RU2071462C1 - Method for production of unsaturated fluorine-containing carbohydrates, fluorine- and chlorine-containing carbohydrates, fluorochlorocarbons or fluorocarbons - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: unsaturated carbohydrates or halide carbohydrates or halide carbons are fluorinated. Uranium hexafluoride, or molybdenum hexafluoride or vanadium pentafluoride are used as said fluorinated agent. The process is carried out at 20-400 C. Compounds having one or two double bonds from $$$ series and further are used as mentioned above unsaturated organic compounds. EFFECT: improves efficiency of the method. 2 cl

Description

The invention relates to methods for producing unsaturated fluorine-containing organic compounds and may find application for the production of chladones, in particular solvents, blowing agents, refrigerants and extinguishing agents with zero ozone-depleting ability (ozone destroy potential ODP 0)
A known method of producing 1,1-difluoroethane and vinyl fluoride by fluorination of vinyl chloride with hydrogen fluoride at an elevated temperature in the presence of a catalyst with subsequent isolation of the target product by known methods, characterized in that in order to intensify the process, fluorine aluminum with the addition of chromium oxide is used as a catalyst (a USSR N 423789 dated 07.07.72 M.C. C07c 19/08; C07c 21/18 (H.U. Usmanov, A.A. Yulchibaev and others). The invention includes the production of both saturated and unsaturated fluorocarbons from unsaturated chlorohydrocarbons.

 The disadvantages of the prototype include the need to use a specially prepared catalyst, the limited time of the catalyst and the resulting insufficient stability of the synthesis process with a relatively low yield of target products.

Unsaturated chlorocarbons and chlorohydrocarbons, for example, CCl ₂ CCl ₂ and CHCl CCl ₂ , are excellent solvents, have zero ozone-depleting potential, but they are toxic (MAC in the working area of about 10 mg / m ³ ).

 The introduction of fluorine in unsaturated chlorocarbons or chlorocarbons will reduce the toxicity of these substances, maintain a high dissolving ability and ODP 0.

A method for producing unsaturated fluorine-containing organic compounds by fluorination of unsaturated hydrocarbons or halogenated hydrocarbons or halocarbons with uranium hexafluoride or molybdenum hexafluoride, or vanadium pentafluoride at a temperature of 20-400 ^o C. Moreover, substances with one or more double bonds are used as starting unsaturated organic compounds, starting from rows C ₃ , C ₄ . The molar ratio of reagents is maintained close to stoichiometric.

 In the known method (USSR AS N 423789 dated 07.07.72), the catalytic hydrofluorination of vinyl chloride leads to the formation of a mixture of saturated and unsaturated fluorocarbons 1,1 difluoroethane and vinyl fluoride, i.e. the process is not selective enough, which can partly be explained by the heterogeneous nature of the reaction, leading to an excess of fluorinating agent in some parts of the catalyst surface. The consequence of this is the saturation of the double bond of the starting reagent with fluorine.

In the proposed method, the catalyst as such is absent, and fluorinating agents (UF ₆ , MoF ₆ , VF ₅ ) under the reaction conditions are gaseous substances, which makes it easy to maintain the stoichiometric phase ratio of the reactants.

 The most affordable of these is dump uranium hexafluoride, which is available in Russia in large quantities and requires conversion to an ecologically safe form, for example, uranium tetrafluoride or uranium oxide and hydrogen fluoride. The molar ratios of the organic and fluorinating reagents and the temperature are selected in such a way as to introduce the necessary amount of fluorine into the composition of the molecule and not to affect the double bond, and in dienes to keep one double bond. The fluorinating agent may be diluted with an inert gas. Fluorination of uranium or molybdenum hexafluorides or vanadium pentafluoride allows to obtain unsaturated organic compounds with high dissolving power and zero ozone-depleting potential (ODP 0).

 Example 1. The process of obtaining unsaturated fluorine-containing compounds was carried out in a laboratory setting. The organic reagent was introduced in the liquid or gas phase. The fluorinating agent supplied in the reaction zone was used with 100% or diluted with an inert gas to 10% vol.

 The resulting lower metal fluoride was separated from the organofluorine reaction products on a porous non-gel filter.

Organofluorine products were dispersed and analyzed by chromatography, IR and NMR on nuclei F ¹⁹ and H ¹ .

Hexachloropropene (CCl ₃ - CCl CCl ₂ ) in the liquid phase was used as the starting material. Fluorination was carried out at a temperature of 50 ^o C and a molar ratio of hexachloropropene and uranium hexafluoride 2.1: 1.

Выход 3-фторпентахлорпропена-1 составил более 90%
Пример 2. Фторирование гексахлорпропена проводили в жидкой фазе при температуре 100^oC гексафторидом урана, разбавленным азотом до 10% об. при мольном соотношении C₃Cl₆ UF₆ 1,05 1.

The yield of 3-fluoropentachloropropene-1 was more than 90%
Example 2. Fluorination of hexachloropropene was carried out in the liquid phase at a temperature of 100 ^o C uranium hexafluoride diluted with nitrogen to 10% vol. at a molar ratio of C ₃ Cl ₆ UF ₆ 1.05 1.

Пример 3. Фторирование гексахлорпропена проводили в газовой фазе при температуре 210^oC гексафторидом урана, разбавленным азотом до 10% об. при мольном соотношении C₃Cl₆ UF₆ 2 3.

Example 3. Fluorination of hexachloropropene was carried out in the gas phase at a temperature of 210 ^o C uranium hexafluoride diluted with nitrogen to 10% vol. at a molar ratio of C ₃ Cl ₆ UF ₆ 2 3.

Пример 4. Фторирование 1,2,3,3-тетрахлорпропена проводили в газовой фазе при температуре 200^oC гексафторидом урана, разбавленным азотом до 10% об. при мольном соотношении 1,05 к UF₆.

Example 4. The fluorination of 1,2,3,3-tetrachloropropene was carried out in the gas phase at a temperature of 200 ^o C uranium hexafluoride diluted with nitrogen to 10% vol. at a molar ratio of 1.05 to UF ₆ .

Пример 5. Гексахлорпропен фторировали гексафторидом молибдена без разбавления азотом при температуре 300^oC и мольном соотношении C₃Cl₆ MoF₆ 1,05 1

Пример 6. Гексахлорпропен фторировали пентафторидом ванадия при 20^oC в жидкой фазе при и мольном соотношении VF₅ C₃Cl₆ 3 1,05

Аналогичными способами могут быть получены фторсодержащие пропилены с низкой температурой кипения, например, CF₂ CF CF₂Cl (t_кип 7,6^oC), который можно использовать и как хладагент и как вспениватель, а также целый ряд непредельных фторхлоруглеводородов для широкой области применения.

Example 5. Hexachloropropene was fluorinated with molybdenum hexafluoride without dilution with nitrogen at a temperature of 300 ^o C and a molar ratio of C ₃ Cl ₆ MoF _{6 of} 1.05 1

Example 6. Hexachloropropene was fluorinated with vanadium pentafluoride at 20 ^o C in the liquid phase at a molar ratio of VF ₅ C ₃ Cl ₆ 3 1.05

Using similar methods, fluorine-containing propylene with a low boiling point can be obtained, for example, CF ₂ CF CF ₂ Cl (t _boiling point 7.6 ^o C), which can be used both as a refrigerant and as a blowing agent, as well as a number of unsaturated fluorocarbons for a wide range of applications .

Example 7. As the starting material used hexachlorobutadiene - 1,3 symmetric conjugated chlorolefin. Fluorination was carried out with uranium hexafluoride without dilution at a temperature of 20 ^o C in the liquid phase at a molar ratio of C ₄ Cl ₆ UF ₆ 1,05 1.

Пример 8. Фторирование проводили при температуре 50^oC в жидкой фазе и разбавлении UF₆ азотом до 20% об. при мольном соотношении С₄Cl₆ UF₆ 1,05 2

Пример 9. Фторирование проводили при температуре 250^oC в газовой фазе разбавлении UF₆ азотом до 20% об. и мольном соотношении C₄Cl₆ UF₆ 1,05 3

Пример 10. Фторирование проводили пентафторидом ванадия при разбавлении азотом до 10% об. температуре 70^oC в жидкой фазе и мольном соотношении C₄Cl₆ VF₅ 1 2

Пример 11. В качестве исходного вещества использовали пентен-1. Фторирование проводили гексафторидом урана, разбавленным до 10% об. при температуре 100^oC в газовой фазе и мольном соотношении органический реагент UF₆ 1 1

Из приведенных примеров следует, что фторирование непредельных соединений с длиной цепи C₃ и более гексафторидами урана, молибдена и пентафторидом, ванадия в условиях, обеспечивающих сохранение двойной связи во фторорганическом продукте реакции, приводит к получению непредельных фторорганических веществ с высокой растворяющей способностью и нулевым озоноразрушающим потенциалом:
CCl₂F CCl CCl₂ 3-фторпентахлорпропен-1
CClF₂ CCl CCl₂ 3,3-дифтортетрахлорпропен-1
CF₃ CCl CCl₂ 3,3,3-трифтортрихлорпропен-1
CHCl CCl CHF₂ 3,3-дифтор-1,2-дихлорпропен-1
CCl₂F CCl CCl CCl₂F 1,4-дифторгексахлорбутен-2
CClF₂ CCl CCl CClF₂ - 1,1,4,4-тетрафтортетрахлорбутен-2
CF₃ CCl CCl CF₃ 1,1,1,4,4,4-гексафтордихлорбутен-2
CH₂F (CH₂)₂ CH CH₂ 5-фторпентен-1
ODP 0 обеспечивается за счет наличия в получаемом фторорганическом соединении двойной связи, которая быстро окисляется в нижних слоях атмосферы и приводит к разложению вещества на нелетучие компоненты, выпадающие на земную поверхность.

Example 8. Fluorination was carried out at a temperature of 50 ^o C in the liquid phase and diluted with UF ₆ nitrogen to 20% vol. at a molar ratio of C ₄ Cl ₆ UF ₆ 1.05 2

Example 9. Fluorination was carried out at a temperature of 250 ^o C in the gas phase, diluting UF ₆ with nitrogen to 20% vol. and a molar ratio of C ₄ Cl ₆ UF ₆ 1.05 3

Example 10. Fluorination was carried out with vanadium pentafluoride when diluted with nitrogen to 10% vol. temperature 70 ^o C in the liquid phase and a molar ratio of C ₄ Cl ₆ VF ₅ 1 2

Example 11. As the starting material used pentene-1. Fluorination was carried out with uranium hexafluoride diluted to 10% vol. at a temperature of 100 ^o C in the gas phase and a molar ratio of organic reagent UF ₆ 1 1

From the above examples, it follows that fluorination of unsaturated compounds with a chain length of C ₃ or more with uranium, molybdenum hexafluorides and pentafluoride, vanadium under conditions ensuring the preservation of a double bond in the organofluorine reaction product leads to the production of unsaturated organofluorine substances with high solubility and zero ozone-depleting potential :
CCl ₂ F CCl CCl ₂ 3-Fluoropentachloropropene-1
CClF ₂ CCl CCl ₂ 3,3-difluorotetrachloropropene-1
CF ₃ CCl CCl ₂ 3,3,3-trifluorotrichloropropene-1
CHCl CCl CHF ₂ 3,3-difluoro-1,2-dichloropropene-1
CCl ₂ F CCl CCl CCl ₂ F 1,4-difluorohexachlorobutene-2
CClF ₂ CCl CCl CClF ₂ - 1,1,4,4-tetrafluorotetrachlorobutene-2
CF ₃ CCl CCl CF ₃ 1,1,1,4,4,4-hexafluorodichlorobutene-2
CH ₂ F (CH ₂ ) ₂ CH CH ₂ 5-fluoropentene-1
ODP 0 is ensured by the presence in the resulting organofluorine compound of a double bond, which is rapidly oxidized in the lower atmosphere and leads to the decomposition of the substance into non-volatile components that fall onto the earth's surface.

Claims (2)

1. A process for preparing unsaturated fluorocarbons, ftorgalogenuglevodorodov, ftorgalogenuglerodov fluorocarbons or from the corresponding unsaturated organic compounds by treatment with a fluorinating agent, characterized in that the fluorinating agent is uranium hexafluoride, molybdenum or vanadium pentafluoride and the process is carried out in a temperature range of 20 400 ^o C and a molar reagent ratio close to stoichiometric. 2. The method according to claim 1, characterized in that hydrocarbons, halocarbons and halocarbons with one or more double bonds of C ₃ C ₈ series are used as unsaturated organic compounds.