CN110372472A - A kind of synthetic method of the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- - Google Patents
A kind of synthetic method of the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- Download PDFInfo
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- CN110372472A CN110372472A CN201910682326.XA CN201910682326A CN110372472A CN 110372472 A CN110372472 A CN 110372472A CN 201910682326 A CN201910682326 A CN 201910682326A CN 110372472 A CN110372472 A CN 110372472A
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- butylene
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- nitrae
- isosorbide
- fluoro
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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
Abstract
The invention discloses a kind of 2- chloro- 1,1, Isosorbide-5-Nitrae, the synthetic methods of 4,4- hexafluoro -2- butylene, with 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene are raw material, in the presence of gas phase or liquid-phase fluorination catalyst, with anhydrous hydrogen fluoride reaction, obtain 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene.The present invention provides 1,2- of one kind bis- chloro- 1, Isosorbide-5-Nitrae, the catalytic fluorination method of 4,4- five fluoro- 2- butylene is mainly used for 2- chloro- 1,1, Isosorbide-5-Nitrae, the synthesis of 4,4- hexafluoro -2- butylene.
Description
Technical field
The present invention relates to a kind of 2- chloro- 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4- hexafluoro -2- butylene belongs to fluorine chemical field.
Background technique
The serious environmental problem such as ozone layer or greenhouse effect value height is destroyed since traditional fluoro hydrocarbon blowing agent exists, it is novel
The industrially prepared technology of foaming agent has become the research hotspot of fluorine chemical field.Cis- 1,1,1,4,4,4- hexafluoro -2- butylene (Z-
HFO-1336mzz) foaming, heat-insulated, thermal insulation property and conventional foaming agents are suitable, and ozone-depleting value (ODP) of dive is zero, and greenhouse is imitated
The value that should dive (GWP) is 9, and effect on environment very little is considered as new generation of green environment-friendly foaming agent.
As the important intermediate of synthesis Z-HFO-1336mzz, 2- chloro- 1,1, Isosorbide-5-Nitrae, the big rule of 4,4- hexafluoro -2- butylene
Mould synthesis is one of the key technology for realizing that Z-HFO-1336mzz is industrially prepared.Document (CN104072333B and
CN105418361A it) reports and 2- chloro- 1,1 is synthesized under Antimony pentachloride catalysis by hexachlorobutadiene and anhydrous hydrogen fluoride,
Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, however, Antimony pentachloride there are valence state reduce inactivation, thermal stability is poor the disadvantages of, catalyst life
It is extremely short, it is difficult to realize extensive synthesis；Document CN106008147B reports hexachlorobutadiene and anhydrous hydrogen fluoride in gas phase fluorine
Change and synthesizes 2- chloro- 1,1 under catalyst, Isosorbide-5-Nitrae, the method for 4,4- hexafluoro -2- butylene, but it is stably catalyzed using chlorine due to needing
Agent causes selectivity of product to be remarkably decreased；Document CN106536462A and CN103524297B then pass through 2,3- bis- chloro- 1,1,1,
4,4,4- hexafluoro -2- butylene are reacted by hydrogenation-dechlorination synthesizes 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, but due to adding hydrogen
The problems such as reaction is difficult to control, and the technique is poor there are selectivity of product.
Summary of the invention
The technical problem to be solved by the present invention is in view of the deficiencies of the prior art, the high, thermostabilization by using reactivity
Property good reaction raw materials 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene, it is good to obtain a kind of catalyst stability, product selection
Property high, the general 2- of gas, liquid flaorination process chloro- 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4- hexafluoro -2- butylene.
2- chloro- 1,1 of the present invention, Isosorbide-5-Nitrae, the synthetic method of 4,4- hexafluoro -2- butylene, using 1,2- bis- chloro- 1,1,
4,4,4- five fluoro- 2- butylene are that raw material, with anhydrous hydrogen fluoride reaction, obtains 2- in the presence of gas phase or liquid-phase fluorination catalyst
Chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, reaction equation is as follows:
Gas phase fluorination condition are as follows: in the presence of fluorination catalyst, control 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2-
Butylene and anhydrous hydrogen fluoride molar ratio are 3~20:1 by calandria type fixed bed reactor, 100~500 DEG C of reaction temperature, are contacted
0.1~10s of time, wherein catalysts for gas phase fluorination is oxide, fluoride or the fluorine oxide of iron, chromium, aluminium or magnesium；Liquid
Phase fluorination reaction response condition are as follows: the bis- fluoro- 2- butylene of chloro- 1,1,4,4,4- five of 1,2- is 3~10 with anhydrous hydrogen fluoride molar ratio:
1, liquid-phase fluorination catalyst and 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, the molar ratio of 4,4- five fluoro- 2- butylene is 0.25~2:1, reaction temperature
It is 50~200 DEG C, the reaction time is 2~8h, wherein liquid-phase fluorination catalyst is chloride, the fluoride of antimony, titanium, niobium or tantalum
Or fluorine chlorine compound.
The catalysts for gas phase fluorination be ferric flouride, charomic fluoride, aluminum fluoride, magnesium fluoride, fluorine iron oxide, fluorine chromium oxide,
Fluorine alumina, magnesia or the loaded catalyst prepared using them as carrier.
The liquid-phase fluorination catalyst be antimony trichloride, Antimony pentachloride, fluorine antimony chloride, titanium dioxide, vanadium pentoxide,
Niobium pentaoxide, tantalum pentoxide, titanium tetrachloride, phosphoric alum, columbium pentachloride, tantalic chloride, titanium tetrafluoride, five fluorination alum,
Niobium (Nb) pentafluoride or tantalum pentafluoride.
The gas phase fluorination condition are as follows: in the presence of fluorination catalyst, control 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five
Fluoro- 2- butylene and anhydrous hydrogen fluoride molar ratio are that 6~10:1 passes through calandria type fixed bed reactor, reaction temperature 200~300
DEG C, 1~5s of time of contact.
The liquid phase fluorination reaction reaction condition are as follows: the bis- fluoro- 2- butylene of chloro- 1,1,4,4,4- five of 1,2- and anhydrous fluorination
Hydrogen molar ratio is 4~6:1, and liquid-phase fluorination catalyst and 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, the molar ratio of 4,4- five fluoro- 2- butylene is 0.50
~1:1, reaction temperature are 80~130 DEG C, and the reaction time is 3~6h.
The present invention has the advantages that
(1) 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butene reaction activity are high, are not easy coking, therefore, catalyst life
It is long；(2) with 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene are raw material by gas phase or liquid phase fluorination reaction, and product is 2-
Chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, reaction process is that traditional gas, liquid fluorination is general.
Specific embodiment
Below by specific embodiment, invention is further described in detail, but not does in any form to the present invention
Limitation.
Embodiment 1:
Gas phase fluorination operating method
In the nickel tube fixed-bed tube reactor that internal diameter is 38mm, it is packed into 60ml and is fluorinated chrome catalysts, be passed through HF and 1,
2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene are reacted, control HF/1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene
Molar ratio is 3/1, and time of contact is 6.9 seconds, and 265 DEG C of reaction temperature, reaction product is used after washing, alkali cleaning remove HCl and HF
Gas chromatographic analysis, reacts after being carried out continuously 100 hours, 1,2- bis- chloro- 1, and the conversion ratio of Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene is
100%, 2- chloro- 1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene are selectively 97.4%.
Liquid phase fluorination reaction operating method
15 grams of Antimony pentachlorides and 50 grams of anhydrous hydrogen fluorides, nitrogen is added into 300mL stainless steel band stirring autoclave
Indentation 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene, mixture are warming up to 100 DEG C of reactions 3-4 hours after being stirred at room temperature,
Discharge material is collected with cold-trap, product yield 87.9%.
Product is detected through nuclear-magnetism, and data are as follows:
1H NMR(500MHz,CDCl3) δ 6.64 (q, 1H, J=6.5Hz)；
13C NMR(500MHz,CDCl3) δ 132.0 (qq, J=39.3Hz, J=5.4Hz), 121.9 (q, J=37.5Hz),
120.6 (q, J=270Hz), 119.1 (q, J=272.5Hz)；
19F NMR(470MHz,CDCl3)δ-71.3(m,CF3),-61.3(m,CF3).
Above-mentioned data prove that it is exactly the chloro- 1,1,1,4,4,4- hexafluoro -2- butylene of 2- that product, which is made,.
Embodiment 2~4
Embodiment 2~4 prepares the chloro- 1,1,1,4,4,4- six of 2- according to gas phase fluorination method identical in embodiment 1
Fluoro- 2- butylene, except that the catalyst in embodiment 1 is charomic fluoride, and catalyst is respectively to be fluorinated in embodiment 2~4
Iron, aluminum fluoride, magnesium fluoride.The reaction result of embodiment 2~4 is as shown in table 1.
The screening of 1 catalysts for gas phase fluorination of table
| Embodiment | Catalyst | Conversion ratio (%) | Selectivity (%) |
| 2 | FeF3 | 99.5 | 87.3 |
| 3 | AlF3 | 100 | 98.9 |
| 4 | MgF2 | 100 | 95.5 |
Embodiment 5~9
Embodiment 5~9 prepares the chloro- 1,1,1,4,4,4- six of 2- according to liquid phase fluorination reaction method identical in embodiment 1
Fluoro- 2- butylene, except that the catalyst in embodiment 1 is Antimony pentachloride, and catalyst is respectively four in embodiment 5~9
Titanium chloride, vanadium pentoxide, columbium pentachloride, tantalum pentafluoride, antimony pentafluoride.The reaction result of embodiment 5~9 is as shown in table 1.
The screening of 2 liquid-phase fluorination catalyst of table
Claims (4)
1. a kind of 2- chloro- 1,1, Isosorbide-5-Nitrae, the synthetic method of 4,4- hexafluoro -2- butylene, it is characterised in that with 1,2- bis- chloro- 1, Isosorbide-5-Nitrae,
4,4- five fluoro- 2- butylene are that it is chloro- to obtain 2- with anhydrous hydrogen fluoride reaction in the presence of gas phase or liquid-phase fluorination catalyst for raw material
1,1, Isosorbide-5-Nitrae, 4,4- hexafluoro -2- butylene, gas phase fluorination condition are as follows: in the presence of fluorination catalyst, 1,2- bis- chloro- 1 is controlled,
Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene and anhydrous hydrogen fluoride molar ratio are that 3~20:1 passes through calandria type fixed bed reactor, reaction temperature
100~500 DEG C, 0.1~10s of time of contact, wherein catalysts for gas phase fluorination is oxide, the fluoride of iron, chromium, aluminium or magnesium
Or fluorine oxide；Liquid phase fluorination reaction reaction condition are as follows: the bis- fluoro- 2- butylene of chloro- 1,1,4,4,4- five of 1,2- and anhydrous fluorination
Hydrogen molar ratio is 3~10:1, and the molar ratio of liquid-phase fluorination catalyst and 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene is
0.25~2:1, reaction temperature be 50~200 DEG C, the reaction time be 2~8h, wherein liquid-phase fluorination catalyst be antimony, titanium, niobium or
Chloride, fluoride or the fluorine chlorine compound of tantalum.
2. 2- chloro- 1,1 according to claim 1, Isosorbide-5-Nitrae, the synthetic method of 4,4- hexafluoro -2- butylene, it is characterised in that institute
Stating catalysts for gas phase fluorination is ferric flouride, charomic fluoride, aluminum fluoride, magnesium fluoride, fluorine iron oxide, fluorine chromium oxide, fluorine alumina, oxidation
Magnesium or the loaded catalyst prepared using them as carrier.
3. 2- chloro- 1,1 according to claim 1, Isosorbide-5-Nitrae, the synthetic method of 4,4- hexafluoro -2- butylene, it is characterised in that institute
State liquid-phase fluorination catalyst be antimony trichloride, Antimony pentachloride, fluorine antimony chloride, titanium dioxide, vanadium pentoxide, niobium pentaoxide,
Tantalum pentoxide, titanium tetrachloride, phosphoric alum, columbium pentachloride, tantalic chloride, titanium tetrafluoride, five fluorination alum, niobium (Nb) pentafluoride or five
It is fluorinated tantalum.
4. 2- chloro- 1,1 according to claim 1, Isosorbide-5-Nitrae, the synthetic method of 4,4- hexafluoro -2- butylene, it is characterised in that gas
Phase fluorination reaction condition are as follows: in the presence of fluorination catalyst, control 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, 4,4- five fluoro- 2- butylene with it is anhydrous
Hydrogen fluoride molar ratio is 6~10:1 by calandria type fixed bed reactor, 200~300 DEG C of reaction temperature, 1~5s of time of contact；
Liquid phase fluorination reaction reaction condition are as follows: the bis- fluoro- 2- butylene of chloro- 1,1,4,4,4- five of 1,2- and anhydrous hydrogen fluoride molar ratio be 4~
6:1, liquid-phase fluorination catalyst and 1,2- bis- chloro- 1, Isosorbide-5-Nitrae, the molar ratio of 4,4- five fluoro- 2- butylene are 0.50~1:1, reaction temperature
Degree is 80~130 DEG C, and the reaction time is 3~6h.
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| CN111558386A (en) * | 2020-04-10 | 2020-08-21 | 西安近代化学研究所 | Iron fluoride-based catalyst for synthesizing hydrofluoroolefin by gas phase fluorination and preparation method and application thereof |
| CN112552141A (en) * | 2020-12-18 | 2021-03-26 | 西安近代化学研究所 | Preparation method of 2-chloro-1, 1,1,4,4, 4-hexafluoro-2-butene |
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