CN1080630A - A kind of method for preparing hydrogen flourohalocarbon and hydrogen fluorohydrocarbon - Google Patents

A kind of method for preparing hydrogen flourohalocarbon and hydrogen fluorohydrocarbon Download PDF

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CN1080630A
CN1080630A CN 92108469 CN92108469A CN1080630A CN 1080630 A CN1080630 A CN 1080630A CN 92108469 CN92108469 CN 92108469 CN 92108469 A CN92108469 A CN 92108469A CN 1080630 A CN1080630 A CN 1080630A
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nitrogenous compound
mole
reaction
hydrogen fluoride
hydrogen
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CN1037960C (en
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胡昌明
涂明虎
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

The present invention is a kind of method for preparing hydrogen halogen fluorohydrocarbon or hydrogen fluorohydrocarbon from anhydrous hydrogen fluoride and fluorine halogen alkene in the presence of catalyzer, used catalyzer is the mixture of group VIII metallic element or nitrogenous compound or group VIII metallic element and nitrogenous compound, present method is easy, is easy to suitability for industrialized production.

Description

A kind of method for preparing hydrogen flourohalocarbon and hydrogen fluorohydrocarbon
The invention belongs to the method for anhydrous hydrogen fluoride and the addition reaction under catalyst of fluorine halogen alkene.
Because Chlorofluorocarbons (CFCs) (CFC) and Kazakhstan dragon (Halon) have great destruction to atmospheric ozone layer, they are restricted day by day in the widespread use of refrigeration, chemical industry, electronic industry etc. at present, and will be eliminated gradually.Therefore the surrogate of developing Chlorofluorocarbons (CFCs) and Ha Long has caused countries in the world scientist's great attention.In recent years, the chemist discovers, Hydrochlorofluorocarbons (HCFC) and hydrogen fluorohydrocarbon (HFC) are more gratifying surrogates, as 1,1,1,2-Tetrafluoroethane (HFC-134a) is very effective in the application of refrigerator refrigeration and air conditioning equipment of car etc. as the surrogate of Refrigerant 12 (CFC-12).But the synthetic synthetic difficulty more than Chlorofluorocarbons (CFCs) and Ha Long of Hydrochlorofluorocarbons and hydrogen fluorohydrocarbon, and expense also wants expensive.In general, how to introduce the key point that hydrogen atom is synthetic Hydrochlorofluorocarbons and hydrogen fluorohydrocarbon.
Anhydrous hydrogen fluoride is a kind of very economic fluorination reagent, is widely used in organic synthesis.But in general, the difficult and fluorine halogen alkene generation electrophilic addition reaction of anhydrous hydrogen fluoride, as under BF3 catalysis, the addition reaction speed of anhydrous hydrogen fluoride and fluorine halogen alkene is very slow, and there is by product such as polymkeric substance to generate (A.L.Henne and R.C.Arnold, J.Am.Chem.Soc., 70,758(1948)); Under AgF catalysis, the addition productive rate of anhydrous hydrogen fluoride and R 1216 has only 47%(W.T.Miller, M.B.Freedman, and J.H.Fried and H.F.Kock, J.Am.Chem.Soc., 83,4105(1961)).At C-CaSO 4Catalysis under, the productive rate of this reaction can reach 80%, the reaction times but reaches 100 hours (I.L.Knunyants, V.V.Shokina and N.D.Kuleshova, Izv.Akad.Nauk SSSR, 1693(1990)).In recent ten years, because the addition reaction of anhydrous hydrogen fluoride and fluorine halogen alkene is in the importance of industrial circle, people are always at the more effective catalyst system of development research, discovery Cr 2O 3Be more effective catalyzer (J.I.Darragh and S.E.Potter, Ger.Offen 2,837,515(1979)) under 350 ℃, found CrF afterwards again 3Be effective more catalyzer, desired reaction temperature also much lower (V.Halasz and S.Peter, Ger.Offen 3,009,760(1981)).
The method that the purpose of this invention is to provide a kind of anhydrous hydrogen fluoride and the addition reaction under catalyst of fluorine halogen alkene, can synthesize Hydrochlorofluorocarbons and hydrogen fluorohydrocarbon by this method, and raw material is easy to get, experimental implementation is simple, life of catalyst is long, and the yield of conversion of raw material, product and purity are all very high.
The present invention is the method for anhydrous hydrogen fluoride and the addition reaction under catalyst of fluorine halogen alkene.The general formula of fluorine halogen olefin(e) compound is C mW nCl xBr yI z, addition reaction product general formula is C mW gCl xBr yI z, in two formulas:
W is F or H;
M is 2-6;
N+x+y+z is less than or equal to 2m, and n, x, y, z are 0-2m;
G is more than or equal to n+2.
In the addition reaction of anhydrous hydrogen fluoride and fluorine halogen alkene, used catalyzer can be:
(1). the group VIII metal element, as Fe, Co, Ni, Ru, Rh, Pd, Pt etc.When adopting above-mentioned base metal, preferably adopt reducing metal; (2) .NR 1R 2R 3(R 1, R 2, R 3Be H, C kH 2k+1And C kH 2k-1Deng, K=1-8), nitrogenous compounds such as pyridine, pyrroles, trimeric cyanamide; (3) .(1) with the mixture of (2), consumption is the same.In addition reaction, amount of metal catalyst is every mole of fluorine halogen alkene 0.01-10 gram.The nitrogenous compound catalyst consumption is every mole of fluorine halogen alkene 0.1-6 mole, and the mol ratio of nitrogenous compound and anhydrous hydrogen fluoride is 1: 0.1-1000.In addition reaction, catalyzer can be reused, and therefore reaction can be carried out in serialization, and this makes this be reflected at certain application prospect in the suitability for industrialized production.In addition reaction, when using the mixed catalyst of (1) and (2), the acceleration of addition reaction energy; In addition.Nitrogenous compound and anhydrous hydrogen fluoride form complex compound and make that reaction product is easy to separate with anhydrous hydrogen fluoride, for the purifying of product provides very big convenience.
Along with the difference of fluorine halogen alkene, catalyzer, nitrogenous compound and the variation of relative content thereof, the variation of nitrogenous compound and anhydrous hydrogen fluoride mol ratio, temperature of reaction and reaction times that addition reaction is required have nothing in common with each other, generally speaking, temperature of reaction is controlled at 10-200 ℃, recommend 80-150 ℃, the required reaction times is 0.5-10 hour, is generally 0.5-2 hour.
As the example application of additive reaction method of the present invention, below the several important Hydrochlorofluorocarbons and the preparation of hydrogen fluorohydrocarbon are illustrated.
Utilize the inventive method, can be easily by anhydrous hydrogen fluoride and the synthetic HFC-134a of trifluoro-ethylene; 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124) are the important intermediate of the synthetic HFC-134a of hydrogenolysis, utilize the inventive method to synthesize HCFC-124 by anhydrous hydrogen fluoride and trifluorochloroethylene easily; Pentafluoride ethane (HFC-125) can be used as fire-fighting medium, and it can synthesize by the addition of anhydrous hydrogen fluoride among the present invention and tetrafluoroethylene; 1,1,1,2,3,3,3-heptafluoro-propane (HFC-227) is a kind of important hydrogen fluorohydrocarbon, and it can synthesize by the addition of anhydrous hydrogen fluoride among the present invention and R 1216.
In order to understand the present invention better, now be exemplified below:
Example 1 Preparation of catalysts
(1) with water miscible Fe 2+Fe 3+Co 2+Co 3+Ni 2+With the reduction of Zn powder,, get reductibility Fe, Co, Ni respectively through water washing and anhydrous methanol washing; In addition, with Fe 2(NO 3) 3, Co 2(NO 3) 3, Ni(NO 3) 2Roasting at high temperature, and then use hydrogen reducing, also can get reductibility Fe, Co, Ni.These reducing metals all can be used as catalyzer of the present invention and use.
(2) the Al-Ni alloy is handled with the NaOH aqueous solution, can be obtained dissimilar RaneyNi(H.R.Billica and H.Adkins, Org.Syn., Coll.Vol.3,176(1955)), the catalyzer that they also can be used as among the present invention uses.
Example 2 synthetic pentafluoride ethanes (HFC-125)
In 2 liters of autoclaves, add 2 gram Raney Ni, 0.5 mole of anhydrous hydrogen fluoride and 0.50 mol of tetrafluoroethylene, 110 ℃ of heating 4 hours, 19F NMR and GC(5% squalene on silica gel) analyze and to show that all tetrafluoroethylene all transforms, reaction product is a pentafluoride ethane, under the dry ice cooling, collect, pentafluoride ethane 60 restrains productive rate 100%, GC purity 99.0%.
Example 3 Synthetic 2s-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124)
In 2 liters of autoclaves, add 2 gram reductibility Fe, 0.3 mole of Et 2NH, 1.0 moles of anhydrous hydrogen fluorides and 0.50 mole of trifluorochloroethylene, 110 ℃ are reacted half an hour down, 19F NMR and GC analysis revealed trifluorochloroethylene transformation efficiency 100%, separate 2-chlorine 1,1,1,2-Tetrafluoroethane 68.3 gram, productive rate 100%, purity 99.5%.
Example 4 Synthetic 2s-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124)
In 2 liters of autoclaves, add 2.0 moles of n-Bu 3N, 1.0 moles of anhydrous hydrogen fluorides and 0.50 mole of trifluorochloroethylene, 110 ℃ were reacted 10 hours down, 19F NMR and GC analysis revealed trifluorochloroethylene transformation efficiency 100%, separate 2-chloro-1,1,1,2-Tetrafluoroethane 68.3 gram, productive rate 100%, purity 99.0%.
Example 5 synthesizes 1,1,1,2,3,3,3-heptafluoro-propane (HFC-227)
In 2 liters of autoclaves, add 0.01 gram Pd, 0.3 mole of Et 3N, 0.60 mole of anhydrous hydrogen fluoride and 0.50 mole of R 1216,100 ℃ are reacted half an hour down, 19F NMR and GC analysis revealed R 1216 transformation efficiency 100%, separate 1,1,1,2,3,3,3-heptafluoro-propane 85.0 gram, productive rate 100%, purity 99.81%.
Example 6 synthesizes 1,1,1,2-Tetrafluoroethane (HFC-134a)
In 2 liters of autoclaves, add 0.30 mole of pyridine, 0.80 mole of anhydrous hydrogen fluoride and 0.50 mole of trifluoro-ethylene, 150 ℃ were reacted 3 hours down, 19F NMR and GC analysis revealed trifluoro-ethylene transformation efficiency 100%, separate 1,1,1,2-Tetrafluoroethane 48.5 gram, productive rate 95%, purity 99.0%.
Example 7 synthesizes 1,1,1,2,3,3,3-heptafluoro-propane (HFC-227)
In 2 liters of autoclaves, add 21 gram reductibility Co, 0.30 mole of pyridine, 0.60 mole of anhydrous hydrogen fluoride and 0.50 mole of R 1216,100 ℃ are reacted half an hour down, 19F NMR and GC analysis revealed R 1216 transformation efficiency 100%, separate 1,1,1,2,3,3,3-heptafluoro-propane 85.0 gram, productive rate 100%, purity 99.0%.
Example 8 synthesizes 1,1,1,2,3,3,4,4,4-nine fluorine butane
In 2 liters of autoclaves, add 10 gram Fe, 10 moles of pyridines, 0.60 mole of anhydrous hydrogen fluoride and 0.50 mole of perfluor n-butene, 10-40 ℃ was reacted 8 hours, 19F NMR and GC analysis revealed perfluor n-butene transformation efficiency 100%, separate 1,1,1,2,3,3,4,4,4-nine fluorine butane 110 gram, productive rate 100%, purity 99.0%.

Claims (9)

1, a kind of is C from anhydrous hydrogen fluoride and molecular formula mW nCl xBr yI zFluorine halogen alkene to prepare molecular formula in the presence of catalyzer be C mW gCl xBr yI zThe method of compound, wherein W is F or H, m is n-6, n+x+y+z is less than or equal to 2m, n, x, y or z are 0-2m, g is characterized in that 10-200 ℃ of reaction 0.5-10 hour more than or equal to n+2, described catalyzer and mole ratio are one of following three kinds,
(1) group VIII metal element, C mW nCl xBr yI zMole number: HF mole number: group VIII metal element gram=1: 1-2: 0.01-10,
(2) nitrogenous compound, described nitrogenous compound is NR 1R 2R 3, pyridine, pyrroles, bipyridine, trimeric cyanamide, wherein R 1, R 2Or R 3Be H, C kH 2k+1Or C kH 2k-1, K=1-8, C mW nCl xBr yI z, HF and nitrogenous compound mole ratio be 1: 1-2: 0.1-6,
(3) mixture of group VIII metal element and above-mentioned nitrogenous compound, consumption is as described in (1) and (2).
2, a kind of as right 1 described preparation method, it is characterized in that described VIII family element is Fe, Co, Ni or precious metal.
3, a kind of preparation method as claimed in claim 1 is characterized in that described VIII family element is RaneyNi.
4, a kind of preparation method as claimed in claim 1 is characterized in that temperature of reaction is 50-150 ℃.
5, a kind of preparation method as claimed in claim 1 is characterized in that the reaction times is 0.5-2 hour.
6, a kind of as claim 1,2,3,4 or 5 described preparation methods, it is characterized in that described fluorine halogen alkene is 2 chloro-1,1,1, the 2-Tetrafluoroethane.
7, a kind of as claim 1,2,3,4 or 5 described preparation methods, it is characterized in that described fluorine halogen alkene is pentafluoride ethane.
8, a kind of as claim 1,2,3,4 or 5 described preparation methods, it is characterized in that described hydrogen fluorohydrocarbon is 1,1,1,2,3,3, the 3-heptafluoro-propane.
9, a kind of as claim 1,2,3,4 or 5 described preparation methods, it is characterized in that described hydrogen fluorohydrocarbon is 1,1,1,2,3,3,4,4,4-nine fluorine butane.
CN 92108469 1992-06-19 1992-06-19 Preparing process for hydrofluoric halocarbon and hydrofluoric hydrocarbon Expired - Fee Related CN1037960C (en)

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