JPS6254093A - Production of perfluoro-compound - Google Patents

Abstract

PURPOSE:To produce a perfluoro-compound in a high yield by electrochemically fluorinating an org. compound to obtain a perfluoro-compound contg. a polyfluorinated product and by directly fluorinating the polyfluorinated product with gaseous fluorine. CONSTITUTION:When an org. compound is fluorinated to produce a perfluoro- compound, the org. compound is electrochemically fluorinated in the former stage to obtain a perfluoro-compound contg. a polyfluorinated product. The amount of the polyfluorinated product in the reaction product is regulated to about 50-80wt%. The polyfluorinated product is directly fluorinated with gaseous fluorine in the latter stage. Thus, an incompletely fluorinated product remaining in a reaction product obtd. by electrolytic fluorination is efficiently converted into the desired perfluoro-body.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a perfluoro compound.

[Prior Art and its Problems] Conventionally, as a method for producing a corresponding perfluoro compound from an organic compound, an electrolytic fluorination method and a direct hydrogenation method using fluorine gas are known. However, when producing a perfluoro compound by the former method, the produced fluorocarbon generally contains raw material molecules in addition to the target compound.

There are polyfluorinated products in which hydrogen atoms, etc. remain partially unreacted, and byproducts of decomposition of raw materials. In particular, when the target product is used as an oxygen-carrying component of artificial blood or an oxygen-carrying infusion, polyfluorinated substances have high ilJ properties against living organisms, and therefore need to be completely separated and removed. However, since it is difficult to separate polyfluorinated compounds from the target perfluorinated compound, they are boiled in C alkali (Japanese Patent Laid-Open No. 58-2
(No. 25013, Japanese Unexamined Patent Publication No. 114877/1982)
This required a lot of effort, leading to a large decrease in yield. or,
It is known that in the latter method, the raw material molecules tend to undergo cleavage and decomposition, making it difficult to obtain perfluorinated compounds.

[Means for Solving the Problems] The present invention has been made to solve the above-mentioned problems. The present invention provides a method for efficiently preparing perfluorinated compounds by combining the following.

The organic compound of the present invention is not limited in any way as long as it can be electrolytically fluorinated, and various compounds can be employed. In other words, hydrocarbons, halogenated hydrocarbons (
However, perfluorinated compounds are excluded), compounds with nitrogen-containing groups, alcohols, ethers, aldehydes,
These include ketones, carboxylic acids, phenols, alicyclic compounds, carbon polycyclic compounds, and heterocyclic compounds. Among these various organic compounds, polyfluorinated compounds that yield the desired perfluorinated compound obtained by electrolytic fluorination contain reactive functional groups such as acid halides and sulfonyl halides, which are not preferred. like this.

Polyfluorinated products are produced by direct fluorination of fluorine gas.
This is because it is easily decomposed and the target perfluoro compound cannot be obtained in good yield.

By electrolytic fluorination of organic compounds, perfluorinated compounds such as r are obtained, for example.

CHzGICH/Cl → C2F6C2H
3CH? CH20C, H2CH2OC2H5→ C2F
50F20F20CF2GFyOC2F Saku02 H!
+ )3 N →' (C2F5)+N(OH:
+)2CHCbHnN→(CF3)70FC5Fq
NFC, 5H+oN(Ih −+ C3FIONC
F3C5)++oNCsH++ + CsF+oNG
sF++(C!IHI+)3N → (05
F Yi+ hN(OH:+hS −+ChSF5+
(CF3)2sF4Cn-03Ht)2s-+ n-C
JFrSFs+(n-C3Fr)28Fa[(C2H5
)zNCH2(J2S]2→C02F5 )2 NCF
20F23F5((6Hs)2S −+, C-GsF
++SF5+(C-66F++)2sFaCH3S(C
H2) 2SCH3→ ChSF5+GzF5SF4CF
+CH35CII2COCI −+ChSFs÷(C
hhSFnJu02F5SF40F3CH30SO2Cl
→ChOCF3+5o2F2 However, in electrolytic fluorination, the polyfluoride dissolves in the perfluoro compound that is being generated, and the polyfluoride in the perfluoro compound is difficult to undergo electrolytic fluorination. However, the present invention can improve the yield by directly fluorinating such a polyfluorinated product with a fluorinated gas and converting it into a perfluoro compound. If the polyfluorinated compound in the perfluorinated compound can be easily separated because it has a sufficient boiling point difference with the perfluorinated compound, it may be directly fluorinated with fluorine gas after separating the polyfluorinated compound. However, fluorine gas may be directly introduced into a reaction product containing a perfluoro compound, a polyfluoride, etc., and the polyfluoride may be directly fluorinated.
In this case, the polyfluoride in the reaction product preferably has a weight of at least 50 to 80 wt$F.

゛ Perfluorinated compounds that can be advantageously produced according to the present invention include those that cannot be easily separated because the boiling points of the polyfluorinated product obtained by electrolytic fluorination and the perfluorinated compound are close to each other, or those that cannot be easily separated as impurities in the perfluorinated compound. If polyfluorinated substances are contained, the performance is undesirable.0For example, perfluorinated bicyclo compounds such as quinoline and quinolidine compounds 1, which are used in artificial blood and therapeutic drugs for brain cancer, are Since contamination is a concern and separation is not easy, the method of the present invention is effective. In addition, the thermal and chemical stability of perfluoroadamanthines and perfluoroalkylamines used in lubricating oils, hydraulic oils, insulating oils, heat carriers, etc. deteriorates when polyfluoride is mixed in. It is effective to apply the method of the present invention and to use a perfluorinated substance instead.

Electrolytic fluorination of organic compounds may be carried out using any known or 18'1 known method. For example, in an electrolytic cell with a capacity of approximately 1 liter and equipped with 5 nickel anodes and 4 cathodes, the concentration of the starting material is reduced in anhydrous hydrofluoric acid. 2-15wt%, bath temperature -10-1'5
°C, anode current density (1,1~3A/dm2, voltage 4.5
When the electrolytic reaction is carried out at ~8V, reaction products containing perfluorinated compounds, polyfluorinated products, decomposed fluorinated materials of raw materials, etc. are separated from the hydrofluoric acid layer. Electrolytic reactions can be performed using transition metal salts with fluorinating ability, such as cobalt chloride, 11!
The yield of perfluorinated compounds can be improved by carrying out the reaction in the presence of copper chloride, lead chloride, cerium chloride, bismuth chloride, manganese chloride, chromium chloride, iron chloride, cobalt fluoride, or the like.

Direct fluorination of polyfluoride with fluorine gas is a method in which fluorine gas diluted 1 to 20 times (by volume) with fluorine gas or an inert gas such as nitrogen or helium is directly blown into the electrolytic reaction product. is preferred. The amount of fluorine gas (%) to be introduced is 1 to 10 times the mol, preferably l.
The reaction temperature at which 3 to 3 times the mole is appropriate varies depending on the type of polyfluoride, etc., but is -20 to 200°C, preferably -50 to 150°C. If the temperature is lower than this, the reaction rate will decrease rapidly, and if the temperature is -1-, side reactions such as decomposition reactions will easily occur, which is undesirable.
As the reaction pressure, any of reduced pressure, normal pressure, and increased pressure can be employed, but it is usually preferable to carry out the reaction at normal pressure.

A perfluorinated compound having a high purity can be efficiently obtained with high purity through conventional separation operations such as extraction and distillation.

[Example] Example 1 An electrolytic cell and a Hastelloy container: It has 5 nickel anodes and 4 cathodes arranged alternately in a cross-section, and has an effective anode surface! A 8.3ds2 tank equipped with a reflux condenser at the top of the tank was used. 800g of hydrogen fluoride was introduced into this electrolytic cell, and trace amounts of impurities such as water and sulfur were removed by preliminary electrolysis.
Next, 90 g of 4-methyl-octahydroquinolidine (
0.59 mol) was dissolved in fluorophore, and the electrolytic voltage was 9.
Temperature -1θ~-5℃, anode current density 2 until reaching v
Conducted for 700Ahr at A/d■2. After electrolysis, the electrolytic tank r
190 g of fluorocarbon (reaction product) was collected from the sample.

This fluorocarbon is the desired perfluorocarbon 56
g, polyfluorinated product 30 g and ring-fused 9 decomposition product 10
Using gas chromatography and p-glorpenzotriflide as a standard substance,
It was analyzed by 19Fnmr. In this fluorocarbon, F2 gas diluted to 40 mm with N2 gas was added to 13
A total of 1.1 moles of polyfluoride molecules were introduced at a rate of 0°C''r'0.8 mmol/sin (7).
It was confirmed by nsr that the wood element T- remaining in the sample was completely replaced by the fluorine element f, and the polyfluoride was converted into a polyfluoro compound.

Furthermore, after washing the reaction product with water, precision distillation was performed to obtain perfluoro-4
-80 g of methyloctahydroquinolidine were obtained. (Overall yield 27z) Comparative Example 1 After electrolytic fluorination reaction, an equal volume of 701 K was added to 190 g of fluorocarbon having the same composition as in Example 1'.
Add OI (aqueous solution and diisobutylamine).

The mixture was refluxed to decompose and remove residual hydrogen atoms. After washing with water, precision distillation was performed to obtain 48 g of perfluoro-4-methyloctahydroquinolidine. (Overall yield 15.
H) Example 2 In the same manner as in Example 1, 75 g of tributylamine (0,4
0 mol) in 800 g of hydrogen fluoride until the electrolytic voltage reaches 9 V? Power was applied for 70Ahr.

After electrolysis, 178 g of fluorocarbon was collected from the bottom of the tank. 40 volts of N2 gas in this fluorocarbon
F2 gas diluted to 100-150℃ for a total of 4.0s
Mole was introduced.

Furthermore, after washing with water, it was distilled to obtain 130 g of perfluorotributylamine. (Overall yield 48z) Comparative Example 2 After electrolytic fluorination reaction, 1! An equal volume of 70% K was added in 180 g of fluorocarbon having the same composition as in Example 2.
The mixture was refluxed in an aqueous OH solution and diisobutylamine for 120 hours.

Furthermore, after washing with water, 88 g of perfluorotributylamine was obtained by distillation. (Total yield: 25z) Example 3 In the same manner as in Example 1, 85 g (0.1 mole) of tetrahydrofurfuryl amyl ether was charged into 800 g of fluorophore and energized for 6θ7 Ahr. N was present in 146 g of fluorocarbon collected from 1 part of the tank after electrolysis.

Gaste 40vo1% Ni dilution L TaF2i Suwo 100~
A total of 4.5 mol was introduced at 110°C. Furthermore, this fluorocarbon was washed with water and then distilled to give 79.8 g of perfluorotetrahydrofurfuryl perfluoroamyl ether (
Comparative Example 3 After electrolytic fluorination reaction in the same manner as in Example 3, 153 g of fluorocarbon was treated with an aqueous solution of KO)I, washed with water, and distilled. Perfluorotetrahydrofurfuryl perfluoroamyl ether JL/ha 45g (0.08 mo/L/) Te Atsuta. (Total yield: 18 $) [Effect of the invention] According to the present invention, in the production of perfluorinated compounds, incompletely fluorinated compounds remaining in the reaction product obtained by electrolytic fluorination reaction can be efficiently removed by chemical perfluorination. It can be transformed into a body.

Furthermore, if the raw material organic compound is directly subjected to the fluorination reaction, the raw material molecules are likely to be cleaved and decomposed, and it is difficult to obtain a perfluorinated compound. It can be converted to a perfluorinated compound with low yield without cleavage.

Claims (1)

[Claims] 1. In the method of obtaining a perfluoro compound by fluorinating an organic compound, the organic compound is electrochemically fluorinated to obtain a perfluoro compound including a polyfluoride. 1. A method for producing a perfluoro compound, characterized in that the perfluoro compound is obtained by a combination of post-stage reactions in which the perfluoro compound is obtained.