Preparation of Dimer of Fluorine-Containing Halo-Ethane

Home , Dimer (chemistry)

Europaisches Patentamt ||| || 1 1| || || || || || || 1 1| 1 1 1| J European Patent Office A _ _ nr% a n » © Publication number: 0 499 984 B1 Office europeen des brevets

@ Date of filing: 14.02.92

® Priority: 16.02.91 JP 22414/91 © Proprietor: DAI KIN INDUSTRIES, LIMITED Umeda Center Building, @ Date of publication of application: 4-12 Nakazaki-nishi 2-chome, 26.08.92 Bulletin 92/35 Kita-ku Osaka-shi, © Publication of the grant of the patent: Osaka-fu 530 (JP) 09.08.95 Bulletin 95/32 @ Inventor: Ikawa, Tsuneo © Designated Contracting States: 728, Nikaido DE FR GB IT NL Kamakura-shi, Kanagawa-ken (JP) © References cited: Inventor: Morikawa, Yukata EP-A- 0 190 594 5-2-7, Minaminaruse EP-A- 0 376 856 Machida-shi, GB-A- 2 204 313 Tokyo-to (JP) US-A- 2 644 835 Inventor: Ueda, Wataru Sanhowaito M206-21, W. THEILHEIMER 'Synthetische Methoden 2-24-4, Minaminaruse der Organischen Chemie Band 4' 1966 , S. Machida-shi, KARGER, BASEL, CH Tokyo-to (JP)

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid (Art. 99(1) European patent convention). Rank Xerox (UK) Business Services (3. 10/3.09/3.3.3) EP 0 499 984 B1

Description

BACKGROUND OF THE INVENTION

5 Field of the Invention

The present invention relates to a method for preparing a dimer of fluorine-containing ethane.

Description of related art 10 A dimer of fluorine-containing ethane, for example CF3CCI = CCICF3 is useful as a monomer of a polymer. However, a method for preparing the dimer of fluorine-containing ethane in a good selectivity is not known. US-A-2644835 discloses the coupling of non-aromatic compounds having a terminal trihalomethyl 15 radical of the type -CX3 where X is chlorine and/or bromine. The compounds are indicated to contain at least three coon atoms and none of the specific compounds mentioned includes fluorine.

SUMMARY OF THE INVENTION

20 An object of the present invention is to prepare a dimer of fluorine-containing ethane from fluorine- containing ethane in a good selectivity. This and other objects of the present invention are achieved by a method for preparing a dimer of fluorine-containing ethane which comprises contacting a fluorine-containing ethane of the formula:

25 CFg-CCDOX2 (I)

wherein each of X1 and X2 is a fluorine or chlorine atom with a catalyst comprising nickel metal as such or nickel metal supported on a carrier in the presence of hydrogen gas.

30 DETAILED DESCRIPTION OF THE INVENTION

Specific examples of fluorine-containing ethane (I) are 1 ,1 ,1-trichloro-2,2,2-trifluoroethane (CF3CCI3, R- 113a), 1,1-dichloro-1,2,2,2-tetrafluoroethane (CF3CFCI2, R-114a) and 1-chloro-1 ,1 ,2,2,2-pentafluoroethane (CF3CF2CI, R-115). 35 The catalyst comprises nickel. The nickel catalyst is nickel metal as such or nickel metal supported on a carrier. Specific examples of the carrier are Si02, AI2O3, activated carbon, MgO, Ti02 and Si02-AI203. When nickel is supported on the carrier, an amount of nickel is 0.1 to 20 parts by weight based on the total weight of nickel and the carrier. Although a particle size of the catalyst is not critical, it is preferably from 16 to 60 mesh. 40 The supported catalyst may be prepared by any one of known methods. An Ni/Si02 catalyst which contains Ni supported on Si02 can be prepared by, for example, adding silica Aerosil® to an aqueous solution of nickel nitrate and then evaporating the mixture to dryness. An Ni/AI203 catalyst which contains Ni supported on AI2O3 can be prepared by, for example, adding alumina Aerosil® to an aqueous solution of nickel nitrate and then evaporating the mixture to dryness. An Ni/C catalyst which contains Ni supported on 45 activated carbon can be prepared by, for example, adding activated carbon to nickel nitrate, fully mixing them and then drying the mixture. Specific examples of the dimer of fluorine-containing ethane prepared according to the present invention are fluorine-containing butane of the formula:

50 CFgCY^-CY^CFg (II)

wherein each of Y1, Y2, Y3 and Y+ is a hydrogen, chlorine or fluorine atom, fluorine-containing 2-butene of the formula:

55 CF3CY1 =CY3CF3 (III)

wherein each of Y1 and Y3 is a hydrogen, chlorine or fluorine atom, and perfluorinated 2-butyne of the formula:

2 EP 0 499 984 B1

CF3OCCF3 (IV).

A hydrogen gas is preferably used in the method of the present invention. The hydrogen gas can 5 regenerate the catalyst. An amount of the hydrogen gas is usually from 0.5 to 10 mol, preferably from 2 to 6 mol per one mol of fluorine-containing ethane. Preferably, the reaction in the present invention is conducted in a continuous process. A feed rate of a feed gas (SV) is preferably 100 to 10,000 (h_1). SV is herein defined as

10 [feed gas volume per unit time (at reaction temperature)]

[apparent filled volume of catalyst]

15 A reaction pressure is not limited, and any practical reaction pressure can be used. A reaction temperature is usually from 200 to 550 0 C, preferably from 290 to 450 0 C. When the reaction temperature is lower than 200 °C, a conversion is low. When it is higher than 550 °C, a selectivity is low and the catalyst is deteriorated. A reaction gas may be used as such, or the reaction gas may be diluted by a gas which has no effect on the reaction, such as N2, Ar and He. 20 PREFERRED EMBODIMENTS OF THE INVENTION

The present invention will be illustrated by the following Examples which do not Limit the present invention. 25 Examples 1

Silica Aerosil® was added to an aqueous solution of nickel nitrate and the mixture was evaporated to dryness. Then, the mixture wag dried at 120 °C for one day to prepare a catalyst (Ni/Si02) having a nickel 30 amount of 1 % by weight (particle size: 32 to 60 mesh). Before a reaction, the catalyst was not calcined at a high temperature. In a normal pressure fixed bed reaction apparatus (internal diameter of a reaction tube: 12.5 mm), a pretreatment for reducing the catalyst was conducted at 450 0 C for two hours in an H2 stream before the reaction. A feed gas consisting of R-113a (10 cm3/min.), Ar (56 cm3/min.) and H2 (29 cm3/min.) was fed at a 35 flow rate of 95 cm3/min. The reaction temperature was 450 °C and an amount of the catalyst was 1 g. Hydrogen halide generated by the reaction was absorbed by calcium oxide and a resultant gas was analyzed by a gas chromatography. A GC-mass Spectrometer was used so as to identify a product in a small amount. A conversion of R-113a and selectivities of resultant products after the reaction of 2 hours are shown in Table 1. Also after the reaction of 1 hour or 6 hours, the conversion was 100 % and 40 selectivities of CF3CCI = CCICF3,CF3CH = CCICF3 and CF3CH = CHCF3 were high.

Comparative Example 1

The procedure in Example 1 was repeated except that a Cr/Si02 catalyst was used instead of the 45 Ni/Si02 catalyst. An amount of Cr in the Cr/Si02 catalyst was 1 % by weight and a particle size of the catalyst was 32 to 60 mesh. The Cr/Si02 catalyst was prepared by adding silica Aerosil® to an aqueous solution of chromium nitrate, evaporating the mixture to dryness and then drying the mixture at 120°C for one day. Before the reaction, the catalyst was not calcined at a high temperature. A conversion and selectivities of the products after the reaction of 2 hours are shown in Table 1 . 50

3 EP 0 499 984 B1

Table 1

Example 1 Com. Example 1 Conversion (%) 100 27.5 Selectivity (%) R-1112 (trace) 30.5 R-1111 0 6.9 R-114a 0 37.9 R-123 0 4.3 CF3CCI = CCICF3 85.8 0 CF3CH = CCICF3 4.8 0 CF3CH = CHCF3 6.0 0

Example 2

The procedure in Example 1 was repeated except that R-114a was used instead of R-113a in the feed gas. A conversion and selectivities of products after the reaction of two hours are shown in Table 2.

Comparative Example 2

The procedure in Comparative Example 1 was repeated except that R-114a was used instead of R-113a in the feed gas. A conversion and selectivities of products after the reaction of two hours are shown in Table 2.

Table 2

Example 2 Com. Example 2 Conversion (%) 4.5 72.6 Selectivity (%) R-1113 0 0.6 R-1112 0 8.2 R-1111 0 10.0 R-115 0 48.0 R-112a 0 1.5 R-124 56.9 0.3 R-1110 0 3.5 CF3CCIF-CCIFCF3 11.5 0

45 According to the present invention, the dimer of fluorine-containing ethane can be obtained in a good selectivity. Fluorine-containing 2-butene and perfluorinated 2-butyne which are the dimers of fluorine- containing ethane can be used as a copolymerizable monomer used for preparing a polymer having high temperature resistance and/or electrical conductivity. so Claims

1. A method for preparing a dimer of fluorine-containing ethane which comprises contacting a fluorine- containing ethane of the formula:

55 CFg-CCDOX2 (I)

wherein each of X1 and X2 is a fluorine or chlorine atom with a catalyst comprising nickel metal as such or nickel metal supported on a carrier in the presence of hydrogen gas.

4 EP 0 499 984 B1

2. A method according to claim 1, wherein the carrier is SiO, Al2 O3 .activated carbon, MgO, TiCfe or Si02- AI2O3.

3. A method according to claim 1, wherein the fluorine-containing ethane is 1 ,1 ,1 -trichloro-2,2,2- 5 trifluoroethane, 1 ,1 ,-dichloro-1 ,2,2,2,-tetrafluoroethane or 1 -chloro-1 ,1 ,2,2,2-pentafluoroethane.

4. A method according to claim 1 , wherein the dimer of fluorine-containing ethane is a fluorine-containing butane of the formula:

10 CFgCY^-CY^CFg (II)

wherein each of Y1, Y2, Y3 and Y+ is a hydrogen, chlorine or fluorine atom; fluorine-containing 2-butene of the formula:

15 CF3CY1 =CY3CF3 (III)

wherein each of Y1 and Y3 is a hydrogen, chlorine or fluorine atom; or perfluorinated 2-butyne of the formula:

20 CF3OCCF3 (IV)

Patentanspruche

1. Verfahren zur Herstellung von Dimeren aus Fluor enthaltendem Ethan, umfassend das Kontaktieren 25 eines Fluor enthaltenden Ethans mit der Formel

CFg-CCDOX2 (I)

worin X1 und X2 jeweils ein Fluor- oder Chloratom sind, mit einem Katalysator, umfassend Nickelmetall 30 als solches oder Nickelmetall auf einem Trager, in der Gegenwart von Wasserstoffgas.

2. Verfahren gemass Anspruch 1, in dem der Trager Si02, AI2O3, aktivierter Kohlenstoff, MgO, Ti02 oder Si02-Al203 ist.

35 3. Verfahren gemass Anspruch 1, in dem das Fluor enthaltende Ethan 1 ,1 ,1-Trichlor-2,2,2-trifluorethan, 1,1-Dichlor-1,2,2,2-tetrafluorethan oder 1-Chlor-1 ,1 ,2,2,2-pentafluorethan ist.

4. Verfahren gemass Anspruch 1 , in dem das Dimer aus Fluor enthaltendem Ethan ein Fluor enthaltendes Butan mit der Formel: 40 CFgCY^-CY^CFg (II)

worin Y1, Y2, Y3 und Y+ jeweils ein Wasserstoff-, Chlor- oder Fluoratom ist, ein Fluor enthaltendes 2- Buten mit der Formel: 45 CF3CY1 =CY3CF3 (III)

worin Y1 und Y3 jeweils ein Wasserstoff-, Chlor- oder Fluoratom ist, oder ein perfluoriertes 2-Butin mit der Formel: 50 CF3C=CCF3 (IV)

ist.

55 Revendicatlons

1. Procede pour preparer un dimere d'un compose de type ethane contenant du fluor, ce procede comprenant la mise d'un compose de type ethane, contenant du fluor, de formule :

5 EP 0 499 984 B1

CFg-CCDOX2 (I) dans laquelle chacun des symboles X1 et X2 represente un atome de fluor ou de chlore, en contact avec un catalyseur comprenant du nickel metallique, tel quel ou du nickel metallique sur un support, en operant en presence d'hydrogene gazeux.

Procede selon la revendication 1, dans lequel le support est Si02, AI2O3, du charbon actif, MgO, Ti02 ou Si02-Al203.

Procede selon la revendication 1, dans lequel le compose de type ethane contenant du fluor est le 1,1,1-trichloro-2,2,2-trifluoroethane, le 1 ,1 -dichloro-1 ,2,2,2-tetrafluoroethane ou le 1-chloro-1 ,1 ,2,2,2-pentafluoroethane.

Procede selon la revendication 1 , dans lequel le dimere du compose de type ethane contenant du fluor est un butane contenant du fluor, de formule :

CFgCY^-CY^CFg (II) dans laquelle chacun des symboles Y1, Y2, Y3 et Y+ represente un atome d'hydrogene, de chlore ou de fluor ; un 2-butene contenant du fluor, de formule :

CF3CY1 =CY3CF3 (III) dans laquelle chacun des symboles Y1 et Y2 represente un atome d'hydrogene, de chlore ou de fluor ; ou un 2-butyne perfluore de formule :

CF3OCCF3 (IV)