CN105439804B - A kind of preparation method of 1,1,1,2,2 pentafluoropropane - Google Patents
A kind of preparation method of 1,1,1,2,2 pentafluoropropane Download PDFInfo
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- CN105439804B CN105439804B CN201510765329.1A CN201510765329A CN105439804B CN 105439804 B CN105439804 B CN 105439804B CN 201510765329 A CN201510765329 A CN 201510765329A CN 105439804 B CN105439804 B CN 105439804B
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- fluorine
- butyl
- pentafluoropropane
- cation
- antimonic salt
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/087—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
Abstract
The invention discloses the method that one kind prepares 1,1,1,2,2 pentafluoropropane, this method is by hydrogen fluoride and 2, the liquid-phase fluorination synthesis 1,1,1,2 under fluorine-containing antimonic salt catalyst action of 3,3,3 tetrafluoropropenes, 2 pentafluoropropanes, 2,3,3,3 tetrafluoropropenes and HF mol ratio are 0.02~1:The inventory of 1,2,3,3,3 tetrafluoropropene and the mol ratio of fluorine-containing antimonic salt are 0.1~10:1, reaction temperature is 0 DEG C~80 DEG C, wherein the formula of fluorine-containing antimonic salt catalyst is Q+[SbxClyF5x‑y+1]‑, cation Q+For alkali metal cation, quaternary ammonium cation Huo quaternary phosphine cations, 1 ＜ x≤3,0≤y ＜ 3.The method of the pentafluoropropane of preparation 1,1,1,2,2 of the present invention has the advantages that reaction selectivity height, reaction condition are gentle.
Description
Technical field
It is Q the present invention relates to a kind of preparation method of 1,1,1,2,2- pentafluoropropane, more particularly in formula+
[SbxClyF5x-y+1]-Fluorine-containing antimonic salt catalyst in the presence of, hydrogen fluoride and 2,3,3,3- tetrafluoropropene liquid-phase fluorinations synthesis 1,1,
The method of 1,2,2- pentafluoropropanes.
Background technology
As global warming problem was increasingly serious in recent years, third generation refrigerant, which faces, to be eliminated or is washed in a pan in advance
Eliminate.Countries in the world are all in the forth generation novel environment-friendly refrigerant of active development excellent performance.1,1,1,2,2- pentafluoropropanes (HFC-
245cb) as one of component in forth generation refrigerant, its market prospects is had an optimistic view of.
Chinese patent CN103483140A is reported under Cr/Co catalysts, gas phase fluorination trifluoro propane (HCFC-
HFC-245cb 243db) is synthesized, reaction temperature is 325 DEG C, and HCFC-243db 100% is converted, but HFC-245cb selection
Property only has 11.4%.United States Patent (USP) US8309774 is reported under Ni-Cr/AlF3 catalysts, gas phase fluorination 2- chloro- 3,
3,3 trifluoro propenes (HCFC-1233xf) synthesize HFC-245cb, and reaction temperature is 352 DEG C, and reaction product is 2,3,3,3- tetrafluoros
The mixture of propylene (HFO-1234yf) and HFC-245cb, wherein HFC-245cb content are at 27.5%~33.8%, two kind
Product is distributed by thermodynamical equilibrium control.Above two pieces patent, HFC-245cb selectivity is relatively low, and reaction temperature is also very
Height, severe reaction conditions.
The content of the invention
It is an object of the invention to overcome deficiency present in background technology, there is provided a kind of reaction selectivity height, reaction bar
The method for preparing 1,1,1,2,2- pentafluoropropanes of part gently.
In order to realize the purpose of the present invention, of the invention 1, the preparation method of 1,1,2,2- pentafluoropropane, the technology of use
Scheme is：The liquid-phase fluorination under fluorine-containing antimonic salt catalyst action synthesizes 1,1,1,2,2- five to hydrogen fluoride with 2,3,3,3- tetrafluoropropenes
Fluoro-propane, 2,3,3,3- tetrafluoropropenes and HF mol ratio are 0.02~1:The inventory of 1,2,3,3,3- tetrafluoropropene with it is fluorine-containing
The mol ratio of antimonic salt is 0.1~10:1, reaction temperature is 0 DEG C~80 DEG C, wherein the formula of fluorine-containing antimonic salt catalyst is Q+
[SbxClyF5x-y+1]-, cation Q+For alkali metal cation, quaternary ammonium cation Huo quaternary phosphine cations, 1 ＜ x≤3,0≤y ＜ 3.
Described alkali metal cation is K+、Rb+Or Cs+, described quaternary ammonium cation is tetra-allkylammonium, dialkylimidazolium
, trialkylimidazolium, N- alkyl pyridines, N- alkyl-N- crassitudes or N- alkyl-N- methyl piperidines, it is described
Quaternary phosphines cation is alkyl San Ding Ji Phosphonium.Specific preferred cation Q+It is Cs+, tetraethyl ammonium ([NEt4]), 1- ethyls -3-
Methylimidazole ([EMIm]), 1- butyl -3- methylimidazoles ([BMIm]), 1- butyl -2,3- methylimidazoles
([BMMIm]), N- butyl-pyridiniums ([BPy]), N- butyl-N- methyl piperidines ([PP14]), N- butyl-N- crassitudes
([P14]) or 4-butyl-phosphonium ([P4444])。
In described fluorine-containing antimonic salt, anion [SbxClyF5x-y+1]-It is fluorine-containing when only x and y values are suitable for catalytic center
Antimonic salt just has excellent catalytic activity and stability, x and y values preferably scope is respectively 1 ＜ x≤2.5,0≤y ＜ 2, more excellent
The scope of choosing is respectively 1.5 ＜ x≤2,0≤y ＜ 1.
Described fluorine-containing antimonic salt can directly use business product, also can laboratory prepare, laboratory preparation method is as follows：
By hydrogen fluoride salts Q in solvent+F-(HF)m(0 ＜ m ＜ 20) and antimonic salt SbClzF5-z(z=0~5) are mixed with appropriate molar ratio x
Reaction is closed, subsequent desolvation obtains fluorine-containing antimonic salt Q+[SbxClyF5x-y+1]-.Solvent described in method for not with lewis acid
The polar solvent chemically reacted with hydrogen fluoride, specific preferred have SO2、SOClF、CH3CN、CF2ClCF2Cl、CF3CH2Cl、
CF3CHFCl、CF3CH2CF2、CF3CH2CF2CH3Deng.Q in method+F-(HF)mWith SbF5Mixing molar ratio x be 1：1~1：3,
Reaction temperature is 25~100 DEG C, and the reaction time is 1~48 hour.
The method for preparing HFC-245cb of the present invention can be carried out intermittently or serially.In a batch process, HF and HFO-
1234yf is disposably added to reactor, rises to corresponding reaction temperature, reaction condition preferably is HFO-1234yf's and HF
Molar ratio is 0.02~0.1:1, HFO-1234yf inventory and the mol ratio of fluorine-containing antimonic salt are 0.1~10：1, reaction
Temperature is 0 DEG C~80 DEG C, and the reaction time is 0.5h~10h.In a continuous process, HF and HFO-1234yf continuously enter reaction
Device, reaction condition preferably is：HFO-1234yf and HF mol ratio is 0.5~1:1, HFO-1234yf inventory with it is fluorine-containing
The mol ratio of antimonic salt is 0.25~2:1, reaction temperature is 35 DEG C~60 DEG C.
Compared with prior art, the advantage of the invention is that：(1) reaction selectivity is high, the reaction without obvious accessory substance,
HFC-245cb selectivity is close to 100%, and simultaneous reactions conversion ratio is also higher, and HFO-1234yf conversion ratios are more than 80%；
(2) reaction condition is gentle, and reaction temperature is at 0 DEG C~80 DEG C, and temperature preferably is at~50 DEG C, far below 325 DEG C of document report.
Embodiment
It is following the present invention to be described in further detail in conjunction with the embodiments explanation, but do not limit the scope of the invention.
Embodiment 1
Interval liquid phase fluorination reaction is carried out in the 250mL stainless steel autoclaves with stirring.Put into successively into reactor
58.5g CsSb2F11, 40g HF and 11.4g HFO-1234yf, reaction temperature be 50 DEG C, react 5h.Reaction samples warp after terminating
Gas chromatographic analysis after washing deacidification, as a result shows that HFO-1234yf conversion ratio is for 95.5%, HFC-245cb selectivity
100%.
Embodiment 2~9
The method that embodiment 2~9 prepares HFC-245cb is same as Example 1, except that change fluorine-containing antimonic salt, it is anti-
Temperature and reaction time are answered, reaction result is as shown in table 1.
Table 1
Embodiment 10~15
The method that embodiment 10~15 prepares HFC-245cb is same as Example 1, except that changing HFO-1234yf
Mol ratio, HFO-1234yf inventorys and mol ratio, reaction temperature and the reaction time of fluorine-containing antimonic salt with HF, reaction result is such as
Shown in table 2.
Table 2
Embodiment 16
Continuous Liquid Phase fluorination is carried out in 2L stainless steel autoclaves, and the top of autoclave is equipped with destilling tower and reflux condensation mode
Heated using oil cauldron device, bottom.Fluorine-containing antimonic salt [EMIm] [Sb is prepared in autoclave first2F11] catalyst.By 176g 1- second
The methylimidazole hydrofluorination of base -3 salt ([EMIm] (HF)2.3F, 0.1mol)) and 432g SbF5(0.2mol) and 500g SO2Solvent adds
Enter into the stainless steel cauldron equipped with stirring, the reactor is placed in liquid nitrogen.Reactor is slowly increased to room temperature, reaction starts
Notable heat release, maintenance reaction device temperature is cooled down by frozen water.When exothermic heat of reaction slows down, temperature of reactor is risen to 50 DEG C, 4 are maintained
Hour.After reaction terminates, solvent in vacuo is extracted, catalyst preparation is finished.600g HF are put into reactor, 50 are warming up to
DEG C, constant temperature 2h.Then HFO-1234yf and HF are squeezed into reactor by the way that measuring pump is continuous, HFO-1234yf charging speed
Rate is 65g/h, and HF feed rate is 10g/h, and reaction temperature is 50~55 DEG C, and reaction result is shown in Table 3.As shown in Table 3, continuously
Run in 450h, HFO-1234yf conversion ratios are maintained between 91%~94%, HFC-245cb is selectively 100%.
Table 3
Claims (3)
1. the preparation method of the pentafluoropropane of one kind 1,1,1,2,2-, it is characterised in that hydrogen fluoride and 2,3,3,3- tetrafluoropropenes containing
Liquid-phase fluorination synthesizes the mol ratio of 1,1,1,2,2- pentafluoropropane, 2,3,3,3- tetrafluoropropenes and HF under fluorine antimonic salt catalyst action
For 0.02~1:The inventory of 1,2,3,3,3- tetrafluoropropene and the mol ratio of fluorine-containing antimonic salt are 0.1~10:1, reaction temperature is 0
DEG C~80 DEG C, wherein the formula of fluorine-containing antimonic salt catalyst is Q+[SbxClyF5x-y+1]-, cation Q+For alkali metal cation, quaternary ammonium
Cation Huo quaternary phosphine cations, 1 ＜ x≤3,0≤y ＜ 3.
2. according to claim 11, the preparation method of 1,1,2,2- pentafluoropropane, it is characterised in that described alkali metal
Cation is K+、Rb+Or Cs+, described quaternary ammonium cation is tetra-allkylammonium, dialkylimidazolium, trialkylimidazolium, N- alkane
Yl pyridines, N- alkyl-N- crassitudes or N- alkyl-N- methyl piperidines, the quaternary phosphines cation are alkyl three
Ding Ji Phosphonium.
3. according to claims 1 to 21, the preparation method of 1,1,2,2- pentafluoropropane, it is characterised in that described sun from
Sub- Q+It is Cs+, tetraethyl ammonium, 1- ethyl-3-methylimidazoles, 1- butyl -3- methylimidazoles, 1- butyl -2,3- dimethyl miaows
Azoles, N- butyl-pyridiniums, N- butyl-N- methyl piperidines, N- butyl-N- crassitudes or 4-butyl-phosphonium.
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