A method of obtaining a perfluorinated epoxides

 

(57) Abstract:

The invention relates to a method for producing oxides of perfluorinated olefins, which are of practical use as starting compounds to obtain some valuable organofluorine products. Perfluorinated epoxides obtained by oxidation of the corresponding olefins with oxygen at 15 - 120oC in the presence of initiators is chlorine, fluorine, bromine, triftormetilfullerenov, tetrafluoroethylene in an environment halon or perchloromethane fluid. Gaseous olefin is served in the flow of oxidant under a layer of inert solvent. Exit oxide hexaferrite 77% at a conversion of 78%, the yield of tetrafluoroethylene oxide 87% at a conversion of 93%. The developed method allows to increase the yield of fluorinated epoxides and increase the degree of conversion of the initial olefin, and create reliable industrial technology to obtain oxides of perfluoroolefins. 4 C.p. f-crystals, 1 table.

The invention relates to the field of production of oxides of perfluorinated olefins, in particular, oxides of tetrafluoroethylene (OTFE) and oxide hexaferrite (EGFP), which are of practical use as starting products for the synthesis of perfluoroalkyl vinyl ether is TBE caustic soda and chlorine, surfactants, thermo-frost-resistant rubbers, oils, hydraulic fluids and other organofluorine products (Tarrant P. and others, Oxides of perfluoroolefins, IVHO them. Mendeleev, 1970, I. 15, No. 1, page 84).

Known methods of oxidation farolatino hydrogen peroxide (Japan's Bid N 63-27487, 05.02.88), hypochlorites of alkali and alkaline earth metals (Japan's Bid N 59-110687, 26.06.84), nagkakamali (Ed. Mon. RF N 317651, 19.11.71), phenoxyimino acid (Patent Germany N 2557655, 30.06.77), anodic oxidation (Patent Germany N 2658328, 29.06.78). However, to date there is no convenient, safe industrial method of producing oxides of perfluorinated olefins, although work is in progress in several directions.

Of all known methods, the most preferred is the oxidation of farolatino the most affordable and cheap oxidant is oxygen.

A method of obtaining EGFP by liquid-phase oxidation of hexaferrite (HFP) with oxygen at a temperature of 70-120oC at pressures up to 5.0 MPa (50 ATM.) in solvent (Ed. Mon. RF N 608801, 30.05.78) in a steel reactor lined with Teflon, in the presence of a catalyst - Teflon chips, processed products of oxidation of the GUF. For Prigat is up to 140oC. Then begin to barbthroat air at a pressure of 5.0 MPa for 3 hours. After that, the reactor with the oxidation products of the GUF put Teflon shavings, then siphon off the solvent and boiling products. Thus prepared chips are placed in a reactor, fill up the freon and pre-cooled to minus 70oC GUF, heat the reactor up to 70-120oand at a pressure of 50 ATM. bubbled air. Reaction time from 15 to 30 minutes Selectivity reaches 84% at a conversion of 23%.

The disadvantages of this method is the frequency, the complexity of the preparation of the catalyst, low conversion, high pressure and explosion hazards in the process.

A method of obtaining fluorinated oxides by heating galeolaria CF2=CFX, where X is H, F, Cl, CF3, CF2H and others, with oxygen at an elevated pressure at a temperature of 50-250oC in the presence of inert diluent - N2, CO2, Ar, CF4C2F6, cyclo-C4H8ISO-C6F14, CCl4, CF2Cl2, CF2HCl, C2F3Cl3,

CF3CFBrCF2Br and others (U.S. Patent N 3536733, 27.10.70). Under this method in the autoclave load diluent (F-113) and olefin (TPV or d EGFP - 71%, with a conversion of 70%.

The disadvantages of this method is the periodicity of the process and high pressure, which leads to the explosion process.

The closest technical solution is the method of producing a tetrafluoroethylene oxidation of tetrafluoroethylene (TPV) by molecular oxygen in the presence of ozone at a temperature of 0-40oC in the environment of PERFLUORO - or perchlorobenzene liquid - 1,1,2-trichloro-1,2,2-triptoreline, tortiglioni, performatilicious (EXT. Mon. N 95620 to French patent N 1526663, 26.03.71). The molar ratio of C2F4:O3is 10:500. For carrying out the synthesis in a reactor filled PERFLUORO - or chlorpheniramine liquid, then with constant stirring in a reaction medium bubbled TPV and ozonized oxygen through two pipelines located at the base of the reactor. Output OTPA is 46-62% conversion TPV 45-58%.

The disadvantages of this method include low output OTPA and low conversion TPV.

The present invention is to increase the yield of fluorinated epoxides, increase the degree of conversion of the initial olefin, as well as the creation of a universal reliable industrial method of obtaining ainow oxygen in the presence of initiators, when the gaseous perfluoroolefin in the flow of oxidant under a layer of inert liquid at a temperature of 15-120oC.

The process is carried out in a flow reactor, which is a cylindrical vessel with external heating and sockets for input of reactants and reaction products. The reagents are injected into the reactor through two tubes placed one inside the other (pipe in pipe), and the inner tube are doing is shorter than the outer, the output end of which is placed in the reactor under a layer of inert liquid. The reaction gases passing through the layer of liquid are discharged through a bottom outlet. To stabilize the process may further mixing of the reacting gases in an inert solvent.

In the reactor inert fill fluid, the inner tube serves gaseous perfluoroolefin, and on the external oxygen from the initiator. In the case of oxidation of tetrafluoroethylene with oxygen may be filed with an inert diluent, such as nitrogen. When this mixture components and the oxidation of the olefin occurs at the entrance of gaseous olefin in the gaseous stream of oxidizing mixture under a layer of inert solvent.

As the inert solvent used is ausina molecular weight and boiling temperature (150-300oC), and halocarbons, for example, 51-12 (1,6-dichlorphenoxy), 318 (perftorsilanami).

As the initiator uses the halogen is chlorine, fluorine, bromine, tetrafluoroethylene, triftoratsetofenona. For the preparation of oxidation of a mixture of halogen and triftoratsetofenona add to oxygen in an amount of 0.1-15 vol. % and tetrafluoroethylene add to HEXAFLUOROPROPYLENE in an amount of 1-15%. The increase in the content of the initiator of the above limits is impractical because in all cases there is a growing number of by-products (carbonitride, triftoratsetofenona). When the content of the initiator is less than the specified limits sharply reduced conversion of a perfluoroolefin.

The process is carried out continuously at a temperature of 15-70oC for the oxidation of tetrafluoroethylene and at 60-120oC for hexaferrite. At temperatures below the lower limit of the oxidation rate decreases along with the degree of conversion. The temperature increase leads to the increase of by-products at the expense of deeper oxidation.

The reaction products containing perfluorinated epoxide, foramerica and unreacted olefin, condense when cooled to minus 120oC analyze method gazozhidkostnoi the ü hexaferrite with the release of 77.2% of the conversion to 78.3% and tetrafluoroethylene oxide with the release of 87% conversion 93,8%. Found the reception feeding and mixing of components allows to conduct the process in a continuous mode in milder conditions, to exclude his explosiveness and thus makes the process perspective for industrial development.

Distinctive features of the proposed method are used as the initiator of halogen, triftormetilfullerenov and tetrafluoroethylene, and the gaseous olefin in the flow of oxidant under a layer of inert solvent. These features distinguishing the claimed method from the prototype, have been identified in other technical solutions.

The following examples illustrate the invention.

Example 1

In a cylindrical reactor jacketed and heated with a capacity of 310 cm3pour perchlorovinyl liquid 12FEET in the amount of 200 ml In Teflon, axially located tube lowered into the reactor serves gaseous components: internal - HFP with a speed of 3.0 l/h, on the outer - oxidizing mixture of oxygen with triftormetilfullerenov) with a speed of 6.0 liters/hour.

The content of triftormetilfullerenov (CF3OF) to oxygen is equal to 5.5%. The volumetric ratio of HFP and oxidative dare composition, about. %: 51,2 EGFP; 18,4 HFP; 30.4 triftoratsetata and carbonitride. The reaction gases are passed through a 5% solution of sodium hydroxide to remove acidic impurities, and then dried in a column of calcium chloride and condense in the trap at a temperature of minus 120oC.

The obtained raw rectificatum under pressure and produce 67,14 g EGFP 99.5% purity. Selectivity is 77.2% of the conversion of hexaferrite to 78.3%.

Subsequent syntheses (examples 2-12) is carried out analogously to example 1. The conditions of oxidation farolatino and the results are shown in the table.

Literature

1. Tarrant P., E. stump, Oxides of perfluoroolefins, IVHO them. Mendeleev, 15, 1, 84 (1970).

2. Japan's bid N 63-27487, C 07 D 303/48, publ. 5.02.88, RICH 89, N.

3. Japan's bid N 59-110687, C 07 D 301/03, publ. 26.06.84, RICH 85, N.

4. Auth.mon. RF N 317651, C 07 D 301/12, publ. 19.11.71.

5. Patent Germany N 2557655, C 07 D 301/16, publ. 30.06.77. Fig. for RUB, 1977, V. 24, N 13, S. 163.

6. Patent Germany N 2658328, C 25 B 3/02, publ. 29.06.78. Fig. for RUB, 1978, V. 66, No. 11 C. 13.

7. Auth.mon. RF N 608801, C 07 D 303/08, publ. 30.05.78.

8. U.S. patent N 3536733, 260-348.5, publ. 27.10.70.

9. EXT. mon. N 95620 to French patent N 1526663, C 07 D, publ. 26.03.71 (prototype).

2. The method according to p. 1, characterized in that the halogen-free and triftoratsetofenona adds to the oxygen in an amount of 0.1 to 15.0% vol.

3. The method according to p. 1, characterized in that the olefin use HEXAFLUOROPROPYLENE, to which is added the tetrafluoroethylene in an amount of 1.0 to 15.0% vol.

4. The method according to p. 1, wherein the process is conducted at 15 - 120oC.

5. The method according to p. 1, characterized in that as the inert solvent used halocarbons and perchloroethane fluid.

 

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