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CN1051904A - The preparation method of chlorine fluorine propane - Google Patents

The preparation method of chlorine fluorine propane Download PDF

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Publication number
CN1051904A
CN1051904A CN 90109450 CN90109450A CN1051904A CN 1051904 A CN1051904 A CN 1051904A CN 90109450 CN90109450 CN 90109450 CN 90109450 A CN90109450 A CN 90109450A CN 1051904 A CN1051904 A CN 1051904A
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ccl
chf
chcl
cclf
reaction
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艾伦·卡普伦·西弗茨
卡尔·乔治·克雷斯潘
弗兰克·朱利安·韦格特
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C07C19/10—Acyclic saturated compounds containing halogen atoms containing fluorine and chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/125—Halogens; Compounds thereof with scandium, yttrium, aluminium, gallium, indium or thallium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
    • C07C17/278—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of only halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
    • C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/395—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification of at least one compound

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The preparation general formula is C 3HCl 2F 5The method of chlorine fluorine propane, it is included in modified aluminum chloride catalyst and exists down, under 0-150 ℃ temperature, dichloromonofluoromethane is contacted with tetrafluoroethylene.New compound CF is wherein also disclosed 3CCl 2CHF 2

Description

The preparation method of chlorine fluorine propane
The present invention relates to 2 of the preparation method of Chlorofluorocarbons (CFCs) and Xin, 2-two chloro-1,1,1,3,3-pentafluoropropane compound.
Because the development, the particularly development of electronic applications modern technologies of modern technologies, making electronic component have high degree of cleaning has become extremely important and requirement that must reach.For example, in the making with the modern circuit card that has increased circuit and component density, after the welding, it is crucial thoroughly and effectively cleaning these wiring boards.At present, the cleaning circuit plate uses all kinds of SOLVENTS and method to carry out solvent cleaning mostly.
At present, the solvent of selecting for use is 1,1,2-three chloro-1,2,2-Halothane (CFC-113) because this solvent have active solvent the various necessary characteristic that should have, for example atmospheric boiling point, noninflammability, hypotoxicity, all be inertia, very high stability and very strong dissolving power for various component materials.Normal and a spot of solubility promoter of CFC-113 uses together as acetone or methyl alcohol, to improve the certain dissolubility energy.The solvent of CFC-113 and CFC-113 base also is widely used in cleaning the precision optical machinery parts.But in recent years, CFC-113 had the suspicion that stratospheric ozonosphere is reduced.Because it has unusual high stability, in Earth'S atmosphere, can keep steady state so it is generally acknowledged CFC-113, after it enters stratosphere, decompose there, the degradation production of generation has destroyed ozonosphere.
Therefore, obviously, a kind of solvent of industrial urgent need comes substitute CFC-113, and this solvent will have the favourable solvent properties of CFC-113, but has simultaneously very little again or do not reduce the potentially dangerous of stratospheric ozone.
An object of the present invention is to provide a kind of effective chloro fluorocarbon solvent system.Another object of the present invention provides a kind ofly only to be had little or the effective chloro fluorocarbon solvent system of influence not for the stratospheric ozone layer.A further object of the invention provides a kind of improving one's methods of chlorine fluorine propane that prepare.
The invention provides a kind of preparation by formula C 3HCl 2F 5The method of hydrogeneous chlorine fluorine propane of expression, said method are included under the existence of aluminum chloride catalyst of modification, under about 0 ℃-150 ℃ temperature, dichloromonofluoromethane are contacted with tetrafluoroethylene, reclaim hydrogenous chlorine fluorine propane then.The aluminum chloride of said modification is the method preparation by Aluminum chloride anhydrous being contacted with the Chlorofluorocarbons (CFCs) of 1-2 carbon atom and therefrom removing product liquid.It is a kind of new 2 that the present invention also provides, 2-two chloro-1,1,1,3,3-pentafluoropropane compound.
Being used for the solvent system of substitute CFC-113 should have the characteristic very approaching with CFC-113, for example lower atmospheric boiling point (about 47 ℃ of the boiling point of CFC-113), noninflammability, hypotoxicity, the material of various compositions all is stability in inertia, high-solvency and the use, have only very little influence or not influence for ozone minimizing process, replace solvents should have the stability that slightly is different from CFC-113.This solvent all should sufficiently be stablized in various cleaning processes so that use effectively, but should again enough instabilities for the troposphere simultaneously, so that it is able to fully or almost completely decomposition in the troposphere, thus, make to have only and seldom measure or do not have undecomposed solvent to enter stratosphere.
Usually, these professional those of skill in the art know most hydrochlorofluorocarsolvent, and (HCFC ' S) has such stability, its ultimate principle is like this, hydrochlorofluorocarsolvent has carried out dehydrohalogenation now in atmospheric layer, for example dehydrogenation chlorination is so that can not survive until entering stratosphere this compound.
Have now found that, by formula C 3HCl 2F 5Some hydrogenous chloro fluorocarbon derivative of the propane of expression has necessary characteristic discussed above.Therefore, with regard to atmospheric boiling point, the present known C that has reported 3HCl 2F 5The boiling point of isomer promptly is about 50 ℃-56 ℃ very near the boiling point of CFC-113.CHClFCClFCF for example 3The boiling point of (I) is 56 ℃, CHF 2CClFCClF 2The boiling point of (II) is 56.3 ℃, CHCl 2CF 2CF 3The boiling point of (III) is 53.0 ℃, CHClFCF 2CClF 2The boiling point of (IV) is 52.0 ℃, CClF 2CHClCF 3The boiling point of (V) is 50.4 ℃.Boiling point quite meets the requirements near the boiling point of CFC-113, therefore, can use at present used solvent cleaning system and method and does not do too many improvement.
Though the chlorine fluorine propane that discloses above has been known compound and has been solvent useful in the solvent cleaning system also do not have to prepare their method satisfactorily at present, particularly can not satisfy a large amount of industrial application requirements.
At present, most of Chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons, particularly mass-produced Chlorofluorocarbons (CFCs) and Hydrochlorofluorocarbons, all be to prepare with the method that comprises halogen exchange reaction, promptly or by with the reaction of fluorizating agent such as chlorofluorination antimony etc., perhaps by halohydrocarbon and hydrofluoric reaction in the presence of fluorination catalyst such as antimony halides, chromic oxide, aluminum fluoride etc., fluorine atom has replaced that the method for the one or more chlorine atoms in the halohydrocarbon prepares.Such method comprises the hydrochloric ether that preparation is required at least and follows fluorine carries out permutoid reaction on hydrochloric ether two steps.Usually, prepare hydrochloric ether or hydrogeneous hydrochloric ether is only with one or two carbon compound, but, compound with three carbon atoms, it is propane system, for suitable chloro-propane and the halogen exchange reaction thereafter of preparation very big difficulty is arranged all, and normally productive rate is low as can not to make us satisfied.
According to the present invention, have now found that formula C 3HCl 2F 3The hydrogeneous chlorine fluorine propane of some isomery can and make at an easy rate by dichloromonofluoromethane and tetrafluoroethylene reaction in the presence of the aluminum chloride catalyst of modification, and productive rate is fine, this reaction can be with waiting formula I represent:
CHCl 2F+CF 2=CF 2(catalyzer)/() C 3HCl 2F 5(I)
Deng " C in the formula I 3HCl 2F 5" representative hydrogeneous chlorine fluorine propane heterogeneous mixture.The U.S.P 2,462,402 of Joyce and Coffman etc. are at The Journal of the American Chemical Society, and Vol.71 discloses CHCl on P979-980(1949) 2F and CF 2=CF 2The method of hydrogeneous chlorine fluorine propane is produced in reaction, and wherein used catalyzer is common aluminum chloride.The shortcoming that the common aluminum chloride of the disclosed usefulness of above-mentioned document is made the method for catalyzer is that large-scale halogen exchange reaction has taken place.At least one aspect of such permutoid reaction is by CHCl 2F has generated quite a large amount of chloroform (CHCl 3), this just means and has lost quite a large amount of valuable reactants.Another shortcoming that is caused by large-scale halogen exchange is in this special reaction, the chloroform that is produced and most of C 3HCl 2F 5Isomer forms azeotrope, and this just feasible for example distillation with conventional commercial run is reclaimed C 3HCl 2F 5Quite difficulty and expensive becomes.
Have now found that, above-mentioned reaction (1) has obtained the required hydrogeneous chlorine fluorine propane of high yield when the aluminum chloride catalyst with the modification of the common aluminum chloride of following replacement prior art reacts, and surprisingly dichloromonofluoromethane does not almost change into chloroform.
It is 1 that the document of above-cited Joyce and Coffman etc. discloses hydrogeneous chlorine fluorine propane product, 3-two chloro-1,2,2,3,3-pentafluoropropane, i.e. CHClFCF 2CClF 2; Yet Paleta etc. are at Coll.Czech.Chem.Comm.Vol.35, the chlorine fluorine propane product of having reported gained in P1867-1875(1971) be actually by about 41% 1,3-two chloro-1,2,2,3,3-pentafluoropropane, CHClFCF 2CClF 2And about 59% 1,1-two chloro-2,2,3,3,3-pentafluoropropane, CHCl 2CF 2CF 3The heterogeneous mixture of forming.
The applicant has now found that, replace the productive rate of the hydrogeneous chlorine fluorine propane that common chloro aluminium not only obtains higher with the aluminum chloride catalyst of modification, and form the reaction of chloroform or be eliminated or significantly reduce by dichloromonofluoromethane, but also obtained a certain amount of hydrogeneous chlorine fluorine propane of unknown isomery so far, promptly 2,2-two chloro-1,1,3,3, the 3-pentafluoropropane, CHF 2CCl 2CF 3
The dichloro pentafluoropropane CHF of this new isomery 2CCl 2CF 3From structure should be special ideal, because hydrogen atom is positioned on the end carbon atom of propane molecule, and two chlorine atoms are positioned on the intermediary carbon atom.Such structure just can guarantee to carry out at an easy rate the dehydrogenation chlorination under normal pressure, therefore the not dehydrogenation chlorating compound of just not surviving enters stratosphere and participates in ozone and reduces process.This isomer may be littler than other isomer toxicity.
On the other hand, it is important that cleaning combination will have enough stability under the condition of using.This professional people all know the dehydrogenation chlorination fluoridize than dehydrogenation generally easier.The loss hydrogen halide is undesirable under the condition of using, because it can cause the corrosion of metal parts.This new CHF 2CCl 2CF 3Isomer is as three kinds of C 3HCl 2F 5Isomer-CHCl 2CF 2CF 3, CHClFCF 2CClF 2And CHF 2CCl 2CF 3-mixture and NaOH reactant aqueous solution ability (seeing example 10) show such it under the demulcent condition, demonstrate and have enough stability.Distribution before and after this isomer and the NaOH reaction shows CHCl 2CF 2CF 3Isomer is least stable in three kinds of isomer under these conditions.
The claimed reaction method of the application is by in the presence of the aluminum chloride catalyst of modification, and under about 0 ℃-150 ℃ temperature, dichloromonofluoromethane contacts with tetrafluoroethylene and carries out.
Aluminum chloride catalyst with in the methods of the invention modification is to make by handling Aluminum chloride anhydrous with excessive Chlorofluorocarbons (CFCs), Hydrochlorofluorocarbons or hydrofluorination hydrocarbon, and said these hydro carbons can be: CH 3F, CH 2F 2, CHF 3, CCl 2FCCl 3, CClF 2CCl 3, CF 3CCl 3, CF 3CCl 2F, CF 3CClF 2, CHCl 2CCl 2F, CHClFCCl 3, CHCl 2CClF 2, CHClFCCl 2F, CHF 2CCl 3, CHCl 2CF 3, CHClFCClF 2, CHF 2CCl 2F, CHClFCF 3, CHF 2CClF 2, C 2HF 5, CHClFCHCl 2, CH 2ClCCl 2F, CH 2FCCl 3, CHClFCHClF, CHCl 2CHF 2, CH 2ClCClF 2, CH 2FCCl 2F, CHClFCHF 2, CH 2ClCF 3, CH 2FCClF 2, CHF 2CHF 2, CH 2FCF 3, CH 2ClCHClF, CH 2FCHCl 2, CH 3CCl 2F, CH 2ClCHF 2, CH 2FCHClF, CH 3CClF 2, CH 2FCHF 2, CH 3CF 3, CH 2FCH 2Cl, CH 3CHClF, CH 2FCH 2F, CH 3CHF 2, and C 2H 5F; Be preferably CCl 2F 2, CHCl 2F, CHClF 2, CH 2ClF, CCl 2FCCl 2F, CCl 2FCClF 2, CClF 2CClF 2; Be preferably CCl 3F. the propane derivative that has the said structure feature also can be used in the method for the present invention.Reaction between aluminum chloride and Chlorofluorocarbons (CFCs), Hydrochlorofluorocarbons or the hydrogen fluorohydrocarbon is spontaneous and heat release mostly.In some cases, as with C 2The Chlorofluorocarbons (CFCs) reaction, heating may be favourable a little.For containing a CF 3The compound of group such as CHF 3, CCl 3CF 3, CHCl 2CF 3, CH 2ClCF 3And CH 3CF 3, need stronger condition so that itself and AlCl 3Reaction, this reaction is preferably under the spontaneous pressure of reactant to be carried out.
After reaction stopped, general recovering liquid product under reduced pressure obtained the aluminum chloride catalyst of modification, and this catalyzer contains the fluorine of the 3-68% that has an appointment usually.Chlorofluorocarbons (CFCs) and AlCl 3The product liquid of reaction gained comprises by the product that produces with the halogen exchange reaction of aluminum chloride and the Chlorofluorocarbons (CFCs) product of rearrangement.So, when using CCl 3During the modified chlorinated aluminium of F, the halogen exchange product will be CCl 4, when using CHCl 2During F, product is CHCl 3When using CCl 2FCClF 2During modified chlorinated aluminium, the product liquid of reaction comprises CCl 3CF 3, CCl 3CClF 2And C 2Cl 6
By filter, distillation or shift out by product liquid vacuum from the aluminum chloride of modification can be AlCl 3Be separated with the modified chlorinated aluminium product of solid and the product liquid of Chlorofluorocarbons (CFCs) reaction gained, in addition, the aluminum chloride catalyst of this modification also can be used for reaction thereafter with the form of suspensoid.
Because the present invention includes by waiting 1 mole of dichloromonofluoromethane is added in the mol of tetrafluoroethylene shown in the formula I, if necessary, though can use any excessive a little reactant, the suitable mol ratio of reactant should be 1: 1.Although use the aluminum chloride catalyst of modification, the dichloromonofluoromethane of too excessive may cause forming chloroform, so will avoid using the dichloromonofluoromethane of too excessive, though big excessive tetrafluoroethylene is harmless, does not also have purposes.Two kinds of reactant CHCl 2F and CF 2=CF 2All be the commercially available prod, can be easy to buy.The Tetrafluoroethane that method of the present invention is used can suppress with α-Limonene Xi arbitrarily, with the possibility of the polymerization that reduces initiation potential.
Method of the present invention can be carried out with intermittence or continuous mode.In continuation method, under suitable temperature and pressure, dichloromonofluoromethane and tetrafluoroethylene with traditional method, as fractionation, reclaim needed product by the aluminum chloride bed of modification from effluent.
In batch process, all reactants can mix in reactor.Also can, during beginning catalyzer and tetrafluoroethylene are added in the reactor, then with the metering dichlorofluoromethane be added in the reactor by desired speed.If catalyzer and CHCl are housed in the reactor 2F importantly makes this reaction will keep cooling, even so that the CHCl that also might produce under the vantage of the aluminum chloride catalyst that uses modification 2Out-of-proportion situation of F and chloroform narrows down to minimum.
Method of the present invention can be carried out being with or without under the situation of solvent, if use solvent, solvent should be not and the aluminum chloride catalyst reaction of modification, and has and be suitable for final separation of C 3HCl 2F 5The boiling point of isomer mixture.The solvent that can be used for the inventive method comprises nonactive hydrochloric ether such as CH 2Cl 2, or nonactive Chlorofluorocarbons (CFCs) such as CF 3CCl 2CF 3Reasonable solvent is CHCl 2CF 3, best solvent is a product C 3HCl 2F 5Heterogeneous mixture or arbitrary independent isomer.
Temperature of reaction can change in very wide scope, and about 0 ℃-150 ℃, reasonable temperature of reaction is about 10 ℃-100 ℃, preferably about 25 ℃-70 ℃.
Equally, pressure can change in negative pressure one surpasses the very wide scope of barometric point, carries out but preferably be reflected under the higher slightly pressure, particularly carries out under spontaneous and the corresponding to pressure of used temperature of reaction.Reaction pressure is by existing unreacted CHCl in the conditioned reaction device 2F and CF 2=CF 2Amount control.
Reaction times, or be enough to finish reaction and the needed time depend on selected temperature of reaction, still, the change that is easy to by pressure in the reactor of finishing of reaction is determined.Therefore, if reaction is in given temperature, when carrying out under the spontaneous pressure, pressure can descend continuously along with the carrying out of reaction, and the time that pressure stops to descend is exactly the time that reaction finishes.Usually, in preferred temperature range, the reaction times is about 0.25-3 hour.
The amount of the aluminum chloride of the modification of using, promptly catalytic amount should be about 1-20% of reactant weight, preferably about 3-12%.
The product of present method can reclaim with any ordinary method, as before or after the aluminum chloride of modification is by water decomposition with filtering or the distillatory method reclaims.
In certain embodiments, before reclaiming, may need to improve CF in the reaction mixture 3CCl 2CHF 2Content.This can finish by the isomerization of using aluminium oxide catalyst.In the method, as in embodiment 4 further introduce, at 200-400 ℃, reaction product is by a kind of aluminium oxide catalyst of halogenide modification.
At CHF 2CCl 2CF 3In the component, C 3HCl 2F 5The amount of mixture also can improve through liquid-phase isomerization by using the aluminum chloride catalyst of the modification of preparation as stated above.In this case, isomerization reaction can be under 50-200 ℃ temperature, under the spontaneous pressure of reactant, by heating C 3HCl 2F 5The mixture of isomer and aluminum chloride catalyst carries out.Preferred catalyzer is CCl 3The aluminum chloride of F-modification.This method is further introduced at embodiment 5.
Be applicable to the isomerization of dichloro pentafluoropropane mixture, improving in such mixture 1,1,1,3,3-five fluoro-2, the halogenide modification Catalyzed Aluminum catalyzer of 2-propylene dichloride content can prepare as follows.
A certain amount of surface-area greater than 100m 2The aluminum oxide of/g is for example about 18 hours of 100 ℃ of dryings, up to removing all moisture basically.Then the exsiccant catalyzer is moved on in the reactor that will use.
This aluminium oxide catalyst can be used fluorine-containing fluorinated compound such as HF, the CCl of vaporizable before being used for isomerization 3F, CCl 2CF 2, CHF 3Or CCl 2FCClF 2, under for example about 200 ℃-450 ℃ of the temperature that improves, handle, aluminium oxide catalyst is fluoridized, require degree of fluorination until obtaining.The meaning of vaporizable fluorochemicals is, the pretreatment condition that uses this specialty to know, and this compound can be transformed into desired degree of fluorination to the alumina component of catalyzer.Handle and to carry out at the reactor that will be used for isomerization reaction very easily with HF or other vaporizable fluorochemicalss.
Embodiment 1
CCl 3The preparation of the aluminum chloride of F modification
Adding 50g(0.375mole in the flask at the bottom of three mouthfuls of gardens of 500ml) AlCl 3This flask passes a loft drier, and the dry-ice condenser that a feed hopper and top have the nitrogen bubble device is housed.175ml CCl packs in the feed hopper 3F(CFC-11), methyl alcohol/dry ice mixture is housed in the condenser.CFC-11 is added in the flask gradually, and mixture begins rapid backflow.After all CFC-11 added, reaction continued to reflux 1 hour.Reaction stops heating, analyzes supernatant liquid with GC, shows that it is actually pure CCl 4Vacuum is removed volatile matter, and the solid vacuum-drying obtaining obtains the 31g brown powder, analyzes: Al, 28.1%(weight).
Embodiment 2
Optimum implementation of the present invention
Putting in " Hastelloy " C nickelalloy bottle of 400ml by the modified chlorinated aluminium of 13.3gCFC-11 of embodiment 1 preparation, this bottle sealing, be cooled to-78 ℃, use nitrogen purging three times, this bottle is found time once more, 51.5g(0.50mole) CHCl 2F joins in this bottle.Then, this bottle is put in the protective housing, and vibrations are stirred.(50g 0.50mole) according to balance, is not added to this bottle from the compression steel cylinder by tiny valve the tetrafluoroethylene of Yi Zhiing.The temperature of this bottle is raised to 40 ℃, and under this temperature, kept 8 hours.In the meantime, the pressure of this bottle is raised to 63psig and drops to 35psig gradually.Then, this bottle cooling, exhaust are purged, and the thing in this bottle is poured in the jar.The heavy 111g of crude product is made up of the yellow supernatant liquid of brown colloidal solid top.This product chilling in water, the organic layer anhydrous sodium sulfate drying obtains the 65.65g product.With 1HNMR analyzes organic layer and shows and have following compound (mole%): 58%CHCl 2CF 2CF 3, 23%CHF 2CCl 2CF 3, 5%CHClFCF 2CClF 2And 7%CHCl 2CF 2CClF 2, do not detect chloroform.
Embodiment 3
This embodiment shows that this reaction can carry out under higher temperature, do not influence the result basically
Following method is similar to the method for embodiment 2, aluminum chloride of CFC-11 modification (67g) and CHCl 2F(51.5g, 0.50mole) (50g, 0.50mole) reaction was reacted 3 hours down at 68-72 ℃ with tetrafluoroethylene.In the meantime, the pressure in this bottle is raised to 83psig, drops to 68psig then gradually.With 1The HNMR assay products shows and has following compounds (mole%) 63%CHCl 2CF 2CF 3, 24%CHF 2CCl 2CF 3, 5%CHClFCF 2CClF 2, 6%CHCl 2CF 2CClF 2And 2%CHCl 2CCl 2CF 3, do not detect chloroform.
Comparing embodiment 1
Do not report CHF in the document 2CCl 2CF 3(HCFC225aa) conduct is by CHCl 2The product that F and tetrafluoroethylene obtain.The following examples confirm not form HCFC225aa under the described in the literature condition.
Press Paleta O.; Posta, A.; Tesarik, K., Coll.Czech.Chem.Comm., 1971,36(5), 1967 methods of being introduced are reacted with excessive basically dichlorofluoromethane.
In 240mol " Hastelloy " C nickelalloy bottle, add 5.0g aluminum chloride, 90g(0.87mole) dichlorofluoromethane and 30g(0.30mole) tetrafluoroethylene, stirred 3 hours down at about 25 ℃ then.Under vacuum, from crude product mixture, take out volatile liquid 86.4g.The GC analysis revealed, 44.7% of mixture, promptly the 38.6g(productive rate 63%) and be the expection product, 1,1-two chloro-2,2,3,3,3-pentafluoropropane and 1,3-two chloro-1,1,2,2, the ratio of 3-pentafluoropropane is 75: 25.
Wherein also formed the chloroform (22%) of a great deal of, so this mixture fractionation, so that isolate pure propane isomer.Collect the cut of 41-60 ℃ of boiling point, analyze the cut of the representative range of compositions of selecting with NMR. 1H and 19The FNMR spectrum confirms that two kinds of products are identical, also shows not have 2 2-two chloro-1,1,1,3,3-pentafluoropropane.
Embodiment 4
Prepare enrichment CHF by isomerization 2CCl 2CF 3C 3HCl 2F 5Mixture
Containing 66mole%CHCl 2CF 2CF 3(HCFC-225Ca), 29mole%CHClFCF 2CClF 2(HCFC-225cb).5mole%CHF 2CCl 2CF 3(HCFC-225aa) and＜1mole%CHClFCClFCF 3The liquid mixture of HCFC-225 isomer (HCFC-225ba) with the speed of 1ml/h with nitrogen carrier gas (5sccm) by a kind of in Glass tubing aluminium oxide catalyst (Harshaw Al-3945,4g).-78 ℃ of condensed fluid products and with gas-chromatography and 19FNMR analyzes.Forming at 380 ℃ of these products is 70mole% HCFC-225ca.＜1mole%HCFC-225cb, 25mole%HCFC-225aa and 4mole%HCFC-225ba.As can be seen, the concentration of HCFC-225aa increases by 500.
Embodiment 5
Prepare enrichment CHF by liquid-phase isomerization 2CCl 2CF 3C 3HCl 2F 5Isomer mixture is at a 400ml Hastelloy
Figure 901094501_IMG1
33g C packs in the nickelalloy vibrations bottle 3HCl 2F 5The aluminum chloride of mixture of isomers (sample composition described below) and 6.7g CFC-11-modification.This bottle is cooled to-78 ℃, finds time, and use nitrogen purging.Find time the bottle be placed in the protector, and be heated to 150-161 ℃ 8 hours, pressure is 130psig.Then, this bottle cooling, emptying, use nitrogen purging, and the product example in a jar.Product is made up of the yellow supernatant liquid of brown solid top.With GC and 1HNMR analyzes supernatant liquid, shown in this sample composed as follows.Analytical results shows under these conditions, a large amount of CHClFCF 2CClF 2Isomer changes into CHF 2CCl 2CF 3Isomer.In addition, some C 3HCl 2F 5Isomer changes into C 3HCl 3F 4And C 3HCl 4F 3Isomer.
Form mole%
Compound starting material product
CHCl 2CF 2F 365.0 61.7
CHF 2CCl 2CF 314.1 22.0
CHClFCF 2CClF 216.9 8.9
CHCl 2F 0.9 -
CHCl 31.0 1.4
C 3HCl 3F 4′S 2.0 ★4.3 ★
CHCl 2CCL 2CF 3- 1.8
★Estimated value
Embodiment 6
This embodiment shows and is not changing reaction basically
Can increase the amount of catalyzer under result's the situation
Following method is similar to the method for embodiment 2, modified chlorinated aluminium of CFC-11 (13.3g) and CHCl 2F(51.5g is 0.50mole) with tetrafluoroethylene (50.g, 0.50mole) reaction.40 ℃ of reactions 3 hours.With 1The HNMR assay products shows to have following compounds: 63% CHCl 2CF 2CF 3, 24%CHF 2CCl 2CF 3, 4%CHClFCF 2CCLF 2, 7%CHCl 2CF 2CClF 2, 2%CHCl 2CCl 2CF 3, do not detect chloroform.
Embodiment 7
CHCl 2The preparation of the aluminum chloride of F modification
SILVER REAGENT aluminum chloride (50g dripped 203g(2.0mole when 0.37mole) stirring in the 2 hours) dichlorofluoromethane that is suspended in the 100ml chloroform.Suitably cooling keeps temperature to be lower than 32 ℃.Vacuum is removed volatile matter, stays the 33.8g brown solid, and it is stored in the loft drier.Analytical results: 64.5%F(weight).
Embodiment 8
This embodiment explanation and CHCl 2The AlCl of F modification 3
As tetrafluoroethylene and CHCl 2The F catalyst for reaction
CHCl packs in 240ml " Hastelloy " C nickelalloy bottle 2The aluminum chloride of F modification (5.0g).This bottle is found time, and CHCl 2F(52g, 0.50mole) and tetrafluoroethylene (50g 0.50mole) joins in this bottle.Stirred this bottle 8 hours at 25 ℃.Crude reaction product is filled in the refrigerative withdrawer, obtains the 59.6g product.Analyze by GC, prove that this material contains 19%CHCl 2CF 2CCLF 2And 77%C 3HCl 2F 5Isomer does not detect chloroform.This sample of fractionation obtains 43.4gC 3HCl 2F 5Isomer is used 1H and 19The FNMR analysis revealed its by 67%CHCl 2CF 2CF 3, 22%CHF 2CCl 2CF 3And 11%CHClFCF 2CClF 2Form.
Embodiment 9
Preparation CCl 2FCClF 2(CFC-113) aluminum chloride of modification
One be equipped with mechanical stirrer, dropping funnel and top be equipped with at the bottom of the 500ml three neck gardens of 12 ℃ of reflux exchangers of nitrogen bubbler add 44.4g(0.333mole in the flask), SILVER REAGENT AlCl 3CFC-113(250ml) be added in the feed hopper, and another part 50ml also is added to the AlCl of stirring 3In, then remaining CFC-113 is added rapidly.Reaction backflow 1.25h.Analyze by GC and GC-MS, find that the supernatant liquid of reactant contains CF 3CCl 3(CFC-113a), CCl 3CClF 2(CFC-112a) and hexachloroethane.Vacuum is removed volatile products, obtains the 57.3g yellow powder.This material contains 13.6%(weight) Al, and may be CCl obviously 3CCL 2F(CFC-111) and the organic product of hexachloroethane pollute.
Embodiment 10
This embodiment illustrates that the aluminum chloride of using the CFC-113 modification is as tetrafluoroethylene and CHCl 2The F catalyst for reaction
Below method be similar to the method for embodiment 2, the aluminum chloride of CFC-113 modification (13.3g, press embodiment 8 prepares), CHCl 2F(51.5g, 0.50mole) and tetrafluoroethylene (50g, 0.50mole) 40 ℃ the reaction 3 hours.In the meantime, pressure of the inside of a bottle is raised to 192psig, drops to 158psig then gradually.With 1The HNMR assay products shows existence following compound: 47%CHCl 2CF 2CF 3, 7%CHF 2CCl 2CF 3, 22%CHClFCF 2CClF 2, 18%CHCl 2CF 2CClF 2, 4%CHCl 2CCl 2CF 3, 1%1,1,2,2,3,3,3-heptachloropropane and 0.3% chloroform.
Embodiment 11
C 3HCl 2F 5Isomer and NaOH reaction
C 3HCl 2F 5Mixture of isomers (5ml) is handled with the NaOH aqueous solution of 10ml10%, and the two-phase mixture that generates was refluxed 45 hours.The beginning with last C 3HCl 2F 5The composition of mixture is listed in table.In last solution, observe additional compounds, its be by 19FNMR differentiates out, is by CHCl 2CF 2CF 3The CCl that generates of dehydrogenation fluorination 2=CFCF 3
The table I
Initial C 3HCl 2F 5Final C 3HCl 2F 5
Form
Isomer % isomer %
CHCl 2CF 2CF 365 CHCl 2CF 2CF 350
CHF 2CCl 2CF 318 CHF 2CCl 2CF 324
CHClFCF 2CClF 218 CHClFCF 2CClF 226
Embodiment 12
CHCl in HCFC-123 2F and tetrafluoroethylene reaction
Aluminum chloride of CFC-11 modification (13.3g) and HCFC-123(60g, 0.40mole) be placed on 400ml " Hastelloy " and (in the vibrations bottles, seal this bottle, and in the dry ice-propanone bath, be cooled to-78 ℃, alternately find time then and with nitrogen purging three times.This bottle is found time also again CHCl 2F(103g 1.0mole) joins in the bottle.Be put into this bottle in the protector then and begin and stir.By poising action, (19g 0.19mole) is added in this bottle the tetrafluoroethylene that does not suppress through the little valve of the working cylinder of a pressurization.The temperature of this bottle is raised to 30 ℃ in about 1 hour, and pressure is increased to about 120psig.Approximately after the reaction 1.5 hours) 34 ℃ of temperature, pressure 125psig), in addition 10gTFE is added in this bottle.Observe about 8 ℃ of temperature jitter, the pressure in 15 minutes in the bottle drops to 117psig from 134psig.In next 1.8 hours, in addition 4-11gTFE is added in this bottle.At this moment, added 100gTFE altogether, the pressure in the bottle drops to 45 ℃ of 93psig(temperature).Temperature remain on 41-45 ℃ 3 hours.
Then, this bottle cooling, emptying, purging, and the material in the bottle pours in the jar.Product is made up of transparent supernatant liquid above heavy-gravity brown lower floor.The heavy 251g of crude reaction product, this is equivalent to weight increases about 177g. 1HNMR analyzes supernatant liquid, shows by following the composition (mole%): CHCl 2CF 326%, CHCl 2CF 2CF 342%, CHF 2CCl 2CF 38%, CHClFCF 2CClF 216%, CHCl 2CF 2CClF 26%, CHCl 2CCL 2CF 32%.With GC or 1HNMR does not detect chloroform.

Claims (13)

1, Compound C F 3CCl 2CHF 2
2, preparation general formula C 3HCl 2F 5The method of hydrogeneous chlorine fluorine propane, what it was included in catalytic amount contains 3-68%(weight) under the existence of the aluminum chloride catalyst of the modification of fluorine, under 0 ℃-150 ℃ temperature, make the reaction of dichloromonofluoromethane and tetrafluoroethylene, the formation reaction product, and from reaction product, reclaim hydrogenous chlorine fluorine propane.
3, according to the method for claim 2, wherein reaction product does not have chloroform basically.
4, according to the method for claim 2, wherein the aluminum chloride catalyst of modification is by handle the Aluminum chloride anhydrous preparation with excessive following compounds:
CH 3F, CH 2F 2, CHF 3, CCl 2FCCl 3, CClF 2CCl 3, CF 3CCl 3, CF 3CCl 2F, CF 3CClF 2, CHCl 2CCl 2F, CHClFCCl 3, CHCl 2CClF 2, CHClFCCl 2F, CHF 2CCl 3, CHCl 2CF 3, CHClFCClF 2, CHF 2CCl 2F, CHClFCF 3, CHF 2CClF 2, C 2HF 5, CHClFCHCl 2, CH 2ClCCl 2F, CH 2FCCl 3, CHClFCHClF, CHCl 2CHF 2, CH 2ClCClF 2, CH 2FCCl 2F, CHClFCHF 2, CH 2ClCF 3, CH 2FCClF 2, CHF 2CHF 2, CH 2FCF 3, CH 2ClCHClF, CH 2FCHCl 2, CH 3CCl 2F, CH 2ClCHF 2, CH 2FCHClF, CH 3CClF 2, CH 2FCHF 2, CH 3CF 3, CH 2FCH 2Cl, CH 3CHClF, CH 2FCH 2F, CH 3CHF 2, C 2H 5F, CCl 2F 2, CHCl 2F, CHClF 2, CH 2ClF, CCl 2FCCl 2F, CCl 2FCClF 2, CClF 2CClF 2, or CCl 3F.
5, according to the method for claim 4, wherein Chlorofluorocarbons (CFCs) is selected from CCl 3F, CCl 2F 2, CHCl 2F, CHClF 2, CH 2ClF, CCl 2FCCl 2F, CCl 2FCClF 2And CClF 2CClF 2
6, according to the method for claim 4, wherein Chlorofluorocarbons (CFCs) is CCl 3F.
7, according to the method for claim 4, wherein Chlorofluorocarbons (CFCs) is CHCl 2F.
8, according to the method for claim 2, wherein in the presence of inert solvent, carry out.
9, according to the method for claim 7, wherein solvent is C 3HCl 2F 5Or CF 3CHCl 2
10, according to claim 2,3,4,5,6,7,8 or 9 method, wherein hydrogeneous chlorine fluorine propane is CF 3CCl 2CHF 2
11, according to the method for claim 2, wherein before reclaiming reaction product, product is contacted with the aluminum oxide isomerization catalyst, to increase CF 3CCl 2CHF 2Content.
12, increase general formula C 3HCl 2F 5The chlorine fluorine propane mixture in CF 3CCl 2CHF 2The method of content, it is included under 200 ℃-400 ℃ the temperature, and this mixture is contacted with the aluminum oxide isomerization catalyst of halogenide modification.
13, increase general formula C 3HCl 2F 5The chlorine fluorine propane mixture in CF 3CCl 2CHF 2The method of content, it is included under the spontaneous pressure, at 50-200 ℃, makes mixture and contains 3-68%(weight) modified aluminum chloride catalyst of fluorine contacts.
CN 90109450 1989-10-16 1990-10-16 The preparation method of chlorine fluorine propane Pending CN1051904A (en)

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