () be 1.4 grams of copper chlorides of addition in 500mL Ti Alloy Strip stirring autoclave, 3.2 gram 2, and 2-bipyridyl is molten Solution, in 20mL methyl alcohol, with air in nitrogen displacement still, is pressed into 312 grams of R123 and 63 grams of CH with nitrogen2=CHCl, reaction temperature 120 DEG C, reaction pressure 1.2MPa, 10 hours reaction time, after reaction crude product with air-distillation removing R123 and methyl alcohol, R123 with Methanol Recovery utilizes, and continues decompression distillation and collects CF3CHClCH2CHCl2, conversion ratio 91.3%, selective 87.6%.
B () adds 150 grams of CF in 500mL quartz actinic reactor3CHClCH2CHCl2It is dissolved in 300mL carbon tetrachloride Solution, be under agitation slowly introducing about 140 grams of chlorine, react 24 hours in 0 DEG C, to go out carbon tetrachloride follow-up for decompression separated Continuous collection product CF3CHClCH2CCl3, conversion ratio 90.5%, selective 78.7%.
C (), in the nickel pipe fixed-bed tube reactor that internal diameter is 38mm, loads 60ml fluorination catalyst, is passed through HF and 1, 1,1-tri-fluoro-2,4,4,4-tetra-chlorobutane CF3CHClCH2CCl3React, control HF/CF3CHClCH2CCl3Mol ratio be 6:1, time of contact is 6.9 seconds, reaction temperature 350 DEG C, and after reaction is carried out continuously 20 hours, product is removed through washing, alkali cleaning After removing HCl and HF, use gas chromatographic analysis CF3CHClCH2CCl3Conversion ratio be 100%, trans selective is 95.8%.
Embodiment 2～20 is according to synthetic method synthesis CF identical in step (a)3CHClCH2CClX2, except that real Execute example 2～20 and respectively reaction temperature, pressure, reaction time and alkene kind are carried out condition optimizing.
Table 1 reaction temperatures affect
Embodiment Catalyst (%) Reaction temperature Conversion ratio (%) Selectivity (%)
2 2 100 94.7 96.6
3 2 120 97.0 90.3
4 2 140 85.7 80.6
5 2 80 32.9 86.4
6 2 180 89.3 38.7
Table 2 pressure is on reaction impact
Embodiment Reaction temperature (DEG C) Reaction pressure (MPa) Conversion ratio (%) Selectivity (%)
7 120 0.8 80.3 93.7
8 120 1.2 95.7 90.8
9 120 2.0 93.5 90.2
10 120 3.0 76.3 85.7
11 120 5.0 60.4 75.3
Table 3 reaction time is on reaction impact
Embodiment Reaction temperature (DEG C) Reaction time (h) Conversion ratio (%) Selectivity (%)
12 120 1 61.8 97.6
13 120 6 90.9 95.4
14 120 12 91.7 94.3
15 120 24 93.7 92.2
16 120 36 94.5 76.5
17 120 48 95.1 70.3
Table 4 alkene kind is on reaction impact
Embodiment Alkene Reaction temperature Conversion ratio (%) Selectivity (%)
18 CH2=CH2 130 100 94.5
19 CHCl=CH2 130 96.3 89.2
20 CCl2=CH2 130 74.3 63.1
From the point of view of embodiment 2～20 result, the reaction optimal conditions of step (a) is: reaction temperature 100～130 DEG C, reaction Pressure 1.2～2.0MPa, the reaction time is 5～24h.
Embodiment 21～42 is according to synthetic method synthesis CF identical in step (b)3CHClCH2CCl3, except that real Execute example 21～42 and respectively reaction temperature, reaction time, reaction dissolvent and the material ratio of step (b) is carried out condition optimizing.
Table 5 reaction temperatures affect
Embodiment Solvent Reaction temperature (DEG C) Conversion ratio (%) Selectivity (%)
21 CCl4 -20 65.2 75.8
22 CCl4 -40 43.6 79.1
23 CCl4 5 91.7 76.3
24 CCl4 20 92.4 71.2
25 CCl4 50 93.7 65.8
26 CCl4 80 95.3 40.8
Table 6 reaction time is on reaction impact
Embodiment Reaction temperature (DEG C) Reaction time (h) Conversion ratio (%) Selectivity (%)
27 -5 5 53.6 54.1
28 -5 10 65.9 75.3
29 -5 24 93.7 78.9
30 -5 36 94.5 72.4
31 -5 48 95.1 40.3
The impact on reaction of table 7 reaction dissolvent
Embodiment Solvent Reaction temperature (DEG C) Conversion ratio (%) Selectivity (%)
32 - 0 90.5 58.9
33 CFCl2CF2Cl 0 91.6 75.8
34 Chlorobenzene 0 93.4 80.2
35 CCl4 0 95.5 81.7
36 Acetonitrile 0 62.3 42.7
37 Dimethyl sulfoxide (DMSO) 0 20.3 50.6
Table 8 chlorine consumption is on reaction impact
Embodiment Solvent Chlorine mol ratio Conversion ratio (%) Selectivity (%)
38 CCl4 1:1 43.6 78.7
39 CCl4 1.2:1 98.6 80.2
40 CCl4 1.5:1 96.2 75.9
41 CCl4 2.0:1 96.9 68.3
42 CCl4 3.0:1 97.8 57.8
From the point of view of embodiment 21～42 result, the reaction optimal conditions of step (b) is: reaction temperature-10～40 DEG C, reaction Time 12～36h, chlorine and CF3CHClCH2CClX2Mol ratio 1.2～1.4:1.
Embodiment 43～58 is according to synthetic method synthesis of trans-1,1,1,4,4,4-hexafluoro-2-fourth identical in step (c) Alkene, except that embodiment 43～58 to have carried out condition reaction temperature, mol ratio and time of contact to step (c) respectively excellent Change.
Table 9 reaction temperatures affect
Embodiment Mol ratio Reaction temperature (DEG C) Conversion ratio (%) Selectivity (%)
43 1:6 100 43.6 70.2
44 1:6 200 65.7 80.9
45 1:6 300 100 95.3
46 1:6 400 100 96.8
47 1:6 500 100 91.2
Table 10 mol ratio is on reaction impact
Embodiment Reaction temperature Mol ratio Conversion ratio (%) Selectivity (%)
48 350 1:3 70.5 84.7
49 350 1:5 94.6 90.3
50 350 1:10 100 95.7
51 350 1:15 100 92.1
52 350 1:20 100 90.7
Reaction is affected time of contact by table 11
Embodiment Reaction temperature (DEG C) Time of contact (h) Conversion ratio (%) Selectivity (%)
53 400 0.1 50.3 71.6
54 400 1 75.2 80.4
55 400 3 96.5 95.2
56 400 5 98.9 96.7
57 400 8 100 95.6
58 400 10 100 90.2
From the point of view of embodiment 43～58 result, the reaction optimal conditions of step (c) is: reaction temperature 300～400 DEG C, HF With CF3CHClCH2CCl3Mol ratio 1:6～10, time of contact 3～8s.

Claims (8)

1. an anti-form-1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, anti-form-1,1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-butylene Structural formula such as formula (I) shown in:
Comprise the following steps:
The fluoro-2,2-dichloroethanes of (a) raw material 1,1,1-tri-and CH2=CX2Mol ratio 1～10:1, helps with catalysis telomerizing catalyst In the presence of agent, in polar solvent, reaction temperature 80～180 DEG C, under reaction pressure 0.8～5.0MPa, react 1～48h, obtain CF3CHClCH2CClX2, wherein, X is Cl or H, and telomerizing catalyst is 0 valency, 1 valency or the mantoquita of divalent；
(b) chlorine and CF3CHClCH2CClX2Mol ratio 1～3:1 under light illumination, temperature-40～80 DEG C, react 5～48h, obtain CF3CHClCH2CCl3；
C (), in the presence of fluorination catalyst, controls CF3CHClCH2CCl3It is that 1:6～10 is fixed by shell and tube with HF mol ratio Bed reactor, reaction temperature 300～400 DEG C, time of contact 3～8s, synthesis obtains anti-form-1, and 1, Isosorbide-5-Nitrae, 4,4-hexafluoro-2-fourths Alkene, wherein, fluorination catalyst is Fe base catalysts for gas phase fluorination, by 10～the ferro element of 50%, 48～the element A of 89.5% and 0.5～2% rare earth element constitute.
Anti-form-1 the most according to claim 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterised in that former Material CH2=CX2For CH2=CH2、CH2=CHCl or CH2=CCl2。
Anti-form-1 the most according to claim 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterised in that CF3CHClCH2CClX2For CF3CHClCH2CH2Cl、CF3CHClCH2CHCl2Or CF3CHClCH2CCl3。
Anti-form-1 the most according to claim 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterised in that step Suddenly telomerize described in (a) catalyst be that elemental copper, halo copper, halo be cuprous, Cupric salicylate, cupric oxalate or acetylacetone copper.
Anti-form-1 the most according to claim 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterised in that step Suddenly catalyst aid described in (a) is 2,2-bipyridyl, pentamethyl-diethylenetriamine, three (2-pyridylmethyl) amine or three (2-bis- Methylaminoethyl) amine.
Anti-form-1 the most according to claim 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterised in that step Suddenly the polar solvent described in (a) is acetonitrile, methyl alcohol, acetone, dimethylformamide or dimethyl sulfoxide (DMSO).
Anti-form-1 the most according to claim 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterised in that step Suddenly the rare earth metal described in (c) is La or Ce, element A one in Ca, Al, Mg and Ti.
Anti-form-1 the most according to claim 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4-hexafluoro-2-butylene, it is characterised in that:
(a) raw material CH2=CX2With 1,1,1-tri-fluoro-2,2-dichloroethanes mol ratio 2～5:1, at mantoquita and organic amine part In the presence of, in methyl alcohol, acetonitrile or dimethyl sulfoxide react 5～24h, reaction temperature 100～130 DEG C, reaction pressure 1.2～ 2.0MPa, synthesis obtains CF3CHClCH2CClX2, wherein, X is Cl or H；
Under (b) high voltage mercury lamp radiation, chlorine and CF3CHClCH2CClX2Mol ratio 1.2～1.4:1 in carbon tetrachloride, 1,1,2-tri- In chloro-trifluoro-ethane or chlorobenzene ,-10～40 DEG C, reacting 12～36h, synthesis obtains CF3CHClCH2CCl3；
In the presence of (c) Fe base catalysts for gas phase fluorination, control CF3CHClCH2CCl3Shell and tube is passed through with HF mol ratio 1:6～10 Fixed bed reactors, reaction temperature 300～400 DEG C carry out fluorination reaction, time of contact 3～8s, obtain anti-form-1, and 1, Isosorbide-5-Nitrae, 4, 4-hexafluoro-2-butylene, wherein, fluorination catalyst is Fe base catalysts for gas phase fluorination, by 10～the ferro element of 50%, 48～ The element A of 89.5% and 0.5～2% rare earth element constitute.
CN201410667275.0A 2014-11-20 2014-11-20 A kind of anti-form-1, the synthetic method of 1,1,4,4,4-hexafluoro-2-butylene Active CN104370690B (en)

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CN109553506B (en) * 2018-12-20 2021-10-01 西安近代化学研究所 Method for synthesizing trans-1, 1,1,4,4, 4-hexafluoro-2-butene
US20220162141A1 (en) * 2019-04-05 2022-05-26 The Chemours Company Fc, Llc Process for producing 1,1,1,4,4,4-hexafluorobut-2-ene
CN110590494A (en) * 2019-09-24 2019-12-20 浙江三美化工股份有限公司 Method for synthesizing 1,1,1,4,4, 4-hexafluoro-2-butene in illumination environment
CN111574321B (en) * 2020-06-17 2021-09-03 广东电网有限责任公司电力科学研究院 Preparation method of trans-1, 1,1,4,4, 4-hexafluoro-2-butene
CN114262255B (en) * 2021-12-01 2023-10-20 西安近代化学研究所 Method for synthesizing trans-1, 4-hexafluoro-2-butene
CN116037118B (en) * 2023-03-31 2023-07-25 北京宇极科技发展有限公司 Preparation method of perfluoro-3-methyl-2-butanone
CN116874344B (en) * 2023-09-06 2023-12-08 北京宇极科技发展有限公司 Process for the continuous preparation of E-1, 4, 5-heptafluoro-4- (trifluoromethyl) pent-2-ene

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5463150A (en) * 1993-02-19 1995-10-31 Bayer Aktiengesellschaft Process for preparing hexafluorobutene
CN102884030A (en) * 2010-03-26 2013-01-16 霍尼韦尔国际公司 Method for making hexafluoro-2-butene
CN103209943A (en) * 2010-11-17 2013-07-17 纳幕尔杜邦公司 Catalytical synthesis of internal fluorobutenes and internal fluoropentenes

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994012454A1 (en) * 1992-11-20 1994-06-09 Daikin Industries, Ltd. Process for producing 1,1,1,4,4,4-hexafluoro-2-butene and 1,1,1,4,4,4,-hexafluorobutane
JP5341978B2 (en) * 2008-03-19 2013-11-13 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Method for producing 1,1,1,4,4,4-hexafluoro-2-butene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5463150A (en) * 1993-02-19 1995-10-31 Bayer Aktiengesellschaft Process for preparing hexafluorobutene
CN102884030A (en) * 2010-03-26 2013-01-16 霍尼韦尔国际公司 Method for making hexafluoro-2-butene
CN103209943A (en) * 2010-11-17 2013-07-17 纳幕尔杜邦公司 Catalytical synthesis of internal fluorobutenes and internal fluoropentenes

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