Process for producing a 2,2-difluoropropane

TECHNICAL FIELD
The present invention relates to a process for producing a 2,2-difluoropropane.
BACKGROUND TECHNIQUE
As a synthetic route for a 2,2-difluoropropane, a method has been known which comprises adding dichlorodifluoromethane or trichlorofluoromethane to an ethylene having a difluoromethylene unit, such as 1,1-dichloro-2,2-difluoroethylene or 1-chloro-1,2,2trifluoroethylene, in the presence of aluminum chloride.
However, such a method has a drawback that it produces not only the desired product but also a reaction by-product having a methylene group other than the 2,2-difluoromethylene and having a boiling point close to that of the desired product, whereby a multi stage purification process is required in order to obtain a product of a high purity. Further, a method for synthesizing 1-chloro-1,1,2,2-tetrafluoropropane is known which comprises fluorinating propyne (CH.sub.3 C.tbd.CH) with hydrogen fluoride to obtain 2,2-difluoropropane (CH.sub.3 CF.sub.2 CH.sub.3), then selectively chlorinating only three hydrogen atoms at 1-position with chlorine to obtain 1,1,1-trichloro-2,2-difluoropropane (CCl.sub.3 CF.sub.2 CH.sub.3), and further selectively fluorinating only two out of the three chlorine atoms substituted on the carbon atom at the 1-position to obtain 1-chloro-1,1,2,2-tetrafluoropropane (J. Am. Chem. Soc., 65, 2342 (1943)). This method requires many steps and thus has a drawback that it is difficult to improve the yield, and the method is not suitable for industrial production. Further, a method for preparing 1-chloro-2,2,3,3-tetrafluoropropane is known which comprises producing 2,2,3,3-tetrafluoropropanol from tetrafluoroethylene and methanol, then reacting it with sulfuryl chloride to obtain a chlorosulfonic acid ester, and then reacting it with an alkali metal chloride. This method requires many steps, whereby it is difficult to improve the yield, and thus has a drawback that such a method is not suitable for industrial production.
Further, a method for preparing 1-chloro-2,2,3-trifluoropropane is known which comprises dehydrochlorinating 1,2,3-trichloropropane to obtain 2,3-dichloropropene, reacting it with potassium fluoride to obtain 2-chloro-3-fluoropropene, then adding chlorine thereto to obtain 1,2,2-trichloro-3-fluoropropane, and then fluorinating it with antimony dichloride trifluoride. Such a method requires many steps. Therefore, the method has a drawback that it is difficult to improve the yield. As such, the method is not suitable for industrial production.
DISCLOSURE OF THE INVENTION
The present inventors have conducted extensive researches for a process of effectively producing a 2,2-difluoropropane and, as a result, they have found it possible to obtain a 2,2-difluoropropane of the following formula (2) in good yield by fluorinating a chlorine-containing 2,2-halogenopropane of the formula (1) with hydrogen fluoride or a fluorinating agent. The present invention is based on this discovery.
The present invention provides a process for producing a 2,2-difluoropropane of the following formula (2), which comprises fluorinating a chlorine-containing 2,2-halogenopropane of the following formula (1) by hydrogen fluoride or a fluorinating agent:
C.sub.3 H.sub.a Cl.sub.b F.sub.c ( 1)
C.sub.3 H.sub.a Cl.sub.b-x F.sub.c+x ( 2)
wherein a, b, c and x are integers satisfying the following conditions:
a.gtoreq.0, b.gtoreq.1, c.gtoreq.0, x.gtoreq.1, a+b+c=8.
The 2,2-difluoropropane is useful as an etching agent for the production of electronic parts. Further, a chlorine-containing 2,2-difluoropropane is expected to be useful as a foaming agent, a cooling medium, a propellant or a solvent like conventional chlorofluorocarbons. Particularly, it is expected to be useful as a solvent which can be a substitute for 1,1,2-trichlorotrifluoroethane. Further, it hardly depletes the ozone layer in the stratosphere. It is also useful as an intermediate for the production of a hydrogen-2,2-difluoropropane containing no chlorine.

BEST MODE OF CARRYING OUT THE INVENTION
Now, the present invention will be described in detail with reference to the preferred embodiments.
The fluorination in the present invention is preferably conducted by hydrogen fluoride in the presence of a fluorination catalyst, or by a fluorinating agent.
As the fluorination catalyst, a halide of niobium, tantalum or antimony, such as niobium fluoride, niobium chloride, tantalum pentafluoride, tantalum pentachloride, antimony pentafluoride, antimony pentachloride, antimony trifluorodichloride or antimony trifluorodibromide, may be used. When such a fluorination catalyst is employed, the fluorination reaction may be conducted in a gas phase, but is preferably conducted in a liquid phase under atmospheric pressure or under pressurization at a temperature within a range of from 0.degree. to 200.degree. C., preferably from room temperature to 150.degree. C.
The reaction is conducted usually in the absence of a solvent. However, a solvent may be employed. In such a case, there is no particular restriction as to the solvent, so long as it is capable of dissolving the propane as the starting material and it is hardly fluorinated as compared with the starting material. The pressure for the reaction is not particularly limited, but it is usually within a range of from 0 to 30 kg/cm.sup.2. If a solvent is used, the pressure may vary depending upon the type of the solvent.
Hydrogen fluoride may be charged together with the propane as the starting material to the reactor prior to the reaction. However, it is preferred to introduce it into the liquid phase at the time of the reaction.
The ratio between hydrogen fluoride and the chlorine-containing 2,2-halogenopropane starting material may be varied in a wide range. However, in order to substitute the chlorine atoms,.it usually uses stoichiometrical amount of hydrogen fluoride. It is however possible to use hydrogen fluoride in an amount substantially larger than the stoichiometrical amount(for example, 4 mol times or higher, relative to the total molar amount of the starting material.
The contact time is usually from 10 seconds to 10 hours, preferably from 30 seconds to 1 hour.
As other catalysts, fluorination catalysts composed of halides or oxides containing at least one element selected from the group consisting of Al, Cr, Mg, Ca, Ba, Sr, Fe, Ni, Co and Mn, may be used. To prepare such catalysts, any method may be employed so long as it is capable of uniformly dispersing the halides or oxides containing at least one element selected from the group consisting of the above ten elements. For example, a coprecipitation method or a kneading method may be mentioned. Particularly preferred is a method in which hydrates are co-precipitated from an aqueous solution of salts of the above metal elements, or a method wherein a cake of hydroxides is kneaded and pulverized by a ball mill or by a homogenizer. The hydroxides may be those precipitated from aqueous solutions of inorganic salts such as nitrates or sulfates by means of aqueous ammonia or urea, or those prepared by the hydrolysis of organic salts.
A catalyst in the state of a hydrate is preferably dried at a temperature of from 129.degree. to 150.degree. C., followed by calcining at a temperature of from 300.degree. to 600.degree. C., preferably from 350.degree. to 450.degree. C.
It is preferred to activate the catalyst. Such activation can be accomplished usually by applying fluorinating treatment at a temperature of from 100.degree. to 450.degree. C., preferably from 200.degree. to 350.degree. C. Otherwise, such activation can be conducted in the fluorination reaction system, or by heat treatment together with a fluorinated hydrocarbon.
When the above catalyst is used, the fluorination reaction may be conducted in a liquid phase. However, it is preferred to conduct the fluorination reaction in a gas phase under atmospheric pressure or under pressurization at a temperature within a range of from 150.degree. to 550.degree. C., more preferably from 250.degree. to 450.degree. C.
The ratio between hydrogen fluoride and the chlorine-containing 2,2-halogenopropane starting material, may be varied in a wide range. However, in order to substitute the chlorine atoms, it usually uses stoichiometrical amount of hydrogen fluoride. However, hydrogen fluoride may be used in an amount substantially larger than the stoichiometrical amount, for example, 4 mol times or more, relative to the total molar amount of the starting material. The contact time is usually from 0.1 to 300 seconds, preferably from 5 to 30 seconds.
To maintain the catalytic activity, oxygen or chlorine is preferably added in an amount of from 0.1 to 10% by volume relative to the chlorine-containing 2,2-halogenopropane starting material.
When the fluorination reaction is conducted with a fluorinating agent, a fluorinating agent composed of a fluoride, fluorohalide or oxyfluoride containing at least one element selected from the group consisting of Mn, Ag, Sb, Ta, Nb, Ce, Co, Al, Cr, Mg, Ca, Ba, Zn, Si, Li, Na, K, Cs and Rb, may be used. The reaction can be conducted in a gas phase or in a liquid phase. Specifically, MnF.sub.3, AgF, AgF.sub.2, SbF.sub.3, SbF.sub.3 Cl.sub.2, SbF.sub.5, TaF.sub.5, NbF.sub.5, CeF.sub.4, CoF.sub.3, AlClF.sub.2, CrO.sub.2 F.sub.2, LiF, NaF, KF, CsF, RbF, KF-MgF.sub.2, KF-CaF.sub.2, KF-BaF.sub.2, ZnF.sub.2, SiF.sub.2 and NaSiF.sub.6, may be mentioned.
There is no particular restriction as to the amount of fluorinating agent to be used for the fluorination reaction. It is preferred to use a stoichiometric amount of the fluorinating agent relative to the number of chlorine atoms to be substituted in the starting material. However, in order to substantially completely react all the chlorine atoms to be substituted, the fluorinating agent may be used in an amount substantially larger than the stoichiometrical amount, for example, 2 mol times or more, relative to the number of chlorine atoms to be substituted in the starting material. After the reaction, the fluorinating agent is recovered in the form of a chloride or oxychloride, and may be regenerated by means of hydrogen fluoride or fluorine gas. The conditions for the fluorination reaction vary depending upon the fluorinating agent to be employed. However, the reaction temperature is usually from 0.degree. to 450.degree. C., preferably from 50.degree. to 300.degree. C. The reaction time is usually from 1 minute to 20 hours, preferably from 1 to 10 hours. The reaction may be conducted in the absence of a solvent. However, depending upon the fluorinating agent, it is preferred to employ a solvent. As a solvent to be used for the reaction, benzene, toluene, benzotrifluoride, a glycol such as ethylene glycol, or an aprotic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, dimethylsulfone, sulforane, hexamethylphosphotriamide, N-methyl-2-pyrrolidone, acetonitrile, benzonitrile, nitromethane, dioxane, diglime, tetraglime or acetone, may be mentioned. Particularly when an alkali metal fluoride such as KF or CsF is used as the fluorinating agent, sulforane or N,N-dimethylformamide is preferred. A phase transfer catalyst may be added as a reaction accelerating agent. As such a phase transfer catalyst, a quaternary ammonium salt such as tetramethyl ammonium chloride or tetrabutyl ammonium bromide, or a quaternary phosphonium salt such as tetrabutylphosphonium bromide or tetraphenylphosphonium bromide, or crown ether may be mentioned. Such a phase transfer catalyst is added usually in an amount of from 0.01 to 100% by weight, preferably from 0.1 to 30% by weight, relative to the alkali metal fluoride. When SbF.sub.3, SbF.sub.3 Cl.sub.2 or SbF.sub.5 is used as the fluorinating agent, SbCl.sub.3 or SbCl.sub.5 may be added as a catalyst. SbCl.sub.3 or SbCl.sub.5 may be added usually in an amount of 0.01 to 100% by weight, preferably from 0.1 to 20% by weight, relative to SbF.sub.3, SbF.sub.3 Cl.sub.2 or SbF.sub.5.
The following reactions (3) to (7) may be mentioned as specific embodiments for producing a 2,2-difluoropropane of the formula (2) by fluorinating a chlorine-containing 2,2-halogenopropane of the formula (1).
C.sub.3 Cl.sub.6-m.sup.1 F.sub.2+m.sup.1.fwdarw. C.sub.3 Cl.sub.6-n.sup.1 F.sub.2+n.sup.1 (3)
0.ltoreq.m.sup.1 .ltoreq.5 1.ltoreq.n.sup.1 .ltoreq.6, m.sup.1 <n.sup.1
The chlorine-containing 2,2-halogenopropane (C.sub.3 Cl.sub.6-m.sup.1 F.sub.2+m.sup.1 wherein 0.ltoreq.m.sup.1 .ltoreq.5) to be used as the starting material includes 1,1,1,3,3,3-hexachloro-2,2-difluoropropane (R-212ca), 1,1,1,3,3-pentachloro-2,2,3-trifluoropropane (R-213ca), 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca), 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb), 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (R-215ca), 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb), 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca), 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-216cb) and 1-chloro-1,1,2,2,3,3,3-heptafluoropropane (R-217ca).
The 2,2-difluoropropane (C.sub.3 Cl.sub.6-n.sup.1 F.sub.2+n.sup.1) wherein 1.ltoreq.n.sup.1 .ltoreq.6) to be formed by the reaction includes 1,1,1,3,3-pentachloro-2,2,3-trifluoropropane (R-213ca), 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca), 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb), 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (R-215ca), 1,1,1-trichloro-2,2,3,3,3-pentafluoro-propane (R-215cb), 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca), 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-216cb), 1-chloro-1,1,2,2,3,3,3-heptafluoropropane (R-217ca) and octafluoropropane (R-218). These products can be separated by a usual method such as distillation.
C.sub.3 HCl.sub.5-m.sup.2 F.sub.2+m.sup.2 .fwdarw.C.sub.3 HCl.sub.5-n.sup.2 F.sub.2+n.sup.2 (4)
0.ltoreq.m.sup.2 .ltoreq.4 1.ltoreq.n.sup.2 .ltoreq.5, m.sup.2 <n.sup.2
The chlorine-containing 2,2-halogenopropane (C.sub.3 HCl.sub.5-m.sup.2 F.sub.2+m.sup.2 wherein 0.ltoreq.m.sup.2 .ltoreq.4) to be used as the starting material includes 1,1,1,3,3-pentachloro-2,2-difluoropropane (R-222ca), 1,1,3,3-tetrachloro-1,2,2-trifluoropropane (R-223ca), 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb), 1,1,3-trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cb), 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 1-chloro-1,2,2,3,3,3-hexafluoropropane (R-226ca) and 1-chloro-1,1,2,2,3,3-hexafluoropropane (R-226cb). The 2,2-difluoropropane (C.sub.3 HCl.sub.5-n.sup.2 F.sub.2+n.sup.2 wherein 1.ltoreq.n.sup.2 .ltoreq.5) to be formed by the reaction includes 1,1,3,3-tetrachloro-1,2,2-trifluoropropane (R-223ca), 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb), 1,1,3-trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cc), 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 1-chloro-1,2,2,3,3,3-hexafluoropropane (R-226ca), 1-chloro-1,1,2,2,3,3-hexafluoropropane (R-226cb) and 1,1,1,2,2,3,3,-heptafluoropropane (R-227ca). These products can be separated by a usual method such as distillation.
C.sub.3 H.sub.2 Cl.sub.4-m.sup.3 F.sub.2+m.sup.3 .fwdarw.C.sub.3 H.sub.2 Cl.sub.4-n.sup.3 F.sub.2+n.sup.3 (5)
0.ltoreq.m.sup.3 .ltoreq.3 1.ltoreq.n.sup.3 .ltoreq.4, m.sup.3 <n.sup.3
The chlorine-containing 2,2-halogenopropane (C.sub.3 H.sub.2 Cl.sub.4-m.sup.3 F.sub.2+m.sup.3 wherein 0.ltoreq.m.sup.3 .ltoreq.3) to be used as the starting material includes 1,1,1,3-tetrachloro-2,2-difluoropropane (R-232cb), 1,1,3,3-tetrachloro-2,2-difluoropropane (R-232ca), 1,1,3-trichloro-1,2,2-trifluoropropane (R-233cb), 1,1-dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,3-dichloro-1,1,2,2-tetrafluoropropane (R-234cc), 1,1-dichloro-2,2,3,3-tetrafluoropropane (R-234cb), 1,3-dichloro-1,2,2,3-tetrafluoropropane (R-234ca), 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc), 3 chloro-1,1,1,2,2-pentafluoropropane (R-235cb) and 1-chloro-1,2,2,3,3-pentafluoropropane (R-235ca).
The 2,2-difluoropropane (C.sub.3 H.sub.2 Cl.sub.4-n.sup.3 F.sub.2+n.sup.3 wherein 1.ltoreq.n.sup.3.ltoreq. 4) to be formed by the reaction includes 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc), 1,1,3-trichloro-1,2,2-trifluoropropane (R-233cb), 1,1,3-trichloro-2,2,3-trifluoropropane (R-233ca), 1,1-dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,3-dichloro-2,2,3,3-tetrafluoropropane (R-234cb), 1,3-dichloro-1,2,2,3-tetrafluoropropane (R-234ca), 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc), 3-chloro-1,1,1,2,2-pentafluoropropane (R-235cb), 1-chloro-1,2,2,3,3-pentafluoropropane (R-235ca), 1,1,1,2,2,3-hexafluoropropane (R-236cb) and 1,1,2,2,3,3-hexafluoropropane (R-236ca). These products can be separated by a usual method such as distillation.
C.sub.3 H.sub.3 Cl.sub.3-m.sup.4 F.sub.2+m.sup.4 .fwdarw.C.sub.3 H.sub.3 Cl.sub.3-n.sup.4 F.sub.2+n.sup.4 (6)
0.ltoreq.m.sup.4 .ltoreq.2 1.ltoreq.n.sup.4 .ltoreq.3, m.sup.4 <n.sup.4
The chlorine-containing 2,2 halogenopropane (C.sub.3 H.sub.3 Cl.sub.3-m.sup.4 F.sub.2+m.sup.4 wherein 0.ltoreq.m.sup.4 .ltoreq.2) to be used as the starting material includes 1,1,3-trichloro-2,2-difluoropropane (R-242ca), 1,1,1-trichloro-2,2-difluoropropane (R-242cb), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,2,3-trifluoropropane (R-243cb), 1,1-dichloro-1,2,2-tetrafluoropropane (R-244ca), 1-chloro-1,2,2,3-tetrafluoropropane (R-244cb) and 1-chloro-1,1,2,2-tetrafluoropropane (R-244cc).
The 2,2-difluoropropane and trihydrochlorofluoropropane (C.sub.3 H.sub.3 Cl.sub.3-n.sup.4 F.sub.2+n.sup.4 wherein 1.ltoreq.n.sup.4 .ltoreq.3) to be formed by the-reaction include 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,2,3-trifluoropropane (R-243cb), 1,1-dichloro-1,2,2-tetrafluoropropane (R-244ca), 1-chloro-1,2,2,3-tetrafluoropropane (R-244cb), 1-chloro-1,1,2,2-tetrafluoropropane (R-244cc), 1,1,2,2,3-pentafluoropropane (R-245ca) and 1,1,1,2,2-pentafluoropropane (R-245cb). These products can be separated by a usual method such as distillation.
C.sub.3 H.sub.4 Cl.sub.2-m.sup.5 F.sub.2+m.sup.5 .fwdarw.C.sub.3 H.sub.4 Cl.sub.2-n.sup.5 F.sub.2+n.sup.5 (7)
0.ltoreq.m.sup.5 .ltoreq.1 1.ltoreq.n.sup.5 .ltoreq.2, m.sup.5 <n.sup.5
The chlorine-containing 2,2-halogenopropane (C.sub.3 H.sub.4 Cl.sub.2-m.sup.5 F.sub.2+m.sup.5 wherein 0m.sup.5 .ltoreq.1) to be used as the starting material includes 1,3-dichloro-2,2-difluoropropane (R-252ca), 1,1-dichloro-2,2-difluoropropane (R-252cb), 1-chloro-2,2,3-trifluoropropane (R-253ca) and 1-chloro-1,2,2-trifluoropropane (R-253cb).
The 2,2-difluoropropane (C.sub.3 H.sub.4 Cl.sub.2-n.sup.5 F.sub.2+n.sup.5 wherein 1.ltoreq.n.sup.5 .ltoreq.2) to be formed by the reaction includes 1-chloro-2,2,3-trifluoropropane (R-253ca), 1-chloro-1,2,2-trifluoropropane (R-253cb), 1,2,2,3-tetrafluoropropane (R-254ca) and 1,1,2,2-tetrafluoropropane (R-254cb). These products can be separated by a usual method such as distillation.
On the other hand, when liquid phase fluorinations taking a long period of time are taken into account, the following reactions (8) to (12) may be mentioned.
C.sub.3 Cl.sub.8-m.sup.6 F.sub.m.sup.6 .fwdarw.C.sub.3 Cl.sub.8-n.sup.6 F.sub.n.sup.6 (8)
0.ltoreq.m.sup.6 .ltoreq.5 2.ltoreq.n.sup.6 .ltoreq.8, m.sup.6 <n.sup.6
The chlorine-containing 2,2-halogenopropane (C.sub.3 Cl.sub.8-m.sup.6 F.sub.m.sup.6 wherein 0.ltoreq.m.sup.6 .ltoreq.5) to be used as the starting material includes 1,1,1,2,2,3,3,3-octachloropropane (R-210aa), 1,1,1,2,3,3,3-heptachloro-2-fluoropropane (R-211ba), 1,1,1,3,3,3-hexachloro-2,2-difluoropropane (R-212ca), 1,1,1,3,3-pentachloro 2,2,3-trifluoropropane (R-213ca), 1,1,1,3,3-tetrachloro-1,2,2,3-tetrafluoorpropane (R-214ca), 1,1,1,3-tetrachloro-1,2,2,3,3-pentafluoropropane (R-215ca) and 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb).
The 2,2-difluoropropane (C.sub.3 Cl.sub.8-n.sup.6 F.sub.n.sup.6 wherein 2.ltoreq.n.sup.6 .ltoreq.8 and m.sup.6 <n.sup.6) to be formed by the reaction includes 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca), 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb), 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (R-215ca), 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb), 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca), 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-216cb), 1-chloro-1,1,2,2,3,3,3-heptafluoropropane (R-217ca) and octafluoropropane (R-218ca). These products can be separated by a usual method such as fractional distillation.
C.sub.3 HCl.sub.7-m.sup.7 F.sub.m.sup.7 .fwdarw.C.sub.3 HCl.sub.7-n.sup.7 F.sub.n.sup.7 (9)
0.ltoreq.m.sup.7 .ltoreq.4 2.ltoreq.n.sup.7 .ltoreq.7, m.sup.7 <n.sup.7
The chlorine-containing 2,2-halogenopropane (C.sub.3 HCl.sub.7-m.sup.7 Fm.sup.7 wherein 0.ltoreq.m.sup.7 .ltoreq.4) to be used as the starting material includes 1,1,1,2,2,3,3-heptachloropropane (R-220aa), 1,1,1,2,3,3-hexachloro-2-fluoropropane (R-221ba), 1,1,1,3,3-pentachloro-2,2-difluoropropane (R-222ca), 1,1,3,3-tetrachloro-1,2,2-trifluoropropane (R-223ca), 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-2123cb), 1,3,3-trichloro-1,1,2,2-tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-2224cb) and 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc).
The 2,2-difluoropropane (C.sub.3 HCl.sub.7-n.sup.7 F.sub.n.sup.7 wherein 2.ltoreq.n.sup.7 .ltoreq.7) to be formed by the reaction includes 1,1,3,3-tetrachloro-1,2,2-trifluoropropane (R-223ca), 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb), 1,3,3-trichloro-1,1,2,2-tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cb), 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 3-chloro-1,1,1,2,2,3-hexafluoroproane (R-226ca), 1-chloro-1,1,2,2,3,3-hexafluoropropane (R-226cb) and 1,1,1,2,2,3,3-heptafluoropropane (R-227ca). These products can be separated by a usual method such as fractional distillation.
C.sub.3 H.sub.2 Cl.sub.6-m.sup.8 F.sub.m.sup.8 .fwdarw.C.sub.3 H.sub.2 Cl.sub.6-n.sup.8 F.sub.n.sup.8 (10)
0.ltoreq.m.sup.8 .ltoreq.3 2.ltoreq.n.sup.8 .ltoreq.6, m.sup.8 <n.sup.8
The chlorine-containing 2,2-halogenopropane (C.sub.3 H.sub.2 Cl.sub.6-m.sup.8 F.sub.m.sup.8 wherein 0.ltoreq.m.sup.8 .ltoreq.3) to be used as the starting material includes 1,1,1,2,2,3-hexachloropropane (R-230ab), 1,1,2,2,3,3-hexachloropropane (R-230aa), 1,1,1,2,3-pentachloro-2-fluoropropane (R-231bb), 1,1,1,3-tetrachloro-2,2-difluoropropane (R-232cb), 1,1,3,3-tetrachloro-2,2-difluoropropane (R-232ca) and 1,1,3-trichloro-1,2,2-trifluoropropane (R-233cb). These are known compounds.
The 2,2-difluoropropane (C.sub.3 H.sub.2 Cl.sub.6-n.sup.8 F.sub.n.sup.8 wherein 2.ltoreq.n.sup.8 .ltoreq.6 and m.sup.8 <n.sup.8) to be formed by the reaction includes 1,1,3,3-tetrachloro-2,2-difluoropropane (R-232ca), 1,1,3-trichloro-1,2,2-trifluoropropane (R-233cb), 1,1,3-trichloro-2,2,3-trifluoropropane (R-233ca), 1,1-dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,3-dichloro-1,1,2,2-tetrafluoropropane (R-234cc), 1,1-dichloro-2,2,3,3-tetrafluoropropane (R-234cb), 1,3-dichloro-1,2,2,3-tetrafluoropropane (R-234ca), 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc), 3-chloro-1,1,1,2,2-pentafluoropropane (R-235cb), 1-chloro-1,2,2,3,3-pentafluoropropane (R-235ca), 1,1,1,2,2,3-hexafluoropropane (R-236cb) and 1,1,2,2,3,3-hexafluoropropane (R-236ca). These products can be separated by a usual method such as fractional distillation.
C.sub.3 H.sub.3 Cl.sub.5-m.sup.8 F.sub.m.sup.9 .fwdarw.C.sub.3 H.sub.3 Cl.sub.5-n.sup.9 F.sub.n.sup.9 (11)
0.ltoreq.m.sup.9 .ltoreq.2 2.ltoreq.n.sup.9 .ltoreq.5, m.sup.9 <n.sup.9
The chlorine-containing 2,2 halogenopropane (C.sub.3 H.sub.3 Cl.sub.5-m.sup.9 F.sub.m.sup.9 wherein 0.ltoreq.m.sup.9 .ltoreq.2) to be used as the starting material includes 1,1,2,2,3-pentachloropropane (R-240aa), 1,1,1,2,2-pentachloropropane (R-240ab), 1,1,2,3-tetrachloro-2-fluoropropane (R-241ba), 1,1,1,2-tetrachloro-2-fluoropropane (R-241bb), 1,1,3 trichloro-2,2-difluoropropane (R-242ca) and 1,1,1-trichloro-2,2-difluoropropane (R-242cb).
The 2,2-difluoropropane (C.sub.3 H.sub.3 Cl.sub.5-n.sup.9 F.sub.n.sup.9 wherein 2.ltoreq.n.sup.9 .ltoreq.5) to be formed by the reaction includes 1,1,3-trichloro-2,2-difluoropropane (R-242ca), 1,1,1-trichloro-2,2-difluoropropane (R-242cb), 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,2,3-trifluoropropane (R-243cb), 1,1-dichloro-1,2,2-trifluoropropane (R-243cc), 1-chloro-2,2,3,3-tetrafluoropropane (R-244ca), 1-chloro-1,1,2,2-tetrafluoropropane (R-244cc) and 1,1,1,2,2-pentafluoropropane (R-245cb). These products can be separated by a usual method such as fractional distillation.
C.sub.3 H.sub.4 Cl.sub.4-m.sup.10 F.sub.m.sup.10 .fwdarw.C.sub.3 H.sub.4 Cl.sub.4-n.sup.10 F.sub.n.sup.10 (12)
0.ltoreq.m.sup.10 .ltoreq.1 2.ltoreq.n.sup.10 .ltoreq.4
The chlorine-containing 2,2-halogenopropane (C.sub.3 H.sub.4 Cl.sub.4-m.sup.10 F.sub.m.sup.10 wherein 0.ltoreq.m.sup.10 .ltoreq.1) to be used as the starting material includes 1,2,2,3-tetrachloropropane (R-250aa), 1,1,2,2-tetrachloropropane (R-250ab), 1,2,3-trichloro-2-fluoropropane (R-251ba) and 1,1,2-trichloro-2-fuoropropane (R-251bb). These are known compounds.
The 2,2-difluoropropane (C.sub.3 H.sub.4 Cl.sub.4-n.sup.10 F.sub.n.sup.10 wherein 2.ltoreq.n.sup.10 .ltoreq.4) to be formed by the reaction includes 1,3-dichloro-2,2-difluoropropane (R-252ca), 1,1-dichloro-2,2-difluoropropane (R-252cb), 1-chloro-2,2,3-trifluoropropane (R-253ca), 1-chloro-1,2,2-trifluoropropane (R-253cb) and 1,1,2,2-tetrafluoropropane (R-254cb). These products can be separated by a usual method such as fractional distillation.
Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted by such specific Examples.
EXAMPLE 1-1
Into a 1 l Hastelloy C autoclave, 500 g of 1,1,1,2,2,3,3,3-octachloropropane (CCl.sub.3 CCl.sub.2 CCl.sub.3 R-210aa), 50 g of tantalum pentafluoride and 300 g of hydrogen fluoride were charged. Then, the temperature was raised to 150.degree. C., and hydrogen fluoride was fed in at a rate of 50 g per hour over a period of 3 hours. The reaction was conducted for 20 hours at this state while keeping the reaction temperature at this level. The reaction products were collected in a trap cooled at-78.degree. C. The composition after removing acidic components from the collected product, was analyzed by gas chromatography and by .sup.19 F-NMR. As the results, it was confirmed that fluorine-containing chlorofluoropropanes such as CF.sub.3 CClF.sub.2 CClFCClF.sub.2 (R-215ba), CCl.sub.2 FCClFCClF.sub.2 (R-214ba), CClF.sub.2 CCl.sub.2 CClF.sub.2 (R-214aa), CCl.sub.2 FCClFCCl.sub.2 F (R-213ba), CClF.sub.2 CCl.sub.2 CCl.sub.2 F (R-213aa), CCl.sub.2 FCClFCCl.sub.3 (R-212ba) and CCl.sub.2 F.sub.2 CCl.sub.2 CCl.sub.2 F (R-212aa), were formed in a certain amounts in addition to CF.sub.3 CF.sub.2 CClF.sub.2 (R-217ca), CF.sub.3 CF.sub.2 CCl.sub.2 F (R-216cb), CClF.sub.2 CF.sub.2 CClF.sub.2 (R-216ca), CClF.sub.2 CF.sub.2 CCl.sub.2 F (R-215ca) and CCl.sub.2 FCF.sub.2 CCl.sub.2 F (R-214ca) which have a difluoromethylene group. The results are shown in Table 1-1.
TABLE 1-1______________________________________Fluorination of R-210aaConversion of R-210aa 49%______________________________________Selectivity for R-217 2%(for R-217ca) (1%)Selectivity for R-216 3%(for R-216ca) (1%)(for R-216cb) (1%)Selectivity for R-215 12%(for R-215ca) (5%)Selectivity for R-214 42%(for R-214ca) (2%)Selectivity for R-213 27%Selectivity for R-212 11%Selectivity for others 3%______________________________________
EXAMPLE 1-2
The reaction was conducted in the same manner as in Example 1-1 except that 500 g of 1,1,1,2,3,3,3-heptacholoro-2-fluoropropane (R-211ba) was used in place of 1,1,1,2,2,3,3,3-octachloropropane (R-210aa), 50 g of niobium pentachloride was used in place of tantalum pentafluoride and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that chlorofluoropropanes such as CF.sub.3 CClFCClF.sub.2 (R-216ba), CClF.sub.2 CClFCClF.sub.2 (R-215ba), CCl.sub.2 FCClFCClF.sub.2 (R-214ba), CCl.sub.2 FCClFCCl.sub.2 F (R-213ba) and CCl.sub.2 FCClFCCl.sub.3 (R-212ba), were formed in certain amounts in addition to CF.sub.3 CF.sub.2 CClF.sub.2 (Rca), CF.sub.3 CF.sub.2 CCl.sub.2 F (R-216cb), CClF.sub.2 CF.sub.2 CClF.sub.2 (R-216ca), CClF.sub.2 CF.sub.2 CCl.sub.2 F (R-215ca) and CCl.sub.2 FCF.sub.2 CCl.sub.2 F (R-214ca) which have a difluoromethylene group. The results are shown in
TABLE 1-2______________________________________Fluorination of R-211baConversion of R-211ba 77%______________________________________Selectivity for R-217 2%(for R-217ca) (1%)Selectivity for R-216 5%(for R-216ca) (2%)(for R-216cb) (1%)Selectivity for R-215 21%(for R-215ca) (8%)Selectivity for R-214 38%(for R-214ca) (16%)(for R-214cb) (2%)Selectivity for R-213 17%(for R-213cb) (8%)Selectivity for R-211 13%Selectivity for others 4%______________________________________
EXAMPLE 1-3
The reaction was conducted in the same manner as in Example 1-1 except that 500 g of 1,1,1,3,3,3-hexachloro-2,2-difluoropropane (R-212ca) was used in place of 1,1,1,2,2,3,3,3-octachloropropane (R-210aa), 50 g of antimony pentachloride was used in place of tantalum pentafluoride and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that chlorofluoropropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CClF.sub.2 (R-217ca), CClF.sub.2 CF.sub.2 CClF.sub.2 (R-216ca), CClF.sub.2 CF.sub.2 CCl.sub.2 F (R-215ca) and CCl.sub.2 FCF.sub.2 CCl.sub.2 F (R-214ca), were formed in certain amounts. The results are shown in Table 1-3.
TABLE 1-3______________________________________Fluorination of R-212caConversion of R-212ca 63%______________________________________Selectivity for R-217 2%(for R-217ca) (2%)Selectivity for R-216 8%(for R-216ca) (7%)(for R-216cb) (1%)Selectivity for R-215 20%(for R-215ca) (19%)(for R-215cb) (1%)Selectivity for R-214 52%(for R-214ca) (50%)(for R-214cb) (2%)Selectivity for R-213 17%(for R-213ca) (17%)Selectivity for others 1%______________________________________
EXAMPLE 1-4
The reaction was conducted in the same manner as in Example 1-1 except that 500 g of 1,1,1,3,3-pentachloro-2,2 difluoropropane (R-213ca) was used in place of 1,1,1,2,2,3,3,3-octachloropropane (R-210aa) and the reaction temperature was changed to 130.degree. C. As the results, it was confirmed that chlorofluoropropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CClF.sub.2 (R217ca), CClF.sub.2 CF.sub.2 CClF.sub.2 (R-216ca), CClF.sub.2 CF.sub.2 CCl.sub.2 F (R-215ca) and CCl.sub.2 FCF.sub.2 CCl.sub.2 F (R-214ca), were formed in certain amounts. The results are shown in Table 1-4.
TABLE 1-4______________________________________Fluorination of R-213caConversion of R-213ca 88%______________________________________Selectivity for R-217 4%(for R-217ca) (4%)Selectivity for R-216 19%(for R-216ca) (17%)(for R-216cb) (2%)Selectivity for R-215 30%(for R-215ca) (29%)(for R-215cb) (1%)Selectivity for R-214 46%(for R-214ca) (44%)(for R-214cb) (2%)Selectivity for others 1%______________________________________
EXAMPLE 1-5
The reaction was conducted in the same manner as in Example 1-1 except that 500 g of 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca) was used in place of 1,1,1,2,2,3,3,3-octachloropropane (R-210aa) and the reaction temperature was changed to 130.degree. C. As the results, it was confirmed that fluoropropanes and chlorofluoropropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CF.sub.3 (R-218ca), CF.sub.3 CF.sub.2 CClF.sub.2 (R-217ca), CClF.sub.2 CF.sub.2 CClF.sub.2 (R-216ca), CF.sub.3 CF.sub.2 CCl.sub.2 F (R-216cb) and CClF.sub.2 CF.sub.2 CCl.sub.2 F (R-215ca), were formed in certain amounts. The results are shown in Table 1-5.
TABLE 1-5______________________________________Fluorination of R-214caConversion of R-214ca 92%______________________________________Selectivity for R-218ca 2%Selectivity for R-217ca 14%Selectivity for R-216 44%(for R-216ca) (41%)(for R-216cb) (3%)Selectivity for R-215 33%(for R-215ca) (31%)(for R-215cb) (2%)Selectivity for others 7%______________________________________
EXAMPLE 1-6
The reaction was conducted in the same manner as in Example 1 1 except that 500 g of 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb) was used in place of 1,1,1,2,2,3,3,3-octachloropropane (R-210aa) and the reaction temperature was changed to 110.degree. C. As the results, it was confirmed that fluoropropanes and chlorofluoropropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CF.sub.3 (R-218ca), CF.sub.3 CF.sub.2 CClF.sub.2 (R-217ca), CClF.sub.2 CF.sub.2 CClF.sub.2 (R-216ca), CF.sub.3 CF.sub.2 CCl.sub.2 F (R-216cb) and CClF.sub.2 CF.sub.2 CCl.sub.2 F (R-215ca), were formed in certain amounts. The results are shown in Table 1-6.
TABLE 1-6______________________________________Fluorination of R-214cbConversion of R-214cb 72%______________________________________Selectivity for R-218ca 1%Selectivity for R-217ca 10%Selectivity for R-216 34%(for R-216ca) (31%)(for R-216cb) (3%)Selectivity for R-215 52%(for R-215ca) (51%)(for R-215cb) (1%)Selectivity for others 3%______________________________________
EXAMPLE 1-7
The reaction was conducted in the same manner as in Example 1 1 except that 500 g of 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (R-215ca) was used instead of 1,1,1,2,2,3,3,3-octachloropropane (R-210aa) and the reaction temperature was changed to 110.degree. C. As the results, it was confirmed that fluoropropanes and chlorofluoropropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CF.sub.3 (R-218ca), CF.sub.3 CF.sub.2 CClF.sub.2 (R-217ca), CClF.sub.2 CF.sub.2 CClF.sub.2 (R-216ca) and CF.sub.3 CF.sub.2 CCl.sub.2 F (R-216cb), were formed in certain amounts. The results are shown in Table 1-7.
TABLE 1-7______________________________________Fluorination of R-215caConversion of R-215ca 68%______________________________________Selectivity for R-218ca 2%Selectivity for R-217ca 11%Selectivity for R-216 84%(for R-216ca) (80%)(for R-216cb) (4%)Selectivity for others 3%______________________________________
EXAMPLE 1-8
The reaction was conducted in the same manner as in Example 1 1 except that 500 g of 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb) was used in place of 1,1,1,2,2,3,3,3-octachloropropane (R-210aa). As the results, fluoropropanes and chlorofluoropropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CF.sub.3 (R-218ca), CF.sub.3 CF.sub.2 CClF.sub.2 (R-217ca) and CF.sub.3 CF.sub.2 CCl.sub.2 F (R-216cb), were formed in certain amounts. The results are shown in Table 1-8.
TABLEL 1-8______________________________________Fluorination of R-215cbConversion of R-215cb 72%______________________________________Selectivity for R-218ca 5%Selectivity for R-217ca 21%Selectivity for R-216cb 67%Selectivity for others 7%______________________________________
EXAMPLE 2-1
Into a 1 l Hastelloy C autoclave, 500 g of 1,1,1,2,2,3,3,3-heptachloropropane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 R-220aa) and 50 g of antimony pentachloride were charged. The temperature was raised to 100.degree. C. while hydrogen fluoride was supplied at a rate of 50 g per hour over a period of 5 hours. Then, hydrogen fluoride was further fed in at a rate of 50 g per hour over a period of 3 hours. The reaction was conducted at this state for 20 hours while keeping the reaction temperature at this level. The reaction products were collected in a trap cooled at -78.degree. C. The composition after removal of acid components from the collected products, was analyzed by gas chromatography and by 19F-NMR. As the results, it was confirmed that monohydroheptahalogenopropanes having at least 2 fluorine atoms such as CF.sub.3 CClFCHClF (R-225ba), CHClFCCl.sub.2 CF.sub.3 (R-224aa), CHCl.sub.2 CClFCF.sub.3 (R-224ba) and CF.sub.3 CCl.sub.2 CHCl.sub.2 (R-223aa), were formed in addition to monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHCClF (R-226ca), CF.sub.3 CF.sub.2 CHCl.sub.2 (R-225ca), CCl.sub.2 FCF.sub.2 CHClF (R-224cb) and CCl.sub.2 FCF.sub.2 CHCl.sub.2 (R-223ca). The results are show in Table 2-1.
TABLE 2-1______________________________________Fluorination of R-220aaConversion of R-220aa 58%______________________________________Selectivity for R-226 2%(for R-226ca) (1%)Selectivity for R-225 7%(for R-225ca) (5%)Selectivity for R-224 21%(for R-224cb) (2%)Selectivity for R-223 28%(for R-223ca) (1%)Selectivity for R-222 30%Selectivity for others 12%______________________________________
EXAMPLE 2-2
The reaction was conducted in the same manner as in Example 2-1 except that 500 g of 1,1,1,2,3,3-hexachloro-2-fluoropropane (CCl.sub.3 CClFCHCl.sub.2 : R-221ba) was used in place of 1,1,1,2,2,3,3-heptachloropropane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 : R-220aa), 50 g of niobium pentachloride was used in place of antimony pentachloride and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that monohydroheptahalogenopropanes having at least 2 fluorine atoms such as CF.sub.3 CClFCHClF (R-225ba) and CClF.sub.2 CClFCHClF (R-224bb) were formed in addition to monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHClF (R-226ca), CF.sub.3 CF.sub.2 CHCCl.sub.2 (Rca) and CCl.sub.2 FCF.sub.2 CHClF (R-224cb). The results are shown in Table 2-2.
TABLE 2-2______________________________________Fluorination of R-221baConversion of R-221ba 85%______________________________________Selectivity for R-226 3%(for R-226ca) (2%)Selectivity for R-225 9%(for R-225ca) (6%)Selectivity for R-224 30%(for R-224cb) (2%)Selectivity for R-223 29%Selectivity for R-222 17%Selectivity for others 12%______________________________________
EXAMPLE 2-3
The reaction was conducted in the same manner as in Example 2-1 except that 500 g of 1,1,1,3,3-pentachloro-2,2-difluoropropane (R-222ca) was used in place of 1,1,1,2,2,3,3-heptachloropropane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 : R-220aa), 50 g of niobium pentachloride was used in place of antimony pentachloride and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHF.sub.2 (R-227ca), CF.sub.3 CF.sub.2 CHClF (R-226ca), CF.sub.3 CF.sub.2 CHCl.sub.2 (R-225ca), CClF.sub.2 CF.sub.2 CHClF (R-225cb), CClF.sub.2 CF.sub.2 CHCl.sub.2 (R-224ca), CCl.sub.2 FCF.sub.2 CHClF (R-224cb) and CCl.sub.2 FCF.sub.2 CHCl.sub.2 (R-223ca), were formed. The results are shown in Table 2-3.
TABLE 2-3______________________________________Fluorination of R-222caConversion of R-222ca 78%______________________________________Selectivity for R-227ca 1%Selectivity for R-226 3%(for R-226ca) (2%)(for R-226cb) (1%)Selectivity for R-225 12%(for R-225ca) (8%)(for R-225cb) (3%)(for R-225cc) (1%)Selectivity for R-224 37%(for R-224ca) (25%)(for R-224cb) (11%)(for R-224cc) (1%)Selectivity for R-223 46%(for R-223ca) (35%)(for R-223cb) (11%)Selectivity for others 1%______________________________________
EXAMPLE 2-4
The reaction was conducted in the same manner as in Example 2-1 except that 500 g of 1,1,3,3-tetrachloro-1,2,2-trifluoropropane (R-223ca) was used in place of 1,1,1,2,2,3,3-heptachloropropane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 R-220aa) and 50 g of niobium pentachloride was used in place of antimony pentachloride. As the results, monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHF.sub.2 (R-227ca), CF.sub.3 CF.sub.2 CHClF (R-226ca), CF.sub.3 CF.sub.2 CHCl.sub.2 (R-225ca), CClF.sub.2 CF.sub.2 CHClF (R-225cb), CClF.sub.2 CF.sub.2 CHCl.sub.2 (R-224ca) and CCl.sub.2 F.sub.2 CHClF (R-224cb), were formed. The results are shown in Table 2-4.
TABLE 2-4______________________________________Fluorination of R-223caConversation of R-223ca 88%______________________________________Selectivity for R-227ca 2%Selectivity for R-226 3%(for R-226ca) (3%)(for R-226cb) (1%)Selectivity for R-225 30%(for R-225ca) (21%)(for R-225cb) (7%)(for R-225cc) (1%)Selectivity for R-224 64%(for R-224ca) (46%)(for R-224cb) (17%)(for R-224cc) (1%)Selectivity for others 1%______________________________________
EXAMPLE 2-5
The reaction was conducted in the same manner as in Example 2-1 except that 500 g of 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb) was used in place of 1,1,1,2,2,3,3-heptachloropropane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 : R-220aa) and 50 g of niobium pentachloride was used in place of anitimony pentachloride. As the results, monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHF.sub.2 (R-227ca), CF.sub.3 CF.sub.2 CHClF (R-226ca), CClF.sub.2 CF.sub.2 CHCClF (R-225cb) and CCl.sub.2 FCF.sub.2 CHClF (R-224cb), were formed. The results are shown in Table 2-5.
TABLE 2-5______________________________________Fluorination of R-223cbConversion of R-223cb 72%______________________________________Selectivity for R-227ca 1%Selectivity for R-226 2%(for R-226ca) (2%)Selectivity for R-225 39%(for R-225cb) (37%)(for R-225cc) (2%)Selectivity for R-224 57%(for R-224cb) (57%)(for R-224cc) (1%)Selectivity for others 1%______________________________________
EXAMPLE 2-6
The reaction was conducted in the same manner as in Example 2-1 except that 500 g of 1,3,3-trichloro-1,1,2,2-tetrafluoropropane (R-224ca) was used in place of 1,1,1,2,2,3,3-heptachloropropane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 R-220aa) and 50 g of niobium pentachloride was used in place of antimony pentachloride. As the results, it was confirmed that monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHF.sub.2 (R-227ca), CF.sub.3 CF.sub.2 CHClF (R-226ca), CClF.sub.2 CF.sub.2 CHF.sub.2 (R-226cb), CF.sub.3 CF.sub.2 CHCl.sub.2 (R-225ca) and CClF.sub.2 CF.sub.2 CHClF (R-225cb), were formed. The results are shown in Table 2-6.
TABLE 2-6______________________________________Fluorination of R-224caConversion of R-224ca 65%______________________________________Selectivity of R-227ca 1%Selectivity of R-226 5%(for R-226ca) (4%)(for R-226cb) (1%)Selectivity for R-225 94%(for R-225ca) (83%)(for R-225cb) (10%)(for R-225cc) (1%)Selectivity for others 1%______________________________________
EXAMPLE 2-7
The reactin was conducted in the same manner as in Example 2-1 except that 500 g of 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cb) was used in place of 1,1,1,2,2,3,3-heptachloroproane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 : R-220aa), and 50 g of niobium pentachloride was used in place of antimony pentachloride. As the results, it was confirmed that monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHF.sub.2 (R-227ca), CF.sub.3 CF.sub.2 CHClF (R-226ca), CClF.sub.2 CF.sub.2 CHF.sub.2 (R-226cb) and CClF.sub.2 CF.sub.2 CHClF (R-225cb), were formed. The results are shown in Table 2-7.
TABLE 2-7______________________________________Fluorination of R-224cbConversion of R-224cb 68%______________________________________Selectivity of R-227ca 1%Selectivity of R-226 23%(for R-226ca) (19%)(for R-226cb) (4%)Selectivity of R-225 69%(for R-225cb) (61%)(for R-225cc) (8%)Selectivity for others 7%______________________________________
EXAMPLE 2-8
The reaction was conducted in the same manner as in Example 2-1 except that 500 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc) was used in place of 1,1,1,2,2,3,3-heptachloropropane (CCl.sub.3 CCl.sub.2 CHCl.sub.2 : R-220aa) and 50 g of niobium pentachloride was used in place of antimony pentachloride. As the results, it was confirmed that monohydroheptahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CHF.sub.2 (R-227ca) and CCl.sub.2 FCF.sub.2 CHF.sub.2 (R-225cc) were formed. The results are shown in Table 2-8.
TABLE 2-8______________________________________Fluorination of R-224ccConversion of R-224cc 88%______________________________________Selectivity of R-227ca 5%Selectivity of R-226cb 28%Selectivity of R-225cc 63%Selectivity for others 4%______________________________________
EXAMPLE 3-1
Into a 1 l Hastelloy C autoclave, 500 g of 1,1,1,2,2,3-hexachloropropane (CCl.sub.3 CCl.sub.2 CH.sub.2 Cl: R-230ab) and 50 g of antimony pentachloride, were charged. The temperature was raised to 100.degree. C. while hydrogen fluoride was supplied at a rate of 50 g per hour over a period of 3 hours. Then, hydrogen fluoride was further fed in at a rate of 50 g per hour over a period of 3 hours. The reaction was conducted at this state for 20 hours while keeping the reaction temperature at this level. The reaction products were collected in a trap cooled at -78.degree. C. The composition after removing acidic components from the collected products was analyzed by gas chromatography and by .sup.19 F-NMR. As the results, it was confirmed that dihydrohexahalogenopropanes having at least 2 fluorine atoms such as CF.sub.3 CClFCH.sub.2 Cl (R-234bb), CClF.sub.2 CClFCH.sub.2 Cl (R-233bc) and CClF.sub.2 CCl.sub.2 CH.sub.2 Cl (R-232ab), were formed in addition to dihydrohexahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CH.sub.2 Cl (R-235cb), CClF.sub.2 CF.sub.2 CH.sub.2 Cl (R-234cc) and CCl.sub.2 FCF.sub.2 CH.sub.2 Cl (R-233cb). The results are shown in Table 3-1.
TABLE 3-1______________________________________Fluorination of R-230abConversion of R-230ab 43%______________________________________Selectivity for R-235cb 1%Selectivity for R-234 32%(for R-234cc) (17%)Selectivity for R-233 36%(for R-233cb) (2%)Selectivity for R-232 23%Selectivity for others 8%______________________________________
EXAMPLE 3-2
The reaction was conducted in the same manner as in Example 3-1 except that 500 g of 1,1,2,2,3,3-hexachloropropane (R-230aa) was used in place of 1,1,1,2,2,3-hexachloropropane (R-230ab), 50 g of tantalum pentafluoride was used in place of antimony pentachloride and the reaction temeprature was changed to 120.degree. C. As the results, it was confirmed that dihydrohexahalogenopropanes having at least 2 fluorine atoms such as CHF.sub.2 CClFCClF (R-234ba), CHClFCCl.sub.2 CHF.sub.2 (R-233aa), CHClFCClFCHClF (R-233ba) and CHF.sub.2 ClFCHCl.sub.2 (R-223bb), were formed in addition to dihydrohexahalogenopropanes having a difluoromethylene group such as CHF.sub.2 CF.sub.2 CHClF (R-235ca), CHClFCF.sub.2 CHClF (R-234ca), CHCl.sub.2 CF.sub.2 CHF.sub.2 (R-234cb) and CHCl.sub.2 CF.sub.2 CHClF (R-233ca). The results are shown in Table 3-2.
TABLE 3-2______________________________________Fluorination of R-230aaConversion of R-230aa 68%______________________________________Selectivity for R-235 5%(for R-235ca) (3%)Selectivity for R-234 22%(for R-234cb) (12%)(for R-234ca) (3%)Selectivity for R-233 29%(for R-233ca) (2%)Selectivity for R-232 33%Selectivity for others 11%______________________________________
EXAMPLE 3-3
The reaction was conducted in the same manner as in Example 3-1 except that 500 g of 1,1,1,2,3-pentachloro-2-fluoropropane (R-231bb) was used in place of 1,1,1,2,2,3-hexachloropropane (R-230ab), 50 g of tantalum pentafluoride was used in place of antimony penthachloride and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that dihydrohexahalogenopropanes having at least 2 fluorine atoms such as CF.sub.3 CClFCH.sub.2 Cl (R-234bb), CClF.sub.2 CClFCH.sub.2 Cl (R-233bc) and CCl.sub.2 FCClFCH.sub.2 Cl (R-232bb), were formed in addition to dihydrohexahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CH.sub.2 Cl (R-235cb), CClF.sub.2 CF.sub.2 CH.sub.2 Cl (R-234cc) and CCl.sub.2 FCF.sub.2 CH.sub.2 Cl (R-233cb). The results are shown in Table 3-3.
TABLE 3-3______________________________________Fluorination of R-231bbConversion of R-231bb 73%______________________________________Selectivity for R-235cb 8%Selectivity for R-234 49%(for R-234cc) (27%)Selectivity for R-233 31%(for R-233cb) (13%)Selectivity for R-232 3%Selectivity for others 9%______________________________________
EXAMPLE 3-4
The reaction was conducted in the same manner as in Example 3-1 except that 500 g of 1,1,1,3-tetrachloro-2,2-difluoropropane (R-232cb) was used in place of 1,1,1,2,2,3-hexachloropropane (R-230ab) and the reaction temeprature was changed to 120.degree. C. As the results, it was confirmed that dihydrohexahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CH.sub.2 Cl (R-235cb), CClF.sub.2 CF.sub.2 CH.sub.2 Cl (R-234cc) and CCl.sub.2 FCF.sub.2 CH.sub.2 Cl (R-233cb), were formed. The results are shown in Table 3-4.
TABLE 3-4______________________________________Fluorination of R-232cbConversion of R-232cb 62%______________________________________Selectivity for R-235cb 2%Selectivity for R-234cc 53%Selectivity for R-233cb 38%Selectivity for others 7%______________________________________
EXAMPLE 3-5
The reaction was conducted in the same manner as in Example 3-1 except that 500 g of 1,1,3,3-tetrachloro-2,2-difluoropropane (R-232ca) was used in place of 1,1,1,2,2,3-hexachloropropane (R-230ab), 50 g of tantalum pentafluoride was used in place of antimony pentachloride and the reaction temeprature was changed to 130.degree. C. As the results, it was confirmed that dihydrohexahalogenopropanes having a difluoromethylene group such as CHF.sub.2 CF.sub.2 CHF.sub.2 (R-236ca), CHF.sub.2 CF.sub.2 CHClF (R-235ca), CHClFCF.sub.2 CHClF (R-234ca) and CHCl.sub.2 CF.sub.2 CHF.sub.2 (R-234cb), were formed. The results are shown in Table 3-5.
TABLE 3-5______________________________________Fluorination of R-232caConversion of R-232ca 83%______________________________________Selectivity for R-236ca 1%Selectivity for R-235ca 12%Selectivity for R-234 32%(for R-234cb) (27%)(for R-234ca) (5%)Selectivity for R-233ca 46%Selectivity for others 9%______________________________________
EXAMPLE 3-6
The reaction was conducted in the same manner as in Example 3-1 except that 500 g of 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc) was used in place of 1,1,1,2,2,3-hexachloropropane (R-230ab) and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that dihydrohexahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CH.sub.2 F (R-236cb), CClF.sub.2 CF.sub.2 CH.sub.2 F (R-235cc) and CCl.sub.2 FCF.sub.2 CH.sub.2 F (R-234cd), were formed. The results are shown in Table 3-6.
TABLE 3-6______________________________________Fluorination of R-233ccConversion of R-233cc 65%______________________________________Selectivity for R-236cb 4%Selectivity for R-235cc 13%Selectivity for R-234cd 55%Selectivity for others 28%______________________________________
EXAMPLE 3-7
The reaction was conducted in the same manner as in Example 3-1 except that 500 g of 1,1,3-trichloro-1,2,2-trifluoropropane (R-233cb) was used in place of 1,1,1,2,2,3 hexachloropropane (R-230ab), 100 g of niobium pentachloride was used in place of antimony pentachloride and the reaction temperature was changed to 110.degree. C. As the results, dihydrohexahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CH.sub.2 Cl (R-235cb) and CClF.sub.2 CF.sub.2 CH.sub.2 Cl (R-234cc), were formed. The results are shown in Table 3-7.
TABLE 3-7______________________________________Fluorination of R-233cbConversion of R-233cb 79%______________________________________Selectivity for R-235cb 17%Selectivity for R-234cc 82%Selectivity for others 1%______________________________________
EXAMPLE 3-8
The reaction was conducted in the same manner as in Example 3-1 except that 500 g of 1,1,3-trichloro-2,2,3-trifluoropropane (R-233ca) was used in place of 1,1,1,2,2,3-hexachloropropane (R-230ab), 50 g of tantalum pentafluoride was used in place of antimony pentachloride and reaction temperature was changed to 120.degree. C. As the results, it was confirmed that dihydrohexahalogenopropanes having a difluoromethylene group such as CHF.sub.2 CF.sub.2 CHF.sub.2 (R-236ca), CHF.sub.2 CF.sub.2 CHClF (R-235ca), CHClFCF.sub.2 CHClF (R-234ca) and CHCl.sub.2 CF.sub.2 CHF.sub.2 (R-234cb), were formed. The results are shown in Table 3-8.
TABLE 3-8______________________________________Fluorination of R-233caConversion of R-233ca 91%______________________________________Selectivity for R-236ca 3%Selectivity for R-235ca 41%Selectivity for R-234 55%(for R-234cb) (43%)(for R-234ca) (12%)Selectivity for others 1%______________________________________
EXAMPLE 4-1
Into a 1 l Hastelloy C autoclave, 500 g of 1,1,2,2,3-pentachloropropane (CHCl.sub.2 CCl.sub.2 CH.sub.2 Cl: R-240aa) and 50 g of antimony pentachloride, were charged. The temperature was raised to 100.degree. C. while hydrogen fluoride was supplied at a rate of 50 g/hr over a period of 3 hours. Then, hydrogen fluoride was further fed in at a rate of 50 g/hr over a period of 3 hours. The reaction was conducted at this state for 20 hours while keeping the reaction temperature at this level. The reaction products were collected in a trap cooled at -78.degree. C. The composition after removing acidic components from the collected products, was analyzed by gas chromatography and by .sup.19 FNMR. As the results, it was-confirmed that trihydropentahalogehopropanes having at least 2 fluorine atoms such as CHF.sub.2 CClFCH.sub.2 Cl (R-243ba), CHClFCClFCH.sub.2 Cl (R-242ba), CHCl.sub.2 CClFCH.sub.2 Cl (R-241ba) and CHClFCCl.sub.2 CH.sub.2 Cl (R-241aa), were formed in addition to trihydropentahalogenopropanes having a difluoromethylene group such as CHF.sub.2 CF.sub.2 CH.sub.2 Cl (R-244ca), CHClFCF.sub.2 CH.sub.2 Cl (R-243ca) and CHCl.sub.2 CF.sub.2 CH.sub.2 Cl (R-242ca). The results are shown in Table 4-1.
TABLE 4-1______________________________________Fluorination of R-240aaConversion of R-240aa 38%______________________________________Selectivity for R-244ca 1%Selectivity for R-243 22%(for R-243ca) (7%)Selectivity for R-242 36%(for R-242ca) (2%)Selectivity for R-241 33%Selectivity for others 8%______________________________________
EXAMPLE 4-2
The reaction was conducted in the same manner as in Example 4-1 except that 500 g of 1,1,1,2,2-pentachloropropane (R-240ab) was used in place of 1,1,2,2,3-pentachloropropane-(R-240aa), 50 g of tantalum pentafluoride was used in place of antimony pentachloride and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that trihydropentahalogenopropanes having at least 2 fluroine atoms such as CF.sub.3 CClFCH.sub.3 (R-243ba), CClF.sub.2 CClFCH.sub.3 (R-243bc), CF.sub.3 Cl.sub.2 CH.sub.3 (R-243ab), CClF.sub.2 CClFCH.sub.3 (R-243bc) and CClF.sub.2 CCl.sub.2 CH.sub.3 (R-242ac), were formed in addition to trihydropentahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CH.sub.3 (R-245cb) and CClF.sub.2 CF.sub.2 CH.sub.3 (R-244cc). The results are shown in Table 4-2.
TABLE 4-2______________________________________Fluorination of R-240abConversion of R-240ab 72%______________________________________Selectivity for R-245cb 2%Selectivity for R-244 12%(for R-244cc) (5%)Selectivity for R-243 21%Selectivity for R-242 43%Selectivity for others 22%______________________________________
EXAMPLE 4-3
The reaction was conducted in the same manner as in Example 4-1 except that 500 g of 1,1,2,3-tetrachloro-2-fluoropropane (R-241ba) was used in place of 1,1,2,2,3-pentachloropropane (R-240aa)r 50 g of tantalum pentafluoride was used in place of antimony pentachloride and the reaction temperature was changed to 130.degree. C. As the results, it was confirmed that trihydropentahalogenopropanes having at least fluorine atoms such as CHF.sub.2 CClFCH.sub.2 Cl (R-243ba) and CHClFCClFCH.sub.2 Cl (R-242ba) were formed in addition to trihydropentahalogenopropanes having a difluoromethylene group such as CHF.sub.2 CF.sub.2 CH.sub.2 Cl (R-244ca), CHClFCF.sub.2 CH.sub.2 Cl (R-243ca) and CHCl.sub.2 CF.sub.2 CH.sub.2 Cl (R-242ca). The results are shown in Table 4-3.
TABLE 4-3______________________________________Fluorination of R-241baConversion of R-241ba 69%______________________________________Selectivity for R-244ca 3%Selectivity for R-243 55%(for R-243ca) (37%)Selectivity for R-242 39%(for R-242ca) (5%)Selectivity for others 3%______________________________________
EXAMPLE 4-4
The reaction was conducted in the same manner as in Example 4-1 except that 500 g of 1,1,1,2-tetrachloro-2-fluoropropane (R-241bb) was used in place of 1,1,1,2,2,3-pentachloropropane (R-240aa), 50 g of niobium pentachloride was used in place of antimony pentachloride and the reaction temperature was changed to 130.degree. C. As the results, it was confirmed that trihydropentahalogenopropanes having at least 2 fluorine atoms such as CF.sub.3 CClFCH.sub.3 (R-244bb), CClF.sub.2 CClFCH.sub.3 (R-243bc) and CCl.sub.2 FCClFCH.sub.3 (R-242bc), were formed in addition to trihydropentahalogenopropanes having a difluoromethylene group such as CF.sub.3 CF.sub.2 CH.sub.3 (R-245cb), CClF.sub.2 CF.sub.2 CH.sub.3 (R-244cc), CCl.sub.2 FCF.sub.2 CH.sub.3 (R-243cc) and CCl.sub.3 CF.sub.2 CH.sub.3 (R-242cb). The results are shown in Table 4-4.
TABLE 4-4______________________________________Fluorination of R-241bbConversion of R-241bb 73%______________________________________Selectivity for R-245cb 3%Selectivity for R-244 22%(for R-244cc) (12%)Selectivity for R-243 46%(for R-243cc) (18%)Selectivity for R-242 26%(for R-242cb) (3%)Selectivity for others 3%______________________________________
EXAMPLE 4-5
The reaction was conducted in the same manner as in Example 4-1 except that 500 g of 1,1,3-trichloro-2,2-difluoropropane (R-242ca) was used in place of 1,1,2,2,3-pentachloropropane (R-240aa), 50 g of tantalum pentafluoride was used in place of antimony pentachloride and the reaction temperature was changed to 110.degree. C. The results are shown in Table 4-5.
TABLE 4-5______________________________________Fluorination of R-242caConversion of R-242ca 73%______________________________________Selectivity for R-244ca 8%Selectivity for R-243ca 75%Selectivity for others 17%______________________________________
EXAMPLE 4-6
The reaction was conducted in the same manner as in Example 4-1 except that 500 g of 1,1,1-trichloro-2,2-difluoropropane (R-242cb) was used in place of 1,1,2,2,3-pentachloropropane (R-240aa) and the reaction temperature was changed to 110.degree. C. The results are shown in Table 4-6.
TABLE 4-6______________________________________Fluorination of R-242cbConversion of R-242cb 75%______________________________________Selectivity for R-245cb 5%Selectivity for R-244cc 28%Selectivity for R-243cc 66%Selectivity for others 1%______________________________________
EXAMPLE 5-1
Into a 1 l Hastelloy C autoclave, 500 g of 1,2,2,3-tetrachloropropane (R-250aa) and 50 g of antimony pentachloride, were charged. The reaction was raised to 120.degree. C. while hydrogen fluoride was fed in at a rate of 50 g/hr over a period of 3 hours. Then, hydrogen fluoride was supplied at a rate of 50 g/hr over a period of 3 hours. The reaction was conducted at this state for 20 hours while keeping the reaction temperature at this level. The reaction products were collected in a trap cooled at -78.degree. C. The composition after removing acidic components from the collected products, was analyzed by gas chromatography and by .sup.19 F-NMR. As the results, it was confirmed that CH.sub.2 ClCF.sub.2 CHCl (R-252ca) having a difluoromethylene group was formed. The results are shown in Table 5-1.
TABLE 5-1______________________________________Fluorination of R-250aaConversion of R-250aa 46%______________________________________Selectivity for R-252ca 12%Selectivity for R-251ba 84%Selectivity for others 4%______________________________________
EXAMPLE 5-2
The reaction was conducted in the same manner as in Example 5-1 except that 500 g of 1,1,2,2-tetrachloropropane (R-250ab) was used in place of 1,2,2,3-tetrachloropropane (R-250aa), 50 g of tantalum pentafluoride was used in place of antimony pentachloride and the reaction temperature was changed to 130.degree. C. As the results, it was confirmed that tetrahydrotetrahalogenopropanes having at least 2 fluorine atoms such as CHF.sub.2 CClFCH.sub.3 (R-253bb) and CHClFCClFCH.sub.3 (R-252bb) were formed in addition to tetrahydrotetrahalogenopropanes having a difluoromethylene group such as CHF.sub.2 CF.sub.2 CH.sub.3 (R-254cb), CHClFCF.sub.2 CH.sub.3 (R-253cb) and CHCl.sub.2 CF.sub.2 CH.sub.3 (R-252cb). The results are shown in Table 5-2.
TABLE 5-2______________________________________Fluorination of R-250abConversion of R-250ab 58%______________________________________Selectivity for R-254cb 4%Selectivity for R-253 22%(for R-253cb) (12%)Selectivity for R-252 39%(for R-252cb) (10%)Selectivity for R-251 33%Selectivity for others 2%______________________________________
EXAMPLE 5-3
The reaction was conducted in the same manner as in Example 5-1 except that 500 g of 1,2,3-trichloro-2-fluoropropane (R-251ba) was used in place of 1,2,2,3-tetrachloropropane (R-250aa), 100 g of niobium pentachloride was used in place of antimony pentachloride and the reaction temperature was changed to 100.degree. C. As the results, it was confirmed that tetrahydrotetrahalogenopropanes having a difluoromethylene group such as CH.sub.2 ClCF.sub.2 CH.sub.2 F (R-253ca) and CH.sub.2 ClCF.sub.2 CH.sub.2 Cl (R-252ca), were formed. The results are shown in Table 5-3.
TABLE 5-3______________________________________Fluorination of R-251baConversion of R-251ba 79%______________________________________Selectivity for R-253ca 3%Selectivity for R-252ca 86%Selectivity for others 11%______________________________________
EXAMPLE 5-4
The reaction was conducted in the same manner as in Example 5-1 except that 500 g of 1,1,2-trichloro-2-fluoropropane (R-251bb) was used in place of 1,2,2,3-tetrachloropropane (R-250aa), and 40 g of tantalum pentachloride was used in place of antimony pentachloride and the reaction temperature was changed to 120.degree. C. As the results, it was confirmed that tetrahydrotetrahalogenopropanes having at least 2 fluorine atoms such as CHF.sub.2 CClFCH.sub.3 (R-253bb) and CHClFCClFCH.sub.3 (R-252bb), were formed in addition to tetrahydrotetrahalogenopropanes having a difluoromethylene group such as CHF.sub.2 CF.sub.2 CH.sub.3 (R-254cb), CHClFCF.sub.2 CH.sub.3 (R-253cb) and CHCl.sub.2 CF.sub.2 CH.sub.3 (R-252bb). The results are shown in Table 5-4.
TABLE 5-4______________________________________Fluorination of R-251bbConversion of R-251bb 73%______________________________________Selectivity for R-254cb 3%Selectivity for R-253 14%(for R-253cb) (8%)Selectivity for R-252 74%(for R-252cb) (37%)Selectivity for others 9%______________________________________
PREPARATION EXAMPLE 1
1,200 g of Cr(NO.sub.3).sub.3.9H.sub.2 O and 100 g of Mg(NO.sub.3).sub.2.6H.sub.2 O were dissolved in 2.5 l of water, and this solution and 2,000 g of 28% ammonium hydroxide aqueous solution were added to 4 l of hot water under stirring to give precipitates of the hydroxides. The precipitates were collected by filtration, washed with pure water, dried and then sintered at 450.degree. C. for 5 hours to give the powder of the oxides. The powder was shaped into a cylindrical tablet having a diameter of 5 mm and a height of 5 mm by a tabletting machine. The catalyst thereby obtained was activated by fluorinating at a temperature of from 250 to 400.degree. C. in a gas stream of hydrogen fluoride/nitrogen mixture before using it in the reaction.
PREPARATION EXAMPLE 2
1,100 g of guaranteed reagent of Al(NO.sub.3).sub.3.9H.sub.2 O, 125 g of Cr(NO.sub.3)3.9H.sub.2 O and 40 g of Mg(NO.sub.3).sub.2.6H.sub.2 O, were dissolved in 2.5 l of water, and this solution and 2,000 g of 28% ammonium hydroxide aqueous solution were added to 4 l of hot water to give precipitates of the hydroxides. The precipitates were collected by filtration, washed with pure water, dried and sintered at 450.degree. C. for 5 hours to give the powder of the oxides. The powder was shaped into a cylindrical tablet having a diameter of 5 mm and a height of 5 mm by a tabletting machine. The catalyst thereby obtained was activated by fluorinating at a temperature of from 250.degree. to 400.degree. C. in a gas stream of hydrogen fluoride/nitrogen mixture before using it in the reaction.
PREPARATION EXAMPLES 3 TO 6
The catalysts were prepared in the same manner as in Preparation Example 2 except that 40 g of Ba(NO.sub.3).sub.2, 50 g of Sr(NO.sub.3).sub.2, 40 g of Ca(NO.sub.3).sub.2.4H.sub.2 O and 60 g of Mn(NO.sub.3).sub.2.4H.sub.2 O were used in place of Mg(NO.sub.3).sub.2.6H.sub.2 O, respectively.
PREPARATION EXAMPLE 7
The catalyst was prepared in the same manner as in
Preparation Example 2 except that 300 g of Fe(NO.sub.3).sub.2.9H.sub.2 O and 900 g of Al(NO.sub.3).sub.3.9H.sub.2 O were used in place of Al(NO.sub.3).sub.3.9H.sub.2 O, Cr(NO.sub.3).sub.3.9H.sub.2 O and Mg(NO.sub.3).sub.2.6H.sub.2 O.
PREPARATION EXAMPLE 8
The catalyst was prepared in the same manner as in Preparation Example 2 except that 600 g of Fe(NO.sub.3).sub.2.9H.sub.2 O and 150 g of Cr(NO.sub.3).sub.3.9H.sub.2 O were used in place of Al(NO.sub.3).sub.3.9H.sub.2 O, Cr(NO.sub.3).sub.3.9H.sub.2 O and Mg(NO.sub.3).sub.2.6H.sub.2 O.
PREPARATION EXAMPLE 9
200 g of AlCl.sub.3 was dissolved in 2 l of water. To this solution, 1,000 g of commercially available .gamma.-alumina was added, and then it was dried to remove moisture. Further, the catalyst thereby obtained was activated by the same activating method as in Preparation Example 1.
PREPARATION EXAMPLE 10
The catalyst was prepared in the same manner as in Preparation Example 9 except that 200 g of CrCl.sub.3.6H.sub.2 O was used in place of AlCl.sub.3. Further, the catalyst thereby obtained was activated by the same activating method as in Preparation Example 1.
PREPARATION EXAMPLE 11
The catalyst was prepared in the same manner as in Preparation Example 9 except that 200 g of MnCl.sub.2.4H.sub.2 O was used in place of AlCl.sub.3. Further, the catalyst thereby obtained was activated by the same activating method as in Preparation Example 1.
PREPARATION EXAMPLE 12
The catalyst was prepared in the same manner as in Preparation Example 9 except that 200 g of NiCl.sub.2.6H.sub.2 O was used in place of AlCl.sub.3. Further, the catalyst thereby obtained was activated by the same activating method as in Preparation Example 1.
PREPARATION EXAMPLE 13
The catalyst was prepared in the same manner as in Preparation Example 9 except that 200 g of CoCl.sub.2.6H.sub.2 O was used in place of AlCl.sub.3. Further, the catalyst thereby obtained was activated by the same activating method as in Preparation Example 1.
PREPARATION EXAMPLE 14
The catalyst was prepared in the same manner as in Preparation Example 9 except that 1,000 g of commercial available granulated activated carbon useful as a support for the catalyst was used in place of .gamma.-alumina. Further, the catalyst thereby obtained was activated by the same activating method as in Preparation Example 1.
EXAMPLE 6-1
An Inconnel 600 U-shaped reaction tube having an inner diameter of 2.54 cm and a length of 100 cm packed with 200 ml of fluorination catalyst prepared in the same manner as in Preparation Example 1, was used as a fluorination reactor. To the reactor kept at a temperature of 350.degree. C., gasified 1,1,1-trichloropentafluoropropane, oxygen and hydrogen fluoride were fed in at a rate of 50 ml/minutes, 2 ml/minutes and 100 ml/minutes, respectively and reacted. The reaction products were collected in a trap cooled at -78.degree. C. The gas composition, after removing acidic components from the collected product, was analyzed by gas chromatography and by .sup.19 F NMR. The results are shown in Table 6-1.
EXAMPLE 6-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6 1 except that the catalyst prepared in Preparation Example 2 was used. The results are shown in Table 6-1.
EXAMPLE 6-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 3 by using Ba(NO.sub.3).sub.2 was used. The results are shown in Table 6-1.
TABLE 6-1______________________________________Example No. 6-1 6-2 6-3______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 82 67 52Selectivity (%)CF.sub.3 CF.sub.2 CCl.sub.2 F 24 32 38CF.sub.3 CF.sub.2 CClF.sub.2 67 61 55Others 9 7 7______________________________________
EXAMPLE 6-4
The fluorination reaction and the analysis reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 4 by using Sr(NO.sub.3).sub.2 was used. The results are shown in Table 6-2.
EXAMPLE 6-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 5 by using Ca(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 6-2.
EXAMPLE 6-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 6 by using Mn(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 6-2.
TABLE 6-2______________________________________Example No. 6-4 6-5 6-6______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 44 50 70Selectivity (%)CF.sub.3 CF.sub.2 CCl.sub.2 F 34 40 29CF.sub.3 CF.sub.2 CClF.sub.2 58 50 64Others 8 10 7______________________________________
EXAMPLE 6-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 7 was used. The results are shown in Table 6-3.
EXAMPLE 6-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 8 was used. The results are shown in Table 6-3.
EXAMPLE 6-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 9 was used. The results are shown in Table 6-3.
TABLE 6-3______________________________________Example No. 6-7 6-8 6-9______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 38 41 37Selectivity (%)CF.sub.3 CF.sub.2 CCl.sub.2 F 44 48 46CF.sub.3 CF.sub.2 CClF.sub.2 47 45 50Others 9 7 4______________________________________
EXAMPLE 6-10
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6 1 except that the catalyst prepared in Preparation Example 10 was used. The results are shown in Table 6-4.
EXAMPLE 6-11
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6 1 except that the catalyst prepared in Preparation Example 11 was used. The results are shown in Table 6-4.
EXAMPLE 6-12
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 12 was used. The results are shown in Table 6-4.
TABLE 6-4______________________________________Example No. 6-10 6-11 6-12______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 38 41 37Selectivity (%)CF.sub.3 CF.sub.2 CCl.sub.2 F 44 48 46CF.sub.3 CF.sub.2 CClF.sub.2 47 45 50Others 9 7 4______________________________________
EXAMPLE 6-13
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 13 was used. The results are shown in Table 6-5.
EXAMPLE 6-14
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that the catalyst prepared in Preparation Example 14 was used. The results are shown in Table 6-5.
TABLE 6-5______________________________________Example No. 6-13 6-14______________________________________Reaction temp. (.degree.C.) 300 300Ratio of HF/starting 3 3material (molar ratio)Contact time (sec) 20 20Conversion (%) 38 41Selectivity (%)CF.sub.3 CF.sub.2 CCl.sub.2 F 44 48CF.sub.3 CF.sub.2 CClF.sub.2 47 45Others 9 7______________________________________
EXAMPLE 6-15
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 2,2-difluoro-hexachloropropane was used. The results are shown in Table 6-6.
EXAMPLE 6-16
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1,1,1,3,3-pentachlorotrifluoropropane was used. The results are shown in Table 6-6.
EXAMPLE 6-17
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1,1,3,3-tetrachlorotetrafluoropropane was used. The results are shown in Table 6-6.
TABLE 6-6______________________________________Example No. 6-15 6-16 6-17______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 68 72 87Selectivity (%)CCl.sub.3 CF.sub.2 CClF.sub.2 17 6CCl.sub.2 FCF.sub.2 CCl.sub.2 F 6 14CCl.sub.3 CF.sub.2 CF.sub.3 8CCl.sub.2 FCF.sub.2 CClF.sub.2 37 24 24CCl.sub.2 FCF.sub.2 CF.sub.3 10 7 15CClF.sub.2 CF.sub.2 CClF.sub.2 23 33 54Others 7 8 7______________________________________
EXAMPLE 6-18
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1,1,1,3-tetrachlorotetrafluoropropane was used. The results are shown in Table 6-7.
EXAMPLE 6-19
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1,1,3-trichloropentafluoropropane was used. The results are shown in Table 6-7.
EXAMPLE 6-20
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1,1,1-trichloropentafluoropropane was used. The results are shown in Table 6-7.
TABLE 6-7______________________________________Example No. 6-18 6-19 6-20______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 84 84 89Selectivity (%)CCl.sub.3 CF.sub.2 CF.sub.3 11CCl.sub.2 FCF.sub.2 CClF.sub.2 19CCl.sub.2 FCF.sub.2 CF.sub.3 13 17 24CClF.sub.2 CF.sub.2 CClF.sub.2 42 62CClF.sub.2 CF.sub.2 CF.sub.3 6 14 67Others 9 7 9______________________________________
EXAMPLE 6-21
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1,3-dichloro-hexafluoropropane was used. The results are shown in Table 6-8.
EXAMPLE 6-22
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1,1-dichloro-hexafluoropropane was used. The results are shown in Table 6-8.
EXAMPLE 6-23
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 6-1 except that 1-chloro-heptafluoropropane was used. The results are shown in Table 6-8.
TABLE 6-8______________________________________Example No. 6-21 6-22 6-23______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 71 75 70Selectivity (%)CClF.sub.2 CF.sub.2 CF.sub.3 81 85CF.sub.3 CF.sub.2 CF.sub.3 8 12 93Others 11 3 7______________________________________
EXAMPLE 7-1
An Inconnel 600 U-shaped reaction tube having an inner diameter of 2.54 cm and a length of 100 cm packed with 200 ml of fluorination catalyst prepared in the same manner as in Preparation Example 1, was used as a fluorination reactor. To the reactor kept at a temperature of 300.degree. C., gasified 1,1,3-trichloro-2,2,3,3-tetrafluoropropane (R-224ca), oxygen and hydrogen fluoride were fed in at a rate of 50 ml/minutes, 2 ml/minutes and 100 ml/minuts, respectively and reacted. The reaction products were collected in a trap at -78.degree. C. The gas composition after removing acidic components from the collected product, was analyzed by gas chromatography and by .sup.19 F-NMR. The results are shown in Table 7-1.
EXAMPLE 7-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 2 was used. The results are shown in Table 7-1.
EXAMPLE 7-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 3 by using Ba(NO.sub.3).sub.2 was used. The results are shown in Table 7-1.
EXAMPLE 7-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 4 by using Sr(NO.sub.3).sub.2 was used. The results are shown in Table 7-1.
TABLE 7-1______________________________________Example No. 7-1 7-2 7-3 7-4______________________________________Reaction temp. (.degree.C.) 300 300 300 300Ratio of HF/starting 3 3 3 3material (molar ratio)Contact time (sec) 20 20 20 20Conversion (%) 80 70 62 58Selectivity (%)CClF.sub.2 CF.sub.2 CHClF 85 70 57 65CF.sub.3 CF.sub.2 CHCl.sub.2 5 24 35 29CF.sub.3 C.sub.2 CHClF 3 1 1 0CClF.sub.2 CF.sub.2 CHF.sub.2 2 3 2 1Others 5 2 5 5______________________________________
EXAMPLE 7-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 5 by using Ca(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 7-2.
EXAMPLE 7-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 6 by using Mn(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 7-2.
EXAMPLE 7-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 7 was used. The results are shown in Table 7-2.
EXAMPLE 7-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 8 was used. The results are shown in Table 7-2.
TABLE 7-2______________________________________Example No. 7-5 7-6 7-7 7-8______________________________________Reaction temp. (.degree.C.) 300 300 300 300Ratio of HF/starting 3 3 3 3material (molar ratio)Contact time (sec) 20 20 20 20Conversion (%) 57 72 51 54Selectivity (%)CClF.sub.2 CF.sub.2 CHClF 61 71 68 70CF.sub.3 CF.sub.2 CHCl.sub.2 34 21 27 23CF.sub.3 CF.sub.2 CHClF 0 2 1 1CClF.sub.2 CF.sub.2 CHF.sub.2 1 3 2 2Others 4 3 2 4______________________________________
EXAMPLE 7-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 9 was used. The results are shown in Table 7-3.
EXAMPLE 7-10
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 10 was used. The results are shown in Table 7-3.
EXAMPLE 7-11
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 11 was used. The results are shown in Table 7-3.
EXAMPLE 7-12
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 12 was used. The results are shown in Table 7-3.
TABLE 7-3______________________________________Example No. 7-9 7-10 7-11 7-12______________________________________Reaction temp. (.degree.C.) 300 300 300 300Ratio of HF/starting 3 3 3 3material (molar ratio)Contact time (sec) 20 20 20 20Conversion (%) 50 47 50 53Selectivity (%)CClF.sub.2 CF.sub.2 CHClF 67 63 63 60CF.sub.3 CF.sub.2 CHCl.sub.2 21 29 26 34CF.sub.3 CF.sub.2 CHClF 2 1 2 1CClF.sub.2 CF.sub.2 CHF.sub.2 3 1 3 3Others 7 6 6 2______________________________________
EXAMPLE 7-13
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 13 was used. The results are shown in Table 7-4.
EXAMPLE 7-14
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that the catalyst prepared in Preparation Example 14 was used. The results are shown in Table 7-4.
TABLE 7-4______________________________________Example No. 7-13 7-14______________________________________Reaction temp. (.degree.C.) 300 300Ratio of HF/starting 3 3material (molar ratio)Contact time (sec) 20 20Conversion (%) 41 46Selectivity (%)CClF.sub.2 CF.sub.2 CHClF 66 62CF.sub.3 CF.sub.2 CHCl.sub.2 30 28CF.sub.3 CF.sub.2 CHClF 0 1CClF.sub.2 CF.sub.2 CHF.sub.2 1 1Others 3 8______________________________________
EXAMPLE 7-15
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1,1,3,3-pentachloro-2,2-difluoropropane was used. The results are shown in Table 7-5.
EXAMPLE 7-16
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1,3,3-tetrachloro-1,2,2-trifluoropropane was used. The results are shown in Table 7-5.
EXAMPLE 7-17
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1,1,3-tetrachloro-2,2,3-trifluoropropane was used. The results are shown in Table 7-5.
EXAMPLE 7-18
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1,3-trichloro-2,2,3,3-tetrafluoropropane was used. The results are shown in Table 7-5.
EXAMPLE 7-19
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1,3-trichloro-1,2,2,3-tetrafluoropropane was used. The results are shown in Table 7-5.
TABLE 7-5______________________________________Example No. 7-15 7-16 7-17 7-18 7-19______________________________________Reaction temp. (.degree.C.) 300 300 300 300 300Ratio of HF/starting 3 3 3 3 3material (molarratio)Contact time (sec) 20 20 20 20 20Conversion (%) 74 73 79 75 80Selectivity (%)CCl.sub.2 FCF.sub.2 CHClF 6 9 10 -- --CClF.sub.2 CF.sub.2 CHCl.sub.2 24 24 -- -- --CClF.sub.2 CF.sub.2 CHClF 53 50 54 68 85CF.sub.3 CF.sub.2 CHCl.sub.2 5 7 -- -- 5CCl.sub.2 FCF.sub.2 CHF.sub.2 -- -- 7 -- --CClF.sub.2 CF.sub.2 CHF.sub.2 8 6 20 12 2CF.sub.3 CF.sub.2 CHClF 2 1 4 10 3Others 2 3 5 5 5______________________________________
EXAMPLE 7-20
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1,1-trichloro-2,2,3,3-tetrafluoropropane was used. The results are shown in Table 7-6.
EXAMPLE 7-21
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1-dichloro-2,2,3,3,3-pentafluoropropane was used. The results are shown in Table 7-6.
EXAMPLE 7-22
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,3-dichloro-1,1,2,2,3-pentafluoropropane was used. The results are shown in Table 7-6.
EXAMPLE 7-23
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1,1-dichloro-1,2,2,3,3-pentafluoropropane was used. The results are shown in Table 7-6.
TABLE 7-6______________________________________Example No. 7-20 7-21 7-22 7-23______________________________________Reaction temp. (.degree.C.) 300 300 300 300Ratio of HF/starting 3 3 3 3material (molar ratio)Contact time (sec) 20 20 20 20Conversion (%) 72 83 80 81Selectivity (%)CCl.sub.2 FCF.sub.2 CHF.sub.2 12 -- -- --CClF.sub.2 CF.sub.2 CHF.sub.2 71 -- 57 74CF.sub.3 CF.sub.2 CHClF -- 78 32 --CF.sub.3 CF.sub.2 CHF.sub.2 8 15 7 23Others 9 7 4 3______________________________________
EXAMPLE 7-24
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1-chloro-1,2,2,3,3,3-hexafluoropropane was used. The results are shown in Table 7-7.
EXAMPLE 7-25
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 7-1 except that 1-chloro-1,1,2,2,3,3-hexafluoropropane was used. The results are shown in Table 7-7.
TABLE 7-7______________________________________Example No. 7-24 7-25______________________________________Reaction temp. (.degree.C.) 300 300Ratio of HF/starting 3 3material (molar ratio)Contact time (sec) 20 20Conversion (%) 83 77Selectivity (%)CF.sub.3 CF.sub.2 CHF.sub.2 88 86Others 12 14______________________________________
EXAMPLE 8-1
An Inconnel 600 U-shaped reaction tube having an inner diameter of 2.54 cm and a length of 100 cm packed with 200 ml of fluorination catalyst prepared in the same manner as in Preparation Example 1, was used as a fluorination reactor. To the reactor kept at a temperature of 350.degree. C., gasified 1,3-dichloro-1,1,2,2-tetrafluoropropane, oxygen and hydrogen fluoride were fed in at a rate of 50 ml/minutes, 2 ml/minutes and 100 ml/minutes, respectively and reacted. The reaction products were collected in a trap cooled at -78.degree. C. The gas composition, after removing acidic components from the collected product, was analyzed by gas chromatography or and .sup.19 F-NMR. The results are shown in Table 8-1.
EXAMPLE 8-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 2 was used. The results are shown in Table 8-1.
EXAMPLE 8-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 3 by using Ba(NO.sub.3).sub.2 was used. The results are shown in Table 8-1.
TABLE 8-1______________________________________Example No. 8-1 8-2 8-3______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 85 72 64Selectivity (%)CClF.sub.2 CF.sub.2 CH.sub.2 F 70 55 60CF.sub.3 CF.sub.2 CH.sub.2 Cl 23 47 33Others 7 8 7______________________________________
EXAMPLE 8-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 4 by using Sr(NO.sub.3).sub.2 was used. The results are shown in Table 8-2.
EXAMPLE 8-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 5 by using Ca(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 8-2.
EXAMPLE 8-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 6 by using Mn(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 8-2.
TABLE 8-2______________________________________Example No. 8-4 8-5 8-6______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 61 63 76Selectivity (%)CClF.sub.2 CF.sub.2 CH.sub.2 F 57 53 58CF.sub.3 CF.sub.2 CH.sub.2 Cl 36 41 36Others 7 6 6______________________________________
EXAMPLE 8-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 7 was used. The results are shown in Table 8-3.
EXAMPLE 8-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 8 was used. The results are shown in Table 8-3.
EXAMPLE 8-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 9 was used. The results are shown in Table 8-3.
TABLE 8-3______________________________________Example No. 8-7 8-8 8-9______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 38 42 40Selectivity (%)CClF.sub.2 CF.sub.2 CH.sub.2 F 45 52 44CF.sub.3 CF.sub.2 CH.sub.2 Cl 49 40 48Others 6 8 8______________________________________
EXAMPLE 8-10
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 10 was used. The results are shown in Table 8-4.
EXAMPLE 8-11
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 11 was used. The results are shown in Table 8-4.
EXAMPLE 8-12
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 12 was used. The results are shown in Table 8-4.
TABLE 8-4______________________________________Example No. 8-10 8-11 8-12______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 67 41 42Selectivity (%)CClF.sub.2 CF.sub.2 CH.sub.2 F 50 46 54CF.sub.3 CF.sub.2 CH.sub.2 Cl 43 46 41Others 7 8 5______________________________________
EXAMPLE 8-13
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 13 was used. The results are shown in Table 8-5.
EXAMPLE 8-14
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that the catalyst prepared in Preparation Example 14 was used. The results are shown in Table 8-5.
TABLE 8-5______________________________________Example No. 8-13 8-14______________________________________Reaction temp. (.degree.C.) 300 300Ratio of HF/starting 3 3material (molar ratio)Contact time (sec) 20 20Conversion (%) 62 60Selectivity (%)CClF.sub.2 CF.sub.2 CH.sub.2 F 48 47CF.sub.3 CF.sub.2 CH.sub.2 Cl 44 45Others 8 8______________________________________
EXAMPLE 8-15
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1,3,3-tetrachloro-2,2-difluoropropane was used. The results are shown in Table 8-6.
EXAMPLE 8-16
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1,1,3-tetrachloro-2,2-difluoropropane was used. The results are shown in Table 8-6.
EXAMPLE 8-17
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1,3-trichloro-2,2,3-trifluoropropane was used. The results are shown in Table 8-6.
TABLE 8-6______________________________________Example No. 8-15 8-16 8-17______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 74 70 81Selectivity (%)CClF.sub.2 CF.sub.2 CH.sub.2 F 50 46 54CF.sub.3 CF.sub.2 CH.sub.2 Cl 43 46 41Others 7 8 5______________________________________
EXAMPLE 8-18
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1,3-trichloro-1,2,2-trifluoropropane was used. The results are shown in Table 8-7.
EXAMPLE 8-19
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1,1-trichloro-2,2,3-trifluoropropane was used. The results are shown in Table 8-7.
EXAMPLE 8-20
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1-dichloro-1,2,2,3-tetrafluoropropane was used. The results are shown in Table 8-7.
TABLE 8-7______________________________________Example No. 8-18 8-19 8-20______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 77 83 76Selectivity (%)CCl.sub.2 FCF.sub.2 CH.sub.2 F 10 31CClF.sub.2 CF.sub.2 CH.sub.2 Cl 58CHClFCF.sub.2 CHF.sub.2 72CClF.sub.2 CF.sub.2 CH.sub.2 F 20 64CF.sub.3 CF.sub.2 CH.sub.2 Cl 4CHF.sub.2 CF.sub.2 CHF.sub.2 1 20Others 8 4 8______________________________________
EXAMPLE 8-21
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1-dichloro-2,2,3,3-tetrafluoropropane was used. The results are shown in Table 8-8.
EXAMPLE 8-22
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,3-dichloro-1,1,2,2-tetrafluoropropane was used. The results are shown in Table 8-8.
EXAMPLE 8-23
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1,1-dichloro-1,2,2,3-tetrafluoropropane was used. The results are shown in Table 8-8.
TABLE 8-8______________________________________Example No. 8-21 8-22 8-23______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 64 69 72Selectivity (%)CHClFCF.sub.2 CHF.sub.2 68CClF.sub.2 CF.sub.3 CH.sub.2 F 70 81CF.sub.3 CF.sub.2 CH.sub.2 Cl 18CHF.sub.2 CF.sub.2 CHF.sub.2 28CF.sub.3 CF.sub.2 CH.sub.2 F 5 12Others 4 7 7______________________________________
EXAMPLE 8-24
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 3-chloro-1,1,2,2,3-pentafluoropropane was used. The results are shown in Table 8-9.
EXAMPLE 8-25
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 3-chloro-1,1,1,1,2,2-pentafluoropropane was used. The results are shown in Table 8-9.
EXAMPLE 8-26
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 8-1 except that 1-chloro-1,1,2,2,3-pentafluoropropane was used. The results are shown in Table 8-9.
TABLE 8-9______________________________________Example No. 8-24 8-25 8-26______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 63 60 64Selectivity (%)CHF.sub.2 CF.sub.2 CHF.sub.2 90CF.sub.3 CF.sub.2 CH.sub.2 F 94 92Others 10 6 8______________________________________
EXAMPLE 9-1
An Inconnel 600 U-shaped reaction tube having an inner diameter of 2.54 cm and a length of 100 cm packed with 200 ml of fluorination catalyst prepared in the same manner as in Preparation Example 1, was used as a fluorination reactor. To the reactor kept at a temperature of 350.degree. C., gasified 1,3-dichloro-1,1,2,2-tetrafluoropropane, oxygen and hydrogen fluoride were fed in at a rate of 50 ml/minutes, 2 ml/minutes and 100 ml/minutes, respectively and reacted. The reaction products were collected in a trap cooled at -78.degree. C. The gas composition, after removing acidic components from the collected product, was analyzed by gas chromatography and by 19F-NMR. The results are shown in Table 9-1.
EXAMPLE 9-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 2 was used. The results are shown in Table 9-1.
EXAMPLE 9-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 3 by using Ba(NO.sub.3).sub.2 was used. The results are shown in Table 9-1.
TABLE 9-1______________________________________Example No. 9-1 9-2 9-3______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 83 70 61Selectivity (%)CHClFCF.sub.2 CH.sub.2 F 55 67 70CHF.sub.2 CF.sub.2 CH.sub.2 F 41 27 23Others 4 6 7______________________________________
EXAMPLE 9-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 4 by using Sr(NO.sub.3).sub.2 was used. The results are shown in Table 9-2.
EXAMPLE 9-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 5 by using Ca(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 9-2.
EXAMPLE 9-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 6 by using Mn(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 9-2.
TABLE 9-2______________________________________Example No. 9-4 9-5 9-6______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 63 55 72Selectivity (%)CHClFCF.sub.2 CH.sub.2 F 66 71 59CHF.sub.2 CF.sub.2 CH.sub.2 F 30 22 35Others 4 7 6______________________________________
EXAMPLE 9-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 7 was used. The results are shown in Table 9-3.
EXAMPLE 9-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 8 was used. The results are shown in Table 9-3.
EXAMPLE 9-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 9 was used. The results are shown in Table 9-3.
TABLE 9-3______________________________________Example No. 9-7 9-8 9-9______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 42 44 40Selectivity (%)CHClFCF.sub.2 CH.sub.2 F 73 68 76CHF.sub.2 CF.sub.2 CH.sub.2 F 20 25 18Others 7 7 6______________________________________
EXAMPLE 9-10
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 10 was used. The results are shown in Table 9-4.
EXAMPLE 9-11
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 11 was used. The results are shown in Table 9-4.
EXAMPLE 9-12
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 12 was used. The results are shown in Table 9-4.
TABLE 9-4______________________________________Example No. 9-10 9-11 9-12______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 63 42 48Selectivity (%)CHClFCF.sub.2 CH.sub.2 F 65 72 74CHF.sub.2 CF.sub.2 CH.sub.2 F 30 21 21Others 5 7 5______________________________________
EXAMPLE 9-13
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 13 was used. The results are shown in Table 9-5.
EXAMPLE 9-14
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that the catalyst prepared in Preparation Example 14 was used. The results are shown in Table 9-5.
TABLE 9-5______________________________________Example No. 9-13 9-14______________________________________Reaction temp. (.degree.C.) 300 300Ratio of HF/starting 3 3material (molar ratio)Contact time (sec) 20 20Conversion (%) 63 42Selectivity (%)CHCllFCF.sub.2 CH.sub.2 F 65 72CHF.sub.2 CF.sub.2 CH.sub.2 F 30 21Others 5 7______________________________________
EXAMPLE 9-15
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 1,1,3-trichloro-2,2-difluoropropane was used. The results are shown in Table 9-6.
EXAMPLE 9-16
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 1,1,1-trichloro-2,2-difluoropropane was used. The results are shown in Table 9-6.
EXAMPLE 9-17
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 1,3-dichloro-1,2,2-trifluoropropane was used. The results are shown in Table 9-6.
EXAMPLE 9-18
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 1,1-dichloro-2,2,3-trifluoropropane was used. The results are shown in Table 9-6.
TABLE 9-6______________________________________Example No. 9-15 9-16 9-17 9-18______________________________________Reaction temp. (.degree.C.) 300 300 300 300Ratio of HF/starting 3 3 3 3material (molar ratio)Contact time (sec) 20 20 20 20Conversion (%) 84 77 80 68Selectivity (%)CHClFCF.sub.2 CH.sub.2 Cl 19CHCl.sub.2 CF.sub.2 CH.sub.2 F 22CH.sub.3 CF.sub.2 CCl.sub.2 F 21CHClFCF.sub.2 CH.sub.2 F 43 53 55CHF.sub.2 CF.sub.2 CH.sub.2 Cl 9 29CH.sub.3 CF.sub.2 CClF.sub.2 60CF.sub.3 CF.sub.2 CH.sub.3 12 10 41Others 7 7 8 9______________________________________
EXAMPLE 9-19
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 1,1-dichloro-1,2,2-trifluoropropane was used. The results are shown in Table 9-7.
EXAMPLE 9-20
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 3-chloro-1,1,2,2-tetrafluoropropane was used. The results are shown in Table 9-7.
EXAMPLE 9-21
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 1-chloro-1,2,2,3-tetrafluoropropane was used. The results are shown in Table 9-7.
EXAMPLE 9-22
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 9-1 except that 1-chloro-1,1,2,2-tetrafluoropropane was used. The results are shown in Table 9-7.
TABLE 9-7______________________________________Example No. 9-19 9-20 9-21 9-22______________________________________Reaction temp. (.degree.C.) 300 300 300 300Ratio of HF/starting 3 3 3 3material (molar ratio)Contact time (sec) 20 20 20 20Conversion (%) 62 53 61 68Selectivity (%)CHClFCF.sub.2 CH.sub.2 F 87CF.sub.3 CF.sub.2 CH.sub.3 92CHF.sub.2 CF.sub.2 CH.sub.2 F 7 93 93Others 6 7 7 8______________________________________
EXAMPLE 10-1
An Inconnel 600 U-shaped reaction tube having an inner diameter of 2.54 cm and a length of 100 cm packed with 200 ml of fluorination catalyst prepared in the same manner as in Preparation Example 1, was used as a fluorination reactor. To the reactor kept at a temperature of 350.degree. C., gasified 1,3-dichloro-1,1,2,2-tetrafluoropropane, oxygen and hydrogen fluoride were fed in at a rate of 50 ml/minutes, 2 ml/minutes and 100 ml/minutes, respectively and reacted. The reaction products were collected in a trap cooled at -78.degree. C. The gas composition, after removing acidic components from the collected product, was analyzed by gas chromatography or by .sup.19 F-NMR. The results are shown in Table 10-1.
EXAMPLE 10-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 2 was used. The results are shown in Table 10-1.
EXAMPLE 10-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 3 by using Ba(NO.sub.3).sub.2 was used. The results are shown in Table 10-1.
TABLE 10-1______________________________________Example No. 10-1 10-2 10-3______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 80 74 68Selectivity (%)CHClFCF.sub.2 CH.sub.3 82 80 85CHF.sub.2 CF.sub.2 CH.sub.3 14 13 11Others 6 7 4______________________________________
EXAMPLE 10-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 4 by using Sr(NO.sub.3).sub.2 was used. The results are shown in Table 10-2.
EXAMPLE 10-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 5 by using Ca(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 10-2.
EXAMPLE 10-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 6 by using Mn(NO.sub.3).sub.2.4H.sub.2 O was used. The results are shown in Table 10-2.
TABLE 10-2______________________________________Example No. 10-4 10-5 10-6______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 60 63 76Selectivity (%)CHClFCF.sub.2 CH.sub.3 88 84 86CHF.sub.2 CF.sub.2 CH.sub.3 7 8 9Others 5 8 5______________________________________
EXAMPLE 10-7
The fluorination reaction and the anal reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 7 was used. The results are shown in Table 10-3.
EXAMPLE 10-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 8 was used. The results are shown in Table 10-3.
EXAMPLE 10-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 9 was used. The results are shown in Table 10-3.
TABLE 10-3______________________________________Example No. 10-7 10-8 10-9______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 35 40 36Selectivity (%)CHClFCF.sub.2 CH.sub.3 90 93 92CHF.sub.2 CF.sub.2 CH.sub.3 3 2Others 7 5 8______________________________________
EXAMPLE 10-10
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 10 was used. The results are shown in Table 10-4.
EXAMPLE 10-11
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 11 was used. The results are shown in Table 10-4.
EXAMPLE 10-12
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 12 was used. The results are shown in Table 10-4.
TABLE 10-5______________________________________Example No. 10-13 10-14______________________________________Reaction temp. (.degree.C.) 300 300Ratio of HF/starting 3 3material (molar ratio)Contact time (sec) 20 20Conversion (%) 65 61Selectivity (%)CHClFCF.sub.2 CH.sub.3 90 93CHF.sub.2 CF.sub.2 CH.sub.3 2Others 8 7______________________________________
EXAMPLE 10-15
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that 1,3-dichloro-2,2-difluoropropane was used. The results are shown in Table 10-6.
EXAMPLE 10-16
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that 1,1-dichloro-2,2-difluoropropane was used. The results are shown in Table 10-6.
EXAMPLE 10-17
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that 1-chloro-2,2,3-trifluoropropane was used. The results are shown in Table 10-6.
EXAMPLE 10-18
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that 1-chloro-1,2,2-trifluoropropane 5 was used. The results are shown in Table 10-6.
TABLE 10-6______________________________________Example No. 10-15 10-16 10-17 10-18______________________________________Reaction temp. (.degree.C.) 300 300 300 300Ratio of HF/starting 3 3 3 3material (molar ratio)Contact time (sec) 20 20 20 20Conversion (%) 77 53 64 60Selectivity (%)CH.sub.2 FCF.sub.2 CH.sub.2 Cl 58CH.sub.3 CF.sub.2 CHClF 80CH.sub.2 FCF.sub.2 CH.sub.2 F 34 97CH.sub.3 CF.sub.2 CHF.sub.2 14 91Others 8 6 3 9______________________________________
EXAMPLE 11-1
Into a 1 l Hastelloy C autoclave, 50 g of 1,1,1,3,3,3-hexachloro-2,2-difluoropropane (R-212ca), 90 g of spray-dried potassium fluoride, 9 g of tetrabutylphosphonium bromide and 480 g of sulfolane, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the reaction products were analyzed by gas chromatography and by NMR. As the results, it was confirmed that 1,1,1,3,3,3-pentachloro-2,2,3-trifluoropropane (R-213ca), 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca), 1,1,1,3-tetrachloro-2,2,2,3-tetrafluoropropane (R-214cb), 1,1,3-trichloro-1,2,2,3,3-pentafluoropropane (R-215ca), 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb), 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216ca), 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-216cb), 1-chloro-1,1,2,2,2,3,3,3-heptafluoropropane (R-217ca) and octafluoropropane (R-218), were formed. The results are shown in Table 11-1.
TABLE 11-1______________________________________Conversion of R-212ca 99%______________________________________Selectivity for R-214ca 4%Selectivity for R-215ca 13%Selectivity for R-216ca 24%Selectivity for R-216cb 20%Selectivity for R-217ca 14%______________________________________
EXAMPLE 11-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-1 except that 1,1,1,3,3-pentachloro-2,2,3-trifluoropropane (R-213ca) was used as the starting material. The results are shown in Table 11-2.
TABLE 11-2______________________________________Conversion of R-213ca 99%______________________________________Selectivity for R-214ca 2%Selectivity for R-215ca 6%Selectivity for R-216ca 24%Selectivity for R-216cb 20%Selectivity for R-217ca 27%______________________________________
EXAMPLE 11-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-1 except that as the starting material, 50 g of 1,1,3,3-tetrachloro-1,2,2,3-tetrafluoropropane (R-214ca), 70 g of spray-dried potassium fluoride and 7 g of tetrabutylsulphonium bromide, were used. The results are shown in Table 11-3.
TABLE 11-3______________________________________Conversion of R-214ca 99%______________________________________Selectivity for R-215ca 5%Selectivity for R-216ca 14%Selectivity for R-216cb 8%Selectivity for R-217ca 43%Selectivity for R-218ca 26%______________________________________
EXAMPLE 11-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-1 except that as the starting material, 1,1,1,3-tetrachloro-2,2,3,3-tetrafluoropropane (R-214cb), was used. The results are shown in Table 11-4.
TABLE 11-4______________________________________Conversion of R-214cb 99%______________________________________Selectivity for R-215cb 7%Selectivity for R-216ca 13%Selectivity for R-216cb 9%Selectivity for R-217ca 35%Selectivity for R-218ca 29%______________________________________
EXAMPLE 11-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-1 except that as the starting materials, 50 g of 1,1,3 trichloro-1,2,2,3,3-pentafluoropropane (R-215ca), 55 g of spray-dried potassium fluoride and 6 g of tetrabutylphosphonium bromide, was used. The results are shown in Table 11-5.
TABLE 10-4______________________________________Example No. 10-10 10-11 10-12______________________________________Reaction temp. (.degree.C.) 300 300 300Ratio of HF/starting 3 3 3material (molar ratio)Contact time (sec) 20 20 20Conversion (%) 71 38 38Selectivity (%)CHClFCF.sub.2 CH.sub.3 83 91 92CHF.sub.2 CF.sub.2 CH.sub.3 9Others 8 9 8______________________________________
EXAMPLE 10-13
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 13 was used. The results are shown in Table 10-5.
EXAMPLE 10-14
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 10-1 except that the catalyst prepared in Preparation Example 14 was used. The results are shown in Table 10-5.
TABLE 11-5______________________________________Conversion of R-215ca 99%______________________________________Selectivity for R-216ca 11%Selectivity for R-216cb 9%Selectivity for R-217ca 35%Selectivity for R-218ca 41%______________________________________
EXAMPLE 11-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-5 except that as the starting material, 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb), was used. The results are shown in Table 11-6.
TABLE 11-6______________________________________Conversion of R-215cb 99%______________________________________Selectivity for R-216cb 17%Selectivity for R-217ca 40%Selectivity for R-218ca 37%______________________________________
EXAMPLE 11-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-1 except that as the starting materials, 50 g of 1,3-dichloro-1,1,2,2,3,3-hexafluoropropane (R-216cb), 40 g of spray-dried potassium fluoride and 4 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 11-7.
TABLE 11-7______________________________________Conversion of R-216ca 92%______________________________________Selectivity for R-217ca 35%Selectivity for R-218ca 61%______________________________________
EXAMPLE 11-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-7 except that as the starting material, 1,1-dichloro-1,2,2,3,3,3-hexafluoropropane (R-216cb), was used. The results are shown in Table 11-8.
TABLE 11-8______________________________________Conversion of R-216cb 94%______________________________________Selectivity for R-217ca 33%Selectivity for R-218ca 63%______________________________________
EXAMPLE 11-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 11-1 except that as the starting materials, 50 g of 1-chloro-1,1,2,2,3,3,3-heptafluoropropane (R-217ca), 55 g of cesium fluoride and 6 g of tetrabutylammonium bromide, were used and the reaction temperature was changed to 150.degree. C. The results are shown in Table 11-9.
TABLE 11-9______________________________________Conversion of R-217ca 91%______________________________________Selectivity for R-218ca 96%______________________________________
EXAMPLE 11-10
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb) and 60 g of antimony trifluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration; The crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 11-10.
TABLE 11-10______________________________________Conversion of R-215cb 22%______________________________________Selectivity for R-216cb 70%Selectivity for R-217ca 19%Selectivity for R-218ca 7%______________________________________
EXAMPLE 11-11
Into a 200 ml Hastelloy C autoclave, as the starting material, 150 g of 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb), 60 g of antimony trifluoride and 3 g of antimony trichloride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration. The crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 11-11.
TABLE 11-11______________________________________Conversion of R-215cb 30%______________________________________Selectivity for R-216cb 65%Selectivity for R-217ca 29%Selectivity for R-218ca 4%______________________________________
EXAMPLE 11-12
Into a 200 ml Hastelloy C autoclave, as the starting material, 150 g of 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb), 60 g of antimony trifluoride and 3 g of antimony pentafluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration. The crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 11-12.
TABLE 11-12______________________________________Conversion of R-215cb 31%______________________________________Selectivity for R-216cb 65%Selectivity for R-217ca 25%Selectivity for R-218ca 7%______________________________________
EXAMPLE 11-13
Into a 200 ml Hastelloy C autoclave, 60 g of antimony trifluoride was added, and then 23 g of chlorine gas was introduced to prepare antimony dichloride trifluoride. The thin film of antimony dichloride trifluoride thereby formed was broken, and as the starting material, 150 g of 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb) was charged. The reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 11-13.
TABLE 11-13______________________________________Conversion of R-215cb 34%______________________________________Selectivity for R-216cb 65%Selectivity for R-217ca 26%Selectivity for R-218ca 5%______________________________________
EXAMPLE 11-14
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3,3,3-pentafluoropropane (R-215cb) and 80 g of antimony pentafluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 11-14.
TABLE 11-14______________________________________Conversion of R-215cb 38%______________________________________Selectivity for R-216cb 67%Selectivity for R-217ca 22%Selectivity for R-218ca 6%______________________________________
EXAMPLE 12-1
Into a 1 l Hastelloy C autoclave, as the starting materials, 50 g of 1,1,1,3,3-pentachloro-2,2-difluoropropane (R-222ca), 87 g of spray-dried potassium fluoride, 9 g of tetrabutylsulfonium bromide and 480 g of sulfolane, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration. The reaction products were analyzed by gas chromatography and by NMR. As the results, it was confirmed that 1,1,3,3-tetrachloro-1,2,2-trifluoropropane (R-223ca), 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb), 1,1,3-trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cb), 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R-225ca), 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), 1 chloro-1,2,2,3,3,3-hexafluoropropane [R-226ca), 1-chloro-1,1,2,2,3,3-hexafluoropropane (R-226cb) and 1,1,1,2,2,3,3-heptafluoropropane (R-227ca), were formed. The results are shown in Table 12-1.
TABLE 12-1______________________________________Conversion of R-222ca 99%______________________________________Selectivity for R-224ca 6%Selectivity for R-225cb 25%Selectivity for R-226ca 13%Selectivity for R-226cb 7%Selectivity for R-227ca 2%______________________________________
EXAMPLE 12-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-1 except that as the starting material, 1,1,3,3-tetrachloro-1,2,2,-trifluoropropane (R-223ca) was used. The results are shown in Table 12-2.
TABLE 12-2______________________________________Conversion of R-223ca 99%______________________________________Selectivity for R-224ca 3%Selectivity for R-225cb 30%Selectivity for R-226ca 15%Selectivity for R-226cb 10%Selectivity for R-227ca 5%______________________________________
EXAMPLE 12-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-1 except that as the starting material, 1,1,1,3-tetrachloro-2,2,3-trifluoropropane (R-223cb) was used. The results are shown in Table 12-3.
TABLE 12-3______________________________________Conversion of R-223cb 99%______________________________________Selectivity for R-225cb 25%Selectivity for R-226ca 23%Selectivity for R-226cb 14%Selectivity for R-227ca 8%______________________________________
EXAMPLE 12-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-1 except that as the starting materials, 50 g of 1,1,3-trichloro-2,2,3,3-tetrafluoropropane (R-224ca), 60 g of spray-dried potassium fluoride and 6 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 12-4.
TABLE 12-4______________________________________Conversion of R-224ca 99%______________________________________Selectivity for R-225ca 8%Selectivity for R-225cb 11%Selectivity for R-226ca 26%Selectivity for R-226cb 17%Selectivity for R-227ca 20%______________________________________
EXAMPLE 12-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-4 except that as the starting material, 1,1,3-trichloro-1,2,2,3-tetrafluoropropane (R-224cb), was used. The results are shown in Table 12-5.
TABLE 12-5______________________________________Conversion of R-224cb 99%______________________________________Selectivity for R-225cb 14%Selectivity for R-225cc 12%Selectivity for R-226ca 21%Selectivity for R-226cb 22%Selectivity for R-227ca 21%______________________________________
EXAMPLE 12-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-4 except that as the starting material, 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), was used. The results are shown in Table 12-6.
TABLE 12-6______________________________________Conversion of R-224cc 98%______________________________________Selectivity for R-225cc 23%Selectivity for R-226cb 37%Selectivity for R-227ca 30%______________________________________
EXAMPLE 12-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-1 except that as the starting materials, 50 g of 1,1-dichloro-2,2,3,3,3-pentafluoropropane (R-225ca), 43 g of spray-dried potassium fluoride and 5 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 12-7.
TABLE 12-7______________________________________Conversion of R-225ca 94%______________________________________Selectivity for R-226ca 44%Selectivity for R-227ca 42%______________________________________
EXAMPLE 12-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-7 except that as the starting material, 1,3-dichloro-1,1,2,2,3-pentafluoropropane (R-225cb), was used. The results are shown in Table 12-8.
TABLE 12-8______________________________________Conversion of R-225cb 93%______________________________________Selectivity for R-226ca 22%Selectivity for R-226cb 21%Selectivity for R-227ca 39%______________________________________
EXAMPLE 12-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-7 except that as the starting material, 1,1-dichloro-1,2,2,3,3-pentafluoropropane (R-225cc), was used. The results are shown in Table 12-9.
TABLE 12-9______________________________________Conversion of R-225cc 96%______________________________________Selectivity for R-226cb 34%Selectivity for R-227ca 47%______________________________________
EXAMPLE 12-10
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 12-1 except that as the starting materials, 50 g of 1-chloro-1,2,2,3,3,3-hexafluoropropane (R-226ca), 25 g of spary-dried potassium fluoride and 3 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 12-10
TABLE 12-10______________________________________Conversion of R-226ca 89%______________________________________Selectivity for R-227ca 79%______________________________________
EXAMPLE 12-11
The fluorination reaction-and the analysis of the reaction products were conducted in the same manner as in Example 12-1 except that as the starting materials, 50 g of 1-chloro-1,1,2,2,3,3-hexafluoropropane (R-226cb), 65 g of cesium fluoride and 7 g of tetrabutylammonium bromide, were used. The results are shown in Table 12-11.
TABLE 12-11______________________________________Conversion of R-226cb 85%______________________________________Selectivity for R-227ca 80%______________________________________
EXAMPLE 12-12
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc) and 60 g of antimony trifluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 12-12.
TABLE 12-12______________________________________Conversion of R-224cc 20%______________________________________Selectivity for R-225cc 72%Selectivity for R-226cb 18%Selectivity for R-227ca 6%______________________________________
EXAMPLE 12-13
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 60 g of antimony trifluoride and 3 g of antimony trichloride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 12-13.
TABLE 12-13______________________________________Conversion of R-224cc 29%______________________________________Selectivity for R-225cc 63%Selectivity for R-226cb 28%Selectivity for R-227ca 5%______________________________________
EXAMPLE 12-14
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc), 60 g of antimony trifluoride and 3 g of antimony pentachloride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 12-14.
TABLE 12-14______________________________________Conversion of R-224cc 31%______________________________________Selectivity for R-225cc 64%Selectivity for R-226cb 25%Selectivity for R-227ca 6%______________________________________
EXAMPLE 12-15
Into a 200 ml Hastelloy C autoclave, 60 g of antimony trifluoride was added, and then 23 g of chlorine gas was introduced to prepare antimony dichloride trifluoride. The thin film of antimony dichloride trifluoride thereby formed was broken. Then, as the starting material, 150 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc) was charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 12-15.
TABLE 12-15______________________________________Conversion of R-224cc 35%______________________________________Selectivity for R-225cc 63%Selectivity for R-226cb 26%Selectivity for R-227ca 5%______________________________________
EXAMPLE 12-16
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3,3-tetrafluoropropane (R-224cc) and 80 g of antimony pentafluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 12-16.
TABLE 12-16______________________________________Conversion of R-224cc 36%______________________________________Selectivity for R-225cc 68%Selectivity for R-226cb 22%Selectivity for R-227ca 7%______________________________________
EXAMPLE 13-1
Into a 1 l Hastelloy C autoclave, as the starting material, 50 g of 1,1,1,3-tetrachloro-2,2-difluoropropane (R-232cb), 80 g of spray-dried potassium fluoride, 8 g of tetrabutylsulfonium bromide and 480 g of sulfolane, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the reaction products were analyzed by gas chromatography and by NMR. As the results, it was confirmed that 1,1,1-trichloro-2,2,3-trifluoorpropane (R-233cc), 1,1-dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 1,3-dichloro-1,1,2,2-tetrafluoropropane (R-244cc), 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc) and 1,1,1,2,2,3-hexafluoropropane (R-236cb), were formed. The results are shown in Table 13-1.
TABLE 13-1______________________________________Conversion of R-232cb 99%______________________________________Selectivity for R-233cc 10%Selectivity for R-234cc 27%Selectivity for R-234cd 13%Selectivity for R-235cc 14%Selectivity for R-236cb 10%______________________________________
EXAMPLE 13-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-1 except that as the starting material, 1,1,3,3-tetrachloro-2,2-difluoropropane (R-232ca) was used. The results are shown in Table 13-2.
TABLE 13-2______________________________________Conversion of R-232ca 99%______________________________________Selectivity for R-234ca 15%Selectivity for R-234cb 12%Selectivity for R-235ca 35%Selectivity for R-236ca 10%______________________________________
EXAMPLE 13-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-1 except that as the starting materials, 50 g of 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc), 65 g of spray-dried potassium fluoride and 6.5 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 13-3.
TABLE 13-3______________________________________Conversion of R-233cc 99%______________________________________Selectivity for R-234cd 17%Selectivity for R-235cc 30%Selectivity for R-236cb 38%______________________________________
EXAMPLE 13-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-3 except that as the starting material, 1,1,1-trichloro-1,2,2-trifluoropropane (R-233cb), was used. The results are shown in Table 13-4.
TABLE 13-4______________________________________Conversion of R-233cb 99%______________________________________Selectivity for R-234cc 13%Selectivity for R-234cd 11%Selectivity for R-235cb 23%Selectivity for R-235cc 15%Selectivity for R-236cb 20%______________________________________
EXAMPLE 13-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-3 except that as the starting material, 1,1,3-trichloro-2,2,3-trifluoropropane (R-233cb), was used. The results are shown in Table 13-5.
TABLE 13-5______________________________________Conversion of R-233ca 99%______________________________________Selectivity for R-234ca 11%Selectivity for R-234cb 11%Selectivity for R-235ca 35%Selectivity for R-236ca 25%______________________________________
EXAMPLE 13-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-1 except that as the starting materials, 50 g of 1,1-dichloro-1,2,2,3-tetrafluoropropane (R-234cd), 50 g of spray-dried potassium fluoride and 5 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 13-6.
TABLE 13-6______________________________________Conversion of R-234cd 93%______________________________________Selectivity for R-235cc 27%Selectivity for R-236cb 59%______________________________________
EXAMPLE 13-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-6 except that as the starting material, 1,3-dichloro-1,1,2,2-tetrafluoropropane (R-234cc), as used. The results are shown in Table 13-7.
TABLE 13-7______________________________________Conversion of R-234cc 94%______________________________________Selectivity for R-235cb 31%Selectivity for R-235cc 21%Selectivity for R-236cb 30%______________________________________
EXAMPLE 13-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-6 except that as the starting material, 1,1-dichloro-2,2,3,3-tetrafluoropropane (R-234cb), was used. The results are shown in Table 13-8.
TABLE 13-8______________________________________Conversion of R-234cb 91%______________________________________Selectivity for R-235ca 27%Selectivity for R-236ca 51%______________________________________
EXAMPLE 13-9
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-6 except that as the starting material, 1,3-dichloro-1,2,2,3-tetrafluoropropane (R-234ca), was used. The results are shown in Table 13-9.
TABLE 13-9______________________________________Conversion of R-234ca 94%______________________________________Selectivity for R-235ca 31%Selectivity for R-236ca 52%______________________________________
EXAMPLE 13-10
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-1 except that as the starting materials, 50 g of 1-chloro-1,1,2,2,3-pentafluoropropane (R-235cc), 30 g of spray-dried potassium fluoride and 3 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 13-10.
TABLE 13-10______________________________________Conversion of R-235cc 88%______________________________________Selectivity for R-236cb 80%______________________________________
EXAMPLE 13-11
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-10 except that as the starting material, 3-chloro-1,1,1,2,2-pentafluoropropane (R-235cb), was used. The results are shown in Table 13-11.
TABLE 13-11______________________________________Conversion of R-235cb 85%______________________________________Selectivity for R-236cb 76%______________________________________
EXAMPLE 13-12
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 13-1 except that as the starting material, 50 g of 1-chloro-1,2,2,3,3-pentafluoropropane (R-235ca), 78 g of cesium fluoride and 8 g of tetrabutylammonium bromide, were used and the reaction temperature was changed to 150.degree. C. The results are shown in Table 13-12.
TABLE 13-12______________________________________Conversion of R-235ca 89%______________________________________Selectivity for R-236ca 80%______________________________________
EXAMPLE 13-13
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc) and 70 g of antimony trifluoride, were changed, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Them, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 13-13.
TABLE 13-13______________________________________Conversion of R-233cc 25%______________________________________Selectivity for R-234cd 69%Selectivity for R-235cc 18%Selectivity for R-236cb 9%______________________________________
EXAMPLE 13-14
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc), 70 g of antimony trifluoride and 3 g of antimony trichloride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 13-14.
TABLE 13-14______________________________________Conversion of R-233cc 32%______________________________________Selectivity for R-234cd 64%Selectivity for R-235cc 28%Selectivity for R-236cb 6%______________________________________
EXAMPLE 13-15
Into a 200 ml Hastelloy C autoclave, as the starting material, 150 g of 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc), 70 g of antimony trifluoride and 3 g of antimony pentachloride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 13-15.
TABLE 13-15______________________________________Conversion of R-233cc 33%______________________________________Selectivity for R-234cd 66%Selectivity for R-235cc 22%Selectivity for R-236cb 8%______________________________________
EXAMPLE 13-16
Into a 200 ml Hastelloy C autoclave, 70 g of antimony trifluoride was added, and then 25 g of chlorine gas was introduced to prepare antimony dichloride trifluoride. The thin film of antimony dichloride trifluoride thereby formed was broken, and then as the starting material, 150 g of 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc) was charged. The reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 13-16.
TABLE 13-16______________________________________Conversion of R-233cc 36%______________________________________Selectivity for R-234cd 66%Selectivity for R-235cc 24%Selectivity for R-236cb 8%______________________________________
EXAMPLE 13-17
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1,1-trichloro-2,2,3-trifluoropropane (R-233cc) and 100 g of antimony pentafluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 13-17.
TABLE 13-17______________________________________Conversion of R-233cc 39%______________________________________Selectivity for R-234cd 67%Selectivity for R-235cc 24%Selectivity for R-236cb 7%______________________________________
EXAMPLE 14-1
Into a 1 l Hastelloy C autoclave, as the starting materials, 50 g of 1,1,3-trichloro-2,2-difluoropropane (R-242ca), 70 g of spray-dried potassium fluoride, 7 g of tetrabutylphosphonium bromide and 480 g of sulfolane, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the reaction products were analyzed by gas chromatography and by NMR. As the results, it was confirmed that 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 1,1-dichloro-2,2,3-trifluoropropane (R-243cb), 1-chloro-2,2,3,3-tetrafluoropropane (R-244ca), 1-chloro-1,2,2,3-tetrafluoropropane (R-244cb) and 1,1,2,2,3-pentafluoropropane (R-245ca), were formed. The results are shown in Table 14-1.
TABLE 14-1______________________________________Conversion of R-242ca 99%______________________________________Selectivity for R-243ca 11%Selectivity for R-243cb 10%Selectivity for R-244ca 21%Selectivity for R-244cb 24%Selectivity for R-245ca 9%______________________________________
EXAMPLE 14-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 14-1 except that as the starting material, 1,1,1-trichloro-2,2-difluoropropane (R-242cb) was used. The results are shown in Table 14-2.
TABLE 14-2______________________________________Conversion of R-242cb 99%______________________________________Selectivity for R-243cc 8%Selectivity for R-244cc 39%Selectivity for R-245cb 34%______________________________________
EXAMPLE 14-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 14-1 except that as the starting materials, 50 g of 1,3-dichloro-1,2,2-trifluoropropane (R-243ca), 50 g of spray-dried potassium fluoride and 5 g of tetrabutylsulfonium bromide, were used. The results are shown in Table 14-3.
TABLE 14-3______________________________________Conversion of R-243ca 94%______________________________________Selectivity for R-244ca 22%Selectivity for R-244cb 19%Selectivity for R-245ca 36%______________________________________
EXAMPLE 14-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 14-3 except that as the starting material, 1,1-dichloro-2,2,3-trifluoropropane (R-243cb) was used. The results are shown in Table 14-4.
TABLE 14-4______________________________________Conversion of R-243cb 95%______________________________________Selectivity for R-244cb 34%Selectivity for R-245ca 51%______________________________________
EXAMPLE 14-5
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 14-3 except that as the starting material, 1,1-dichloro-1,2,2-trifluoropropane (R-243cc) was used. The results are shown in Table 14-5.
TABLE 14-5______________________________________Conversion of R-243cc 96%______________________________________Selectivity for R-244cc 18%Selectivity for R-245cc 70%______________________________________
EXAMPLE 14-6
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 14-1 except that as the starting materials, 50 g of 1-chloro-2,2,3,3-tetrafluoropropane (R-244ca), 30 g of spray-dried potassium fluoride and 3 g of tetrabutylphosphonium bromide, were used. The results are shown in Table 14-6.
TABLE 14-6______________________________________Conversion of R-244ca 88%______________________________________Selectivity for R-245ca 89%______________________________________
EXAMPLE 14-7
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 14-6 except that as the starting material, 1-chloro-1,2,2,3-tetrafluoropropane (R-244cb), was used. The results are shown in Table 14-7.
TABLE 14-7______________________________________Conversion of R-244cb 89%______________________________________Selectivity for R-245ca 84%______________________________________
EXAMPLE 14-8
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 14-1 except that as the starting materials, 50 g of 1-chloro-1,1,2,2-tetrafluoropropane (R-244cc), 78 g of cesium fluoride and 8 g of tetrabutylammonium bromide, were used and the reaction temperature was changed to 150.degree. C. The results are shown in Table 14-8.
TABLE 14-8______________________________________Conversion of R-244cb 87%______________________________________Selectivity for R-245cc 82%______________________________________
EXAMPLE 14-9
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1-dichloro-1,2,2-trifluoropropane (R-243cc) and 80 g of antimony trifluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 14-9. Table
TABLE 14-9______________________________________Conversion of R-243cc 30%______________________________________Selectivity for R-244cc 75%Selectivity for R-245cb 22%______________________________________
EXAMPLE 14-10
Into a 200 ml Hastelloy C autoclave, as the starting material, 150 g of 1,1-dichloro-1,2,2-trifluoropropane (R-243cc), 80 g of antimony trifluoride and 3 g of antimony trichloride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 14-10.
TABLE 14-10______________________________________Conversion of R-243cc 36%______________________________________Selectivity for R-244cc 70%Selectivity for R-245cb 28%______________________________________
EXAMPLE 14-11
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1-dichloro-1,2,2-trifluoropropane (R-243cc), 80 g of antimony trifluoride and 3 g of antimony pentachloride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 14-11.
TABLE 14-11______________________________________Conversion of R-243cc 37%______________________________________Selectivity for R-244cc 69%Selectivity for R-245cb 29%______________________________________
EXAMPLE 14-12
Into a 200 ml Hastelloy C autoclave, 80 g of antimony trifluoride was added, and then 30 g of chlorine gas was introduced to prepare antimony dichloride trifluoride. The thin film of antimony dichloride trifluoride thereby formed was broken, and then as the starting material, 150 g of 1,1--dichloro-1,2,2-trifluoropropane (R-243cc), was charged. The reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 14-12.
TABLE 14-12______________________________________Conversion of R-243cc 39%______________________________________Selectivity for R-244cc 75%Selectivity for R-245cb 24%______________________________________
EXAMPLE 14-13
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1,1-dichloro-1,2,2-trifluoropropane (R-243cc) and 110 g of antimony pentafluoride, were charged, and the reaction was conducted at a temperature of 150.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 14-13.
TABLE 14-13______________________________________Conversion of R-243cc 41%______________________________________Selectivity for R-244cc 72%Selectivity for R-245cb 26%______________________________________
EXAMPLE 15-1
Into a 1 l Hastelloy C autoclave, as the starting materials, 50 g of 1,3-dichloro-2,2-difluoropropane (R-252ca), 60 g of spray-dried potassium fluoride, 6 g of tetrabutylphosphonium bromide and 480 g of sulfolane, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the reaction products were analyzed by gas chromatography and by NMR. As the results, it was confirmed that 1-chloro-2,2,3-trifluoropropane (R-253ca) and 1,2,2,3-tetrafluoropropane (R-254ca), were formed. The results are shown in Table 15-1.
TABLE 15-1______________________________________Conversion of R-251ca 89%______________________________________Selectivity for R-253ca 31%Selectivity for R-254ca 55%______________________________________
EXAMPLE 15-2
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 15-1 except that as the starting material, 1,1-dichloro-2,2-difluoropropane (R-252cb) was used. The results are shown in Table 15-2.
TABLE 15-2______________________________________Conversion of R-252ca 91%______________________________________Selectivity for R-253ca 31%Selectivity for R-254ca 55%______________________________________
EXAMPLE 15-3
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 15-1 except that as the starting materials, 50 g of 1-chloro-2,2,3-trifluoropropane (R-253ca), 33 g of spray-dried potassium fluoride and 4 g of tetrabutylphosphonium bromide, were used. The results are shown in Table 15-3.
TABLE 15-3______________________________________Conversion of R-253ca 79%______________________________________Selectivity for R-254ca 70%______________________________________
EXAMPLE 15-4
The fluorination reaction and the analysis of the reaction products were conducted in the same manner as in Example 15-1 except that as the starting materials, 50 g of 1-chloro-1,2,2-trifluoropropane (R-253cb), 86 g of cesium fluoride and 9 g of tetrabutylammonium bromide, were used and the reaction temperature was changed to 150.degree. C. The results are shown in Table 15-4.
TABLE 15-4______________________________________Conversion of R-253ca 82%______________________________________Selectivity for R-254ca 75%______________________________________
EXAMPLE 15-5
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1-chloro-1,2,2-trifluoropropane (R-253cb) and 100 g of antimony trifluoride, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours-under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 15-5.
TABLE 15-5______________________________________Conversion of R-253cb 3%______________________________________Selectivity for R-254cb 95%______________________________________
EXAMPLE 15-6
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1-chloro-1,2,2-trifluoropropane (R-253cb), 100 g of antimony trifluoride and 3 g of antimony trichloride, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 15-6.
TABLE 15-6______________________________________Conversion of R-253cb 4%______________________________________Selectivity for R-254cb 98%______________________________________
EXAMPLE 15-7
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1-chloro-1,2,2-trifluoropropane (R-253cb), 100 g of antimony trifluoride and 3 g of antimony pentachloride, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 15-7.
TABLE 15-7______________________________________Conversion of R-253cb 6%______________________________________Selectivity for R-254cb 97%______________________________________
EXAMPLE 15-8
Into a 200 ml Hastelloy C autoclave, 100 g of antimony trifluoride was added, and then 40 g of chlorine gas was introduced to prepare antimony dichloride trifluoride. The thin film of antimony dichloride trichloride thereby formed was broken, and then as the starting material, 150 g of 1-chloro-1,2,2-trifluoropropane (R-253cb) was charged. The reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 15-8.
TABLE 15-8______________________________________Conversion of R-253cb 10%______________________________________Selectivity for R-254cb 98%______________________________________
EXAMPLE 15-9
Into a 200 ml Hastelloy C autoclave, as the starting materials, 150 g of 1-chloro-1,2,2-trifluoropropane (R-253cb) and 110 g of antimony pentafluoride, were charged, and the reaction was conducted at a temperature of 200.degree. C. for 10 hours under vigorously stirring. After cooling, inorganic salts were removed by filtration, and the crude reaction solution was washed with water and dried. Then, the reaction products were analyzed by gas chromatography and by NMR. The results are shown in Table 15-9.
TABLE 15-9______________________________________Conversion of R-253cb 11%______________________________________Selectivity for R-254cb 96%______________________________________
The present invention is effective for the preparation of 2,2-difluoropropanes selectively by reacting chlorine-containing 2,2-halogenopropanes with hydrogen fluoride or a fluorinating agent.

Number	Date	Country
1-22550	Feb 1989	JPX
1-22621	Feb 1989	JPX
1-23741	Feb 1989	JPX
1-23742	Feb 1989	JPX
1-23743	Feb 1989	JPX
1-23744	Feb 1989	JPX
1-23745	Feb 1989	JPX
1-23750	Feb 1989	JPX
1-25653	Feb 1989	JPX
1-25654	Feb 1989	JPX
1-25655	Feb 1989	JPX
1-25656	Feb 1989	JPX
1-25657	Feb 1989	JPX
1-25658	Feb 1989	JPX
1-25681	Feb 1989	JPX

Number	Name	Date
2005707	Daudt et al.	Jun 1935
2490764	Benning et al.	Dec 1949
2578721	McBee et al.	Dec 1951

Number	Date	Country
0317981	May 1989	EPX
938070	Sep 1963	GBX
945017	Dec 1963	GBX
975498	Nov 1964	GBX
999444	Jul 1965	GBX

Process for producing a 2,2-difluoropropane

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