JPS641473B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to a novel perfluoro(N-vinylhexamethyleneimine) and a method for producing the same. More specifically, the present invention uses perfluoro(N-vinylhexamethyleneimine), which is useful as a synthetic intermediate or polymer monomer for fluorine-containing products such as surfactants, agricultural chemicals, and pharmaceuticals.
The present invention relates to an economical manufacturing method with high yield using readily available raw materials. Background Art In recent years, fluorine-containing olefin compounds have been in the spotlight as synthetic intermediates and raw materials for various fluorine-containing products, such as surfactants, agricultural chemicals, pharmaceuticals, etc. Widely used as a monomer for polymer production. By the way, in perfluoro (N-vinyl cyclic amine), which is a type of fluorine-containing olefin, a perfluoro cyclic amino group is bonded to one of the carbon atoms of the double bond, so this compound can be used as an intermediate raw material. By using it, it is possible to produce various useful compounds containing the perfluorocyclic amino group. In addition, by copolymerizing the compound with other fluoroolefins and introducing a perfluorocyclic amino group into the polymer,
It is possible to reduce the crystallinity and improve the mechanical properties of the polymer. In this case, olefins containing bulky perfluorocyclic amino groups such as seven-membered rings are more effective than perfluoro(N-vinyl cyclic amines) containing five- or six-membered perfluorocyclic amino groups. It is possible to modify the copolymer.
Additionally, perfluorocarboxylic acid, which is easily derived from perfluorovinylamine, is useful as an optically active analytical reagent for measuring the optical purity of amines, but it is known that its performance improves as the cyclic amino group becomes larger. It is being For the above reasons, there has been a desire in the field of fluorine chemistry for the appearance of perfluoro (N-vinyl cyclic amines) having a cyclic amino group larger than a six-membered ring. However, the perfluoro(N-vinyl cyclic amines) known so far are perfluoro(N-vinylpyrrolidine) (Japanese Patent Application No. 162,632/1982),
Perfluoro(N-vinylmorpholine) (J.
Chem.Soc.Perkin I, 1973, 5) (Patent application 1986-
162632), perfluoro((N-vinylpiperidine)) (J.Chem.Soc.(C), 1968, 2608)
60−162632), and perfluoro(N-vinyl,
N′-alkylpiperazine) (patent application 1980-
There are only perfluoro (N-vinyl cyclic amines) that have a 5- or 6-membered ring, such as 162632), and trifluorovinyl compounds that have a 7-membered perfluorocyclic amino group have not been known. . Problems to be Solved by the Invention Under these circumstances, the object of the present invention is to produce perfluorohexamethylene as a bulky perfluorocyclic amino group from easily available raw materials and in good yield through simple processing. An object of the present invention is to provide a novel perfluoro(N-vinyl cyclic amine) containing an imino group and a method for producing the same. Means for Solving the Problems As a result of extensive research in order to achieve the above object, the present inventors found that perfluoropropionyl fluoride or perfluoropropion having a perfluorohex or sameethyleneimino group at the 2- or 3-position is used as a raw material. It was discovered that the object could be achieved by using an acid salt and heat-treating it, and based on this knowledge, the present invention was completed. That is, the present invention uses the formula () Perfluoro(N-vinyl cyclic amine) represented by the general formula (R in the formula is

[Formula] or

The present invention provides a method for producing a perfluoro compound represented by the following formula by heating it at a temperature in the range of 100 to 500°C. In the method of the present invention for producing this compound, perfluoro(2-hexamethyleneiminopropionyl fluoride) and perfluoro(3-hexamethyleneiminopropionyl fluoride) represented by the general formula () are used as raw materials. , this is for example the expression (R′ in the formula is

[Formula] or

[Formula], Y is a chlorine atom, an alkoxy group, or a dialkylamino group) can be easily obtained by electrolytic fluorination in hydrogen fluoride. can. Perfluoro (hexamethyleneimino group-substituted propionate) can be obtained by reacting an alkali metal or alkaline earth metal hydroxide with perfluoro (hexamethyleneimino group-substituted propionyl fluoride) obtained as described above. It is obtained by The compound of the present invention represented by the general formula () can be obtained by simply heat-treating perfluoro (hexamethyleneimino group-substituted propionic acid derivative) represented by the general formula () at a temperature in the range of 100 to 500°C. It can be easily obtained. At this time, acid fluorides, sodium salts, and potassium salts are suitable as propionic acid derivatives containing a perfluorohexamethyleneimino group at the 2- or 3-position because thermal decomposition proceeds easily. As the temperature for the thermal decomposition reaction, a temperature in the range of 100 to 500°C, preferably 100 to 300°C is selected. If this temperature is too high, side reactions such as decomposition are likely to occur, and if this temperature is too low, the conversion rate will decrease. The reaction time required in this case depends on the treatment temperature, but is usually within the range of 10 seconds to 2 hours. When the treatment temperature is high, the reaction time becomes short, and when the treatment temperature is low, the reaction time becomes long. In this thermal decomposition reaction, the reaction pressure is not an important factor, and the reaction can be carried out under reduced pressure, atmospheric pressure, or increased pressure, but the reaction products are relatively easy to recover. From this point of view, it is desirable to carry out the reaction under atmospheric pressure or reduced pressure.
In addition, the thermal decomposition reaction may be performed using inert gases such as nitrogen, helium, argon, carbon dioxide, polyethers, ethylene tetrachloride, n-
It may also be carried out using an aprotic liquid compound such as heptane as a diluent. In this case, the dilution ratio is preferably 100 times or less. Further, in the thermal decomposition reaction, it is important that all materials used in the reaction do not contain water. In the method of the present invention, when perfluoropropionyl fluoride having a perfluorohexamethyleneimino group at the 2- or 3-position is used as a raw material, the thermal decomposition reaction is preferably carried out in the presence of a metal salt or metal oxide. In this case, the desired perfluoro(N-vinylhexamethyleneimine) can be easily obtained by continuously supplying raw materials to a packed layer of metal salts or metal oxides maintained at a predetermined temperature and carrying out a thermal decomposition reaction. It will be done. There are no particular restrictions on the material for the thermal decomposition reaction, but stainless steel or Hastelloy is usually used. Furthermore, there are no particular restrictions on the format of the filling layer;
Any type of bed, such as a fixed bed, moving bed, or fluidized bed, can be used. Examples of the metal salt include sodium carbonate,
Potassium carbonate, lithium carbonate, sodium phosphate, potassium phosphate, barium carbonate, calcium carbonate, magnesium carbonate, potassium sulfate, sodium sulfate, etc.; examples of metal oxides include zinc oxide, cadmium oxide, etc.
Among these, solid bases such as sodium carbonate and potassium carbonate are toxic substances generated in thermal decomposition reactions.
It is particularly suitable because it can decompose _COF2 . Effects of the Invention According to the method of the present invention, novel perfluorinated (N
-vinylhexamethyleneimine) can be obtained in high yield from easily available perfluoro(hexamethyleneimino group-substituted propionic acid derivatives) through an extremely simple process. This method is suitable as an industrial method for producing methyleneimine). In addition, perfluoro(N) obtained by the method of the present invention
-Vinylhexamethyleneimine) has extremely high industrial value, for example as a synthetic intermediate for fluorine-containing products such as surfactants, dyes, agricultural chemicals, and pharmaceuticals, and as a raw material for the production of fluorine-containing plastics. For example, perfluorocarboxylic acid obtained by reacting perfluoro (N-vinyl cyclic amine) with carbonyl fluoride and then hydrolyzing it is useful as an optically active analytical reagent. Because of the improved performance, those derived from the compounds of the present invention may provide much better analytical reagents than those derived from conventional five- or six-membered cyclic imine-bearing compounds. can. Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way. Example 1 A flash evaporator for vaporizing raw materials and a diluent gas flow rate control device were connected to the inlet side, and the outlet side was equipped with a low-temperature trap for condensing and collecting reaction products.Length 48.0 cm A stainless steel tube with an inner diameter of 2.5 cm was used as a horizontal pyrolysis reactor. Fill this with 82.3g of powdered potassium carbonate at a horizontal level so that it comes to about the middle of the reactor.
Both ends were filled with metal wool. First, the reactor was kept at 200°C, helium gas was flowed at 100 ml/min, and 4.00 g of perfluoro(2-hexamethyleneiminopropionyl fluoride) was added to the reactor using a micro metering pump for 31 minutes. After being vaporized and mixed with helium gas, which was quantitatively fed in, it was introduced into the reactor. When the reaction product was condensed and collected in a trap cooled to -78°C on the outlet side, 2.88 g of a fluorocarbon mixture was obtained. This material was subjected to gas chromatography [liquid phase:
1,6-bis(1,1,12-trihydroperfluorododecyloxy)hexane, carrier: 60 to 80 mesh chromosorb PAW, carrier: helium], IR, ¹⁹ F NMR, Mass, etc. analysis revealed that almost no It was pure perfluoro(N-vinylhexamethyleneimine). The conversion rate is
The yield was 100% and 84.0%. Perfluoro(N-vinylhexamethyleneimine) has a boiling point of 102-103.0°C, n ²⁰ _D 1.3046, d ²⁰ ₄ 1.8298
The spectroscopic data are as follows. ^19F NMR data Chemical shift (ppm, CFCl ₃ standard) - 96.1 (d, d) - 106.1 (d, d) - 141.1 (d, d) Coupling constant (Hz) -=47, -=55, -=116 Mass spectrometry data m/z 395 M ⁺ 376 [M-F] ⁺ 345 C ₇ F ₁₃ N ⁺ Infrared absorption spectrum data 1809 cm ^-1 (CF ₂ = CF-) Example 2 Using the same reactor as in Example 1, the raw material as 2
The reaction was carried out in the same manner as in Example 1, except that a product obtained by electrolytically fluorinating hexamethyleneiminopropionate methyl ester (celledrain compound) was used. The product contained 41.1% by weight of perfluoro(2-hexamethyleneiminopropionyl fluoride). 5.02 g of the fluorocarbon mixture (containing 2.06 g of perfluoro(2-hexamethyleneiminopropionyl fluoride)) was fed into the reactor over a period of 30 minutes and heated. As a result, 3.68 g of the fluorocarbon mixture was condensed and collected in the trap cooled to -78°C. When this product was analyzed in the same manner as in Example 1,
It contained 1.54g of perfluoro(N-vinylhexamethyleneimine). The conversion rate was 100%, and the yield of perfluoro(N-vinylhexamethyleneimine) was 87.5% based on the charged perfluoro(2-heximinopropionyl fluoride). Example 3 Using the same reactor as in Example 1, it was filled with 87.5 g of powdered sodium carbonate, and a product obtained by electrolytic fluorination of 3-hexamethyleneiminopropionate methyl ester (celdrain compound) was used as a raw material. The reaction was carried out in the same manner as in the example except that the reaction temperature was 220°C. The product contained 17.7% by weight of perfluoro(3-hexamethyleneiminopropionyl fluoride) and 18.5% of its isomer perfluoro[3-(methylpiperazino)propionyl fluoride].
It contained % by weight. 12.49 g of the fluorocarbon mixture was fed to the reactor over a period of 45 minutes and pyrolyzed, resulting in 7.69 g of fluorocarbon being condensed and collected in the cooling trap. When this product was analyzed in the same manner as in Example 1,
It contained 1.68g of perfluoro(N-vinylhexamethyleneimine) and 1.69g of perfluoro[N-vinyl(methylpiperazine)]. The conversion rate was 100%, and the yield of perfluoro(N-vinylhexamethyleneimine) was:
88.5% based on charged perfluoro(3-hexamethyleneiminopropionyl fluoride)
It was hot.

Claims (1)

[Claims] 1 formula Perfluoro(N-vinylhexamethyleneimine) represented by 2 General formula (R in the formula is [Formula] or [Formula]) A method for producing perfluoro(N-vinylhexamethyleneimine) characterized by heating a perfluoro compound represented by the following at a temperature in the range of 100 to 500°C .