JPS6222756A - Production of novel perfluoro(n-vinyl cyclic amine) - Google Patents

Abstract

PURPOSE:To obtain the titled compound (novel compound excluding some exceptions) useful as an intermediate of a fluorine-containing product such as a surfactant, dye, etc., from an easily available raw material in high efficiency, by heating a perfluoro(2-cyclic aminopropionic acid derivative) at a specific temperature. CONSTITUTION:The objective compound of formula IV (which is novel compound excluding the compounds of formula II and formula III) can be produced from the compound of formula I in high yield with extremely simple process, by heating the compound of formula I [A is chemical bond, CF2, O or NR (R is perfluoroalkyl); X is F, perfluoroalkoxy or OM (M is alkali metal or alkaline earth metal corresponding to univalent state)] at 100-500 deg.C, preferably 100-300 deg.C. The starting compound of formula I can be produced easily e.g. by the electrolytic fluorination of the ester or halide of the compound of formula V [A' is chemical bond, CF2, O or NR' (R' is alkyl)].

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention provides novel perfluoro(N-vinyl cyclic amines)
The present invention relates to a manufacturing method. In more detail,
The present invention makes it possible to easily obtain a new perfluoro(N-vinyl cyclic amine) useful as a synthetic intermediate for fluorine-containing products such as surfactants, dyes, agricultural chemicals, and pharmaceuticals, and as a raw material for producing fluorine-containing plastics. It relates to an efficient manufacturing method using raw materials.

BACKGROUND OF THE INVENTION 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, dyes, agricultural chemicals, pharmaceuticals, etc. It is widely used as a raw material monomer for fluorine plastics.

By the way, it is possible to produce useful compounds of the perfluoro (N-vinyl cyclic amine type).Also, by copolymerizing the compound with other fluoroolefins and introducing perfluoro cyclic amine groups into the polymer. , it is possible to reduce the crystallinity and improve the mechanical properties of the polymer.Thus, perfluoro(N-vinyl cyclic amine) is an extremely useful compound as a synthetic intermediate and a raw material for the production of fluorine-containing plastics. be.

However, since perfluorovinylamines are generally difficult to manufacture, perfluoro(N, N
-dimethylvinylamine) ((OF3)2NOF-○F2] (U.S. Pat. No. 5J11,599), perfluoro(N-vinylpiperidine) and perfluoro(N-vinylmorpholine) are only known. All of these compounds are synthesized through a two-step process: starting materials are perfluoroalkyl nitrogen radical-donating compounds [N-chlorobis(trifluoromethyl)aminothi, perfluoro(N-fluoropiperidine) and perfluoropiperidine, respectively]. (N-fluoromorpholine)] is first subjected to a free radical reaction with an appropriate fluorine-containing olefin to form a 1:1 adduct. Next, these adducts are subjected to a deHF reaction ((OF3 )2NOF is used to form an unsaturated bond. For example, in the first stage of synthesis of perfluoro(N-(vinyl)piperi9F90), which is perfluoro(N' (vinyl)cyclic amine), perfluoro(N'(vinyl)cyclic amine) is formed. -fluoropiperidine) and toberfluorocycloptene under ultraviolet irradiation to synthesize a 1:1 adduct.

The perfluoro(N-(vinyl)piperidine) thus obtained is further thermally decomposed under reduced pressure to produce the desired perfluoro(N-(vinyl)piperidine).

CF2=CF2...
(2) However, this method has the drawbacks that the yield of the 1:1 adduct in reaction formula (1) is poor (' (Y = 44%) and the reaction time is long (irradiation time: 14 hours). ing.

As described above, the manufacturing method has various drawbacks,
However, even if this method is applied to the production of other berylo(N-vinyl cyclic amines), perfluoro(N-fluoropiperidine) and perfluoro(N-
This was not possible because N-(fluoro)perfluorocyclic amines other than fluoromorpholine were not available.

Problems to be Solved by the Invention Under these circumstances, the purpose of the present invention is to obtain various perfluoro(N-vinylamine derivatives) in high yield from easily available raw materials and through simple processing. The object of the present invention is to provide a new manufacturing method that can be used.

The inventors have found that the object can be achieved by using a means for solving the problems or by heat treating the perfluoropropionate, and based on this knowledge, the present invention has been completed.

That is, the present invention uses a compound represented by the general formula % (where M is an alkali metal or alkaline earth metal corresponding to a monovalent metal) as a raw material, and uses this as a raw material.
When heated at a temperature within the range of 500°C,
Mention may be made of the above-mentioned perfluoro(bicyclic amines).

In the method of the present invention for producing this compound, for example, the methyl ester is fluorinated and
2-monomethyl propionate) is produced as a by-product.
This material can also be used as a raw material.

In addition, perfluoro (2-monomer amino propionyl olide) and perfluoro (2-monomer amino propionyl olide) obtained as described above are
Alkali metals or alkaline earth metals can be easily obtained in monocyclic amino methyl propionate. On this occasion,
Perfluoro[2
-(cyclic amine)propionyl fluoride], perfluoro[methyl 2-(cyclic amine)propionate], sodium perfluoro[2-(cyclic amine)propionate] and potassium perfluoro[2-(cyclic amine)propionate] ] is preferred.

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.
On the other hand, if it is too low, the conversion rate will decrease.

The reaction time required at this time 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 preferable to carry out the reaction under atmospheric pressure or reduced pressure. Further, the thermal decomposition reaction may be carried out using an inert gas such as nitrogen, helium, argon, carbon dioxide, etc., or an aprotic liquid compound such as polyethers as a diluent, depending on the reaction form. In this case, the dilution ratio is preferably 100 times or less.

Furthermore, in the thermal decomposition reaction, it is important that all materials used in the reaction do not contain water. In the presence of water or other proton-donating substances, N-(1,2,2,2-
Since the tetrafluoroethyl) perfluorocyclic amine is produced as a by-product, the yield of the desired perfluoro(N-vinyl cyclic amine) decreases.

However, the by-product N-(1,2,2,2-tetrafluoroethyl)perfluorocyclic amine can be defluorinated in the presence of a solid base such as potassium hydroxide, sodium hydroxide, potassium carbonate, or sodium carbonate. By causing a hydrogen reaction, it is possible to convert it into a desired perfluoro(N-vinyl cyclic amine) (see reference side).

In the method of the present invention, when perfluoro (two-ring amino probionyl fluoride) and perfluoro (two-ring amino methyl propionate) are used as raw materials, a thermal decomposition reaction is carried out in the presence of a metal salt or metal oxide. It is preferable to do so.

In this case, the desired perfluoro(N-vinyl cyclic amine) can be easily produced by continuously supplying raw materials to a packed layer of metal salts or metal oxides maintained at a predetermined temperature to carry out a thermal decomposition reaction. is obtained. There are no particular restrictions on the material of the pyrolysis reactor, but stainless steel or Hastelloy is usually used. There is no particular restriction on the type of the packed bed, and any type such as a fixed bed, moving bed, or fluidized bed can be used.

The metal salts include, for example, sodium carbonate, potassium carbonate, lithium carbonate, sodium phosphate, potassium phosphate, barium carbonate, calcium carbonate, magnesium carbonate, potassium sulfate, sodium sulfate, etc., and the metal oxides include, for example, zinc oxide. , cadmium oxide, etc. Among these, solid bases such as sodium carbonate and potassium carbonate are toxic CQF generated in thermal decomposition reactions.
It is particularly suitable because it can decompose 2.

Effects of the Invention According to the method of the present invention, a novel perfluoro(N-vinyl cyclic amine) can be obtained in high yield from easily available raw materials through an extremely simple process. -Vinyl cyclic amine) is suitable as an industrial production method.

In addition, perfluoro (N-vinyl cyclic amine) obtained by the method of the present invention can be used industrially as a synthetic intermediate for fluorine-containing products such as surfactants, dyes, agricultural chemicals, and pharmaceuticals, and as a raw material for producing fluorine-containing plastics. It is extremely valuable.

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 the raw material and a diluent gas flow rate control device were connected to the inlet side, and the outlet side was equipped with a cold trap for condensing and collecting reaction products.
．． A stainless steel tube with an inner diameter of 2.5 mm and a diameter of 2.5 mm was used as a horizontally dug pyrolysis reactor.

Into this, 85.2 ji of powdered potassium carbonate was filled horizontally to approximately the middle of the reactor, and both ends were filled with metal wool.

As a raw material, a product obtained by electrolytic fluorination of methyl 2-pyrrolidinopropionate (celledrain compound) was used as it was. This product contains 71.4 weight parts perfluoro(2-pyrrolidinopropionyl fluoride) and 7 weight parts perfluoro(methyl 2-pyrrolidinopropionate).
．． 5 weight was engaged.

First, the reactor was kept at 200°C and helium gas was added at 50°C.
The fluorocarbon mixture 5,129 (Perfluoro(2-pyrrolidinopropionyl fluoride)) 3,65.9. Perfluoro(2-pyrrolidinopropionyl fluoride) 0.38
[containing g]] was supplied to the flash evaporator over a period of 33 minutes using a minute metering pump, and after being vaporized and mixed with the helium gas that was quantitatively fed, the mixture was introduced into the reactor. When the reaction product was condensed and collected in a trap cooled to -78°C on the outlet side, a fluorocarbon mixture 3.39.9% was obtained.

This product was subjected to gas chromatography [liquid phase: 1.6-
His(1,1,12-trihydroperfluorododecyloxy)hexane, Carrier: 60-80 mesichromosorb PAW, Carrier: Helium 11R, I9FNM
When analyzed by R1Mass etc., the majority was perfluoro(N-vinylpyrrolidine) (2,72fl)
and the other impurity was perfluoro(N-ethylpyrrolidine) (o,6yy).

The conversion rate was 100%, and the yield of perfluoro(N-vinylpyrrolidine) was 83.8% based on perfluoro(2-pyrrolidinopropionyl fluoride) and perfluoro(methyl 2-pyrrolidinopropionate). %Met. The physical properties of perfluoro(N-vinylpyrrolidine) are shown in the attached table.

Example 2 As in Example 1, a product obtained by electrolytic fluorination of methyl 2-pyrrolidinopropionate (celdrain compound) was used as it was as a raw material. This product contains 6 perfluoro(2-pyrrolidinoglobionyl fluoride).
9.8% by weight, and 6.8% by weight of perfluoro(methyl 2-pyrrolidinopropionate).

First, 100. Into a fluororesin flask, 201/ml of water, 1 s of the above fluorocarbon mixture, 6 g, 10.9 g of C perfluoro(2-pyrrolidinoglopionyl fluoride), and a Belf Azt neck (
(Containing 1.1 g of methyl 2-pyrrolidinopropionate)], and the mixture was heated to 80° C. for 1 hour while stirring with a magnetic stirrer. When the fluorocarbon layer was analyzed by GC, perfluoro(2-pyrrolidinoglopionyl fluoride) and perfluoro(methyl 2-pyrrolidinopropionate) no longer remained.

Next, phenolphthalein was added as an indicator to this, and concentrated potassium hydroxide aqueous solution was added dropwise under water cooling until it became slightly alkaline to neutralize it. As a result, most of the fluorocarbon layer migrated to the water layer, but a small amount of fluorocarbon (2,60/i) remained, which was removed using a separating funnel. Next, the contents were transferred to a 200 m round bottom flask, most of the water was removed using a rotary evaporator, and the flask was further heated to 50° C. for 7 hours to vacuum dry.

The thermal decomposition reaction was carried out as follows.

That is, a trap was connected to the flask containing the above-mentioned perfluoro(potassium 2-pyrrolidinopropionate), and the flask was cooled with liquid nitrogen. While reducing the pressure from the end of the trap with a vacuum pump, the flask was heated in an oil bath, and the temperature was raised from 165° C. to 200° C. over 20 minutes, and this temperature was further maintained for 5 minutes.

Next, while flowing helium gas at a rate of 1501111/min, the trap was immersed in a refrigerant at -78°C to vaporize and remove the mixed carbon dioxide gas. The fluorocarbon purified and collected in this way is 5,15
, li+.

When this product was analyzed in the same manner as in Example 1, it was found that perfluoro(N-vinylpyrrolidine) 4.51.9 and N
-(1,2,2,2-tetrafluoroethyl)ophtafluoropyrrolidine 0.64 g was contained.

The yield of perfluoro(N-vinylpyrrolidine) was 46.9% based on the charged perfluoro(2-pyrrolidip[1 pionyl fluoride) and perfluoro(2-pyrrolidip methyl pionate).

Example 3 Using the same reactor as in Example 1, a reaction was carried out in the same manner as in Example 1, except that perfluoro(2-morpholinopropionylnorolide) purified by GC was used as the raw material.

perfluoro(2-morpholinopropionyl fluoride) 3,21 jj was fed to the reactor over a period of 19 minutes;
Upon thermal decomposition, fluorocarbon i, asg was obtained in the cold trap.

When this product was analyzed in the same manner as in Example 1, it was found to be almost pure perfluoro(N-vinylmorpholine).
The conversion rate was 100% and the yield was 69.8%.

The physical properties of perfluoro(N-vinylmorpholine) are shown in the attached table.

Example 4 Using the same reactor as in Example 1, the reaction was carried out in the same manner as in Example 1, except that perfluoro(2-piperidinogropionylnorolide) purified by GC was used as the raw material. Ta.

Perfluoro(2-piperidinogropionyl fluoride) 3,469 was fed to the reactor over a period of 27 minutes and thermally decomposed to yield 2,81.9 of fluorocarbon in the cold trap.

When this product was analyzed in the same manner as in Example 1, it was found to be almost pure perfluorinated (N-vinylpiperidine), with a conversion rate of 100% and a yield of 96. B%.

The physical properties of perfluoro(N-vinylpiperidine) are shown in the attached table.

Example 5 The same reactor as in Example 1 was used, except that perfluoro[N-ethyl-N'-1-(fluorocarbonyl)ethelpiperazine] purified by ()O was used as the raw material. A similar reaction was performed.

When 2.38 g of perfluoro(N-ethyl-N'-'1-(fluorocarbonyl)ethylpiperazine) was fed to the reactor over 12 minutes and thermally decomposed, 1.88 f! of fluorocarbon was found in the cooling trap. Obtained.

When this product was analyzed in the same manner as in Example 1, it was found to be almost pure perfluoro(N-vinyl-N'-ethylpiperazine), with a conversion rate of 100% and a yield of 91.1%. there were.

Perfluoro(N-vinyl-N'-ethylpiperazine)
The physical property values are shown in the attached table.

Reference Example N -(1,2,2,2-tetrafluoroether)decafluoropiperidine was converted to perfluoro(1)-vinylpiperidine) by dehydrofluorination reaction as follows.

As raw materials, N-(1,2,2,2-tetrafluoroethyl)decafluoropiperidine was 57.3 tons by weight, and perfluoro(N-ethylpiperidine) was 23.0 tons by weight.
A fluorocarbon mixture containing %.

The reaction was carried out using the same reactor as in Example 2, filled with 85.49 g of powdered potassium carbonate, and at a reaction temperature of 220°C.
The same method as in Example 2 was conducted except that .

2.78 p of the fluorocarbon mixture (sealed-(1
゜2.2.2-te)・rafluoroethyl)decafluoropiperidine containing 1,59.9%] was supplied to the reactor for 25 minutes to cause a dehydrofluorination reaction, and the cooling trap contained fluorocarbon 2.249 was obtained.

When this product was analyzed in the same manner as in Example 1, it was found that perfluoro(IJ-vinylpiperidine) 0,44 ji,
It contained unreacted N-(1,4-2-tetocyfluoroether)decafluoropiperidine 0.90%.

The conversion rate was 43.3%, and the obtained perfluoro(N
-vinylpiperidine), the yield of consumed N-(1
, 2,2,2-tetrafluoroethyl)decafluoropiperidine was 67.7%.

Procedural Amendment (Voluntary) 60 Special Skills No. 178 January 1985/? Day 1, Indication of the case 1985 Patent Application No. 162682 2, Title of the invention Novel method for producing perfluoro(N-vinyl cyclic amine) 3, Person making the amendment 4, Designated representative 7, Subject of the amendment Description Detailed Explanation Column 8 Contents of Amendment (1) In the 4th part of the specification, line 13, 1. 1. HF is removed from the reaction. However, 1. HC is removed from HC.

designated agent

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A in the formula is a chemical bond, CF_2<, O< or RN<
(However, R is a perfluoroalkyl group), and X is a fluorine atom, a perfluoroalkoxy group, or -OM (However, M is an alkali metal or alkaline earth metal corresponding to a monovalent) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (A in the formula has the same meaning as above), which is characterized by heating aminopropionic acid derivatives) at a temperature within the range of 100 to 500°C. Method for producing perfluoro(N-vinyl cyclic amine) represented by