JP2023046124A - Manufacturing method of unsaturated carboxylic acid hexafluoro isopropyl ester - Google Patents

Abstract

To provide a method for industrially advantageously manufacturing unsaturated carboxylic acid hexafluoro isopropyl ester with a simple operation, high yield and in an economic view point.SOLUTION: The present invention pertains to a manufacturing method of an ester represented by the following formula (1): [In formula (1), X represents a hydrogen atom, a halogen atom, or a methyl group], which comprises contacting hexafluoroisopropanol and an unsaturated carboxylic acid halide represented by the following formula (2) in a mixed solvent containing a water-immiscible organic solvent and water.SELECTED DRAWING: None

Description

The present invention relates to a method for producing unsaturated carboxylic acid hexafluoroisopropyl ester.

Unsaturated carboxylic acid hexafluoroisopropyl ester is a useful compound as a raw material monomer for polymers.
For example, hexafluoroisopropyl α-chloroacrylate, which is one of the unsaturated carboxylic acid hexafluoroisopropyl esters, is used as a raw material monomer for copolymers that are used as main chain scission type positive resists in fields such as semiconductor manufacturing. used (see, for example, Patent Document 1).

As a method for producing such an unsaturated carboxylic acid hexafluoroisopropyl ester, for example, Patent Document 2 discloses that methacrylic acid chloride and 1,1,1,3,3,3-hexafluoro A method of reacting isopropanol (hereinafter sometimes simply referred to as "hexafluoroisopropanol") in pyridine, and a method of reacting acrylic acid with trifluoroacetic anhydride as a dehydration condensation agent to obtain acrylic anhydride. and further reacting the acrylic anhydride with hexafluoroisopropanol.

Further, Patent Document 3 discloses a method of reacting hexafluoroisopropanol and methacrylic acid in the presence of phosphoric anhydride as a dehydration condensation agent as a method for producing unsaturated carboxylic acid hexafluoroisopropyl ester. ing.

Furthermore, in Patent Document 4, as a method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester, water is added when reacting hexafluoroisopropanol with acrylic anhydride or methacrylic anhydride in the presence of a base. A method is disclosed which is characterized by coexistence as a solvent.

JP 2021-067811 A U.S. Pat. No. 3,177,185 JP-A-2-295948 JP 2008-150339 A

Here, since hexafluoroisopropanol, which is a raw material for the unsaturated carboxylic acid hexafluoroisopropyl ester, contains two trifluoromethyl groups, which are strong electron-withdrawing groups, and is a highly acidic secondary alcohol, It has low reactivity and hardly undergoes an esterification reaction of unsaturated carboxylic acids. Therefore, in the method of reacting methacrylic acid chloride and hexafluoroisopropanol in pyridine disclosed in Patent Document 2, the yield of unsaturated carboxylic acid hexafluoroisopropyl ester is extremely low even under heating conditions. . Also, in the method of reacting acrylic acid with trifluoroacetic anhydride as a dehydration condensation agent to produce acrylic anhydride, and further reacting this acrylic anhydride with hexafluoroisopropanol, unsaturated The yield of carboxylic acid hexafluoroisopropyl ester is low.

In the method of Patent Document 3, although unsaturated carboxylic acid hexafluoroisopropyl ester can be obtained in a relatively high yield, phosphoric anhydride, which is a dehydration condensing agent, easily absorbs water, so there is a problem that it is very difficult to handle. . Another problem is that the reacted phosphoric anhydride reacts with water to form phosphoric acid, which makes the reaction mixture viscous and difficult to remove from the reactor. Furthermore, when acrylic acid is used as a raw material, the resulting ester yield is low and oligomers are formed. There is also the problem that only the acid hexafluoroisopropyl ester is obtained.

In the method of Patent Document 4, since water is used as a solvent, the product after the reaction can be easily separated and purified, and the unsaturated carboxylic acid hexafluoroisopropyl ester can be obtained in a high yield. Acrylic anhydride and methacrylic anhydride are difficult to obtain in high purity and in large quantities, and due to this, acrylic and methacrylic anhydride tend to be very expensive. Therefore, industrially, there is a problem that the use of these raw materials is disadvantageous from the point of view of economy.

The present invention has been made under such circumstances, and an object of the present invention is to produce an unsaturated carboxylic acid hexafluoroisopropyl ester in a simple operation with a high yield and industrially advantageous in terms of economy. It is to provide a manufacturing method.

The inventor of the present invention has made intensive studies in order to achieve the above object. Then, the present inventors have found that by contacting hexafluoroisopropanol and an unsaturated carboxylic acid halide in a predetermined mixed solvent, an unsaturated carboxylic acid hexafluoroisopropyl ester can be obtained by a simple operation with a high yield, and , found that it can be produced industrially advantageously in terms of economy, and have completed the present invention.

［式（１）中、Ｘは、水素原子、ハロゲン原子又はメチル基を表す。］で表される不飽和カルボン酸ヘキサフルオロイソプロピルエステルの製造方法であって、１，１，１，３，３，３－ヘキサフルオロイソプロパノールと、下記式（２）：

［式（２）中、Ｘは、式（１）中のＸと同じあり、Ｙは、フッ素原子、塩素原子、臭素原子及びヨウ素原子からなる群から選択されるハロゲン原子を表す。］で表される不飽和カルボン酸ハライドとを、非水混和性有機溶媒及び水を含む混合溶媒下で接触させる工程を含み、前記混合溶媒が、アルカリ金属炭酸塩、アルカリ金属炭酸水素塩、アルカリ金属リン酸塩及びアルカリ金属リン酸水素塩からなる群から選択される少なくとも１種のアルカリ金属塩と、相間移動触媒とを含む、不飽和カルボン酸ヘキサフルオロイソプロピルエステルの製造方法である。このような不飽和カルボン酸ヘキサフルオロイソプロピルエステルの製造方法であれば、不飽和カルボン酸ヘキサフルオロイソプロピルエステルを、簡便な操作で収率良く、且つ、経済性の面で工業的に有利に製造できる。 That is, an object of the present invention is to advantageously solve the above-mentioned problems, and the present invention provides the following formula (1):

[In formula (1), X represents a hydrogen atom, a halogen atom, or a methyl group. ] A method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester represented by the following formula (2):

[In Formula (2), X is the same as X in Formula (1), and Y represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. ] in a mixed solvent containing a water-immiscible organic solvent and water, wherein the mixed solvent is an alkali metal carbonate, an alkali metal hydrogen carbonate, an alkali A method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester comprising at least one alkali metal salt selected from the group consisting of metal phosphates and alkali metal hydrogen phosphates and a phase transfer catalyst. With such a method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester, an unsaturated carboxylic acid hexafluoroisopropyl ester can be produced in a simple operation with a high yield and is economically advantageous from an industrial point of view. .

In the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention, the phase transfer catalyst is preferably at least one salt selected from the group consisting of alkylammonium halide salts and alkylammonium sulfates.
If the phase transfer catalyst is at least one salt selected from the group listed above, the unsaturated carboxylic acid hexafluoroisopropyl ester can be produced in a simpler operation with a higher yield and more economically. It can be produced industrially advantageously.

In the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention, the unsaturated carboxylic acid halide represented by the formula (2) is acrylic acid chloride, α-chloroacrylic acid chloride and α-bromoacrylic acid chloride. It is preferably at least one compound selected from the group consisting of:
If the unsaturated carboxylic acid halide represented by formula (2) is at least one compound selected from the above-listed group, the unsaturated carboxylic acid hexafluoroisopropyl ester is industrially more economical. can be produced advantageously.

In the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention, X in the formula (1) is preferably a hydrogen atom, a chlorine atom or a methyl group.
Unsaturated carboxylic acid hexafluoroisopropyl ester, wherein X in formula (1) is a hydrogen atom, a chlorine atom or a methyl group, has good stability and is therefore more advantageous as a monomer used in the production of polymers. can be used.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester in a simple operation, in a high yield, and economically and industrially advantageous.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the unsaturated carboxylic acid hexafluoroisopropyl ester produced using the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention is not particularly limited, and can be used, for example, for producing a polymer. It can be advantageously used as a monomer. Specifically, a polymer whose main chain is cut and reduced in molecular weight by irradiation with ionizing radiation such as an electron beam or light with a short wavelength such as ultraviolet rays, which can be suitably used as a main chain scission type positive resist. It can be advantageously used for manufacturing and the like.

(Method for producing unsaturated carboxylic acid hexafluoroisopropyl ester)
In the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention, 1,1,1,3,3,3-hexafluoroisopropanol ((CF ₃ ) ₂ CHOH) and formula (2) described later and an unsaturated carboxylic acid halide in the presence of a mixed solvent containing a non-water-miscible organic solvent and water. The mixed solvent includes at least one alkali metal salt selected from the group consisting of alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal phosphates and alkali metal hydrogenphosphates, and a phase transfer catalyst. including.
According to the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention, an unsaturated carboxylic acid hexafluoroisopropyl ester can be produced in a simple operation with a high yield and is industrially advantageous in terms of economy. . Although the reason why the unsaturated carboxylic acid hexafluoroisopropyl ester can be produced in a simple operation with a high yield is not necessarily clear, it is presumed as follows.

First, hexafluoroisopropanol, which is a raw material for unsaturated carboxylic acid hexafluoroisopropyl ester, has six fluorine atoms, but has the property of being mixed with water in an arbitrary ratio. Water can be preferably used as the solvent. In addition, hexafluoroisopropanol contains two trifluoromethyl groups with very high electron-withdrawing properties, and therefore has a property of being highly acidic among alcohols.
In the present invention, by using a mixed solvent containing a water-immiscible organic solvent and water, in water, hexafluoroisopropanol and an alkali metal salt acting as a base are converted into hexafluoroisopropanol by a weak acid-alkali reaction. (Since it is dissolved in water, it can exist in an ionically dissociated state.) is formed. It is believed that contact between the hexafluoroisopropoxide salt thus formed and the unsaturated carboxylic acid halide produces the unsaturated carboxylic acid hexafluoroisopropyl ester. Then, the produced unsaturated carboxylic acid hexafluoroisopropyl ester is present in the water-immiscible organic solvent, and the by-produced alkali metal halide is present in water. can be separated into In addition, the phase transfer catalyst contained in the mixed solvent facilitates the contact between the hexafluoroisopropoxide salt and the unsaturated carboxylic acid halide, thereby promoting the production of the unsaturated carboxylic acid hexafluoroisopropyl ester.
For the above reasons, it is believed that the unsaturated carboxylic acid hexafluoroisopropyl ester can be produced in a high yield by a simple operation.

<Unsaturated carboxylic acid halide>
The unsaturated carboxylic acid halide used in the method for producing unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention is a compound represented by the following formula (2).

In addition, in Formula (2), X is the same as X in Formula (1) demonstrated below. That is, in formula (2), X represents a hydrogen atom, a halogen atom or a methyl group. Since the unsaturated carboxylic acid halide represented by formula (2) is available at a relatively low cost, by using it as a raw material, unsaturated carboxylic acid hexafluoroisopropyl ester can be industrially produced economically. can be produced advantageously.
The unsaturated carboxylic acid halide represented by formula (2) includes, for example, acrylic acid chloride; methacrylic acid chloride, α-fluoroacrylic acid chloride, α-chloroacrylic acid chloride, α-bromoacrylic acid chloride, α-iodine α-substituted acrylic acid chloride such as acrylic acid chloride; acrylic acid bromide; α-substituted acrylic acid bromide such as methacrylic acid bromide, α-chloroacrylic acid bromide and α-bromoacrylic acid bromide. Among these, acrylic acid chloride, methacrylic acid chloride, α-fluoroacrylic acid chloride, α-chloroacrylic acid chloride and α are more inexpensive and readily available, and are more economically advantageous industrially. - It is preferable to use at least one compound selected from the group consisting of bromoacrylic acid chloride, and at least one compound selected from the group consisting of acrylic acid chloride, α-chloroacrylic acid chloride and α-bromoacrylic acid chloride It is more preferred to use compounds of the species.

Since acrylic acid chloride, methacrylic acid chloride and the like are industrially produced, commercially available products can be used as they are. An α-substituted unsaturated carboxylic acid halide substituted with a halogen atom at the α-position can be synthesized according to the method described in the following literature.
α-Fluoroacrylic acid chloride can be synthesized, for example, according to the method described in JP-T-2004-505939. Specifically, 2-chloro-2-fluoropropionic acid obtained by reacting 2,2-dichloropropionic acid with hydrogen fluoride is treated with sodium hydroxide to form 2-fluoroacrylic acid. By mixing the 2-fluoroacrylic acid with thionyl chloride and heating under reflux, the target 2-fluoroacrylic acid chloride (α-fluorine atom luoroacrylic acid chloride) can be obtained.
α-Chloroacrylic acid chloride can be synthesized, for example, according to the method described in JP-A-2002-173467. Specifically, α-chloroacrylic acid chloride can be obtained by reacting α-chloroacrylic acid with thionyl chloride or oxalyl chloride.
α-Bromoacrylic acid chloride can be synthesized, for example, according to the method described in JP-A-2005-126340. Specifically, 2-bromoacrylic acid chloride (α-bromoacrylic acid chloride) can be obtained by reacting 2,3-dibromopropionyl chloride with triethylamine for dehydrobromination.

The amount of the unsaturated carboxylic acid halide represented by formula (1) to be used is preferably 1.1 mol or more, more preferably 1.5 or more, preferably 3 mol or less, and more preferably 1 mol of hexafluoroisopropanol as a raw material. It is 2.5 mol or less.
When the amount of the unsaturated carboxylic acid halide represented by formula (1) used is at least the above lower limit, the yield of the desired unsaturated carboxylic acid hexafluoroisopropyl ester can be improved. On the other hand, when the amount of the unsaturated carboxylic acid halide represented by formula (1) is equal to or less than the above upper limit, undesirable side reactions such as the formation of oligomers of acrylic acids can be suppressed.

<Alkali metal salt>
The alkali metal salt used in the method for producing the unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention is selected from the group consisting of alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal phosphates and alkali metal hydrogen phosphates. is at least one metal salt.
Examples of alkali metal carbonates include lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate.
Examples of alkali metal hydrogencarbonates include sodium hydrogencarbonate, potassium hydrogencarbonate, cesium hydrogencarbonate and the like.
Examples of alkali metal phosphates include trisodium phosphate and tripotassium phosphate.
Examples of alkali metal hydrogen phosphates include disodium hydrogen phosphate and dipotassium hydrogen phosphate.
The alkali metal salt is preferably an alkali metal carbonate such as sodium carbonate, potassium carbonate, or cesium carbonate, since a hexafluoroisoproxide salt can be efficiently formed in water. At least one alkali metal salt selected from the group consisting of potassium carbonate is more preferable, and potassium carbonate is even more preferable because the unsaturated carboxylic acid hexafluoroisopropyl ester can be produced in a higher yield.

The amount of the alkali metal salt used is preferably 1 mol or more, more preferably 1.2 mol or more, preferably 3 mol or less, more preferably 2 mol or less per 1 mol of hexafluoroisopropanol as a raw material.
When the amount of the alkali metal salt used is at least the above lower limit, the hexafluoroisoproxide salt can be efficiently formed in water, and the yield of the unsaturated carboxylic acid hexafluoroisopropyl ester can be improved. On the other hand, if the amount of the alkali metal salt used is equal to or less than the above upper limit, insufficient dissolution in water and precipitation of the alkali metal salt during the reaction can be suppressed, and post-treatment can be facilitated. .

<Mixed solvent>
The mixed solvent used in the method for producing the unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention contains a water-inmiscible organic solvent and water. The mixed solvent contains at least one alkali metal salt selected from the group consisting of alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal phosphates and alkali metal hydrogen phosphates, and a phase transfer catalyst. include.

The amount of water contained in the mixed solvent is not particularly limited as long as it is an amount capable of dissolving the alkali metal salt. Above, preferably 50 times or less, more preferably 10 times or less.
When the amount of water is at least the above lower limit, it is possible to prevent the concentration of the alkali metal salt from becoming too high, and to prevent the reaction from proceeding rapidly and undesired side reactions from occurring at the same time. On the other hand, if the amount of water is equal to or less than the above upper limit, the amount of wastewater is reduced, and post-treatment after the reaction can be facilitated.

The water-immiscible organic solvent contained in the mixed solvent is a solvent that is essentially immiscible with water. As the water-immiscible organic solvent, it is preferable to use a solvent having a boiling point higher than that of the desired unsaturated carboxylic acid hexafluoroisopropyl ester. With such a water-immiscible organic solvent, the produced unsaturated carboxylic acid hexafluoroisopropyl ester can be easily separated from the water-immiscible organic solvent by distillation or the like.
The water-immiscible organic solvent can be appropriately selected according to the type of unsaturated carboxylic acid hexafluoroisopropyl ester. , xylene, benzotrifluoride, bis(trifluoromethyl)benzene, chlorobenzene and other aromatic hydrocarbon solvents. Among these, inexpensive solvents such as toluene, xylene, benzotrifluoride and bis(trifluoromethyl)benzene can be preferably used. In addition, although the reason is not clear, toluene or xylene can be preferably used as the water-immiscible organic solvent because the unsaturated carboxylic acid hexafluoroisopropyl ester can be produced in a higher yield.

The amount of the water-immiscible organic solvent contained in the mixed solvent is preferably 0.5 times or more, more preferably 1 time or more, preferably 5 times or less, more preferably 5 times or less, on a volume basis, with respect to the amount of water. less than twice as much.
When the amount of the water-immiscible organic solvent used is at least the above lower limit, the extraction amount of the target unsaturated carboxylic acid hexafluoroisopropyl ester increases, and the yield can be improved. On the other hand, if the amount of the water-immiscible organic solvent used is equal to or less than the above upper limit, it is possible to suppress an excessive amount of use and economically produce the unsaturated carboxylic acid hexafluoroisopropyl ester.
As used herein, the term “amount of water-immiscible organic solvent contained in the mixed solvent” refers to non It refers to the amount of water-miscible organic solvent.

<Phase transfer catalyst>
The phase transfer catalyst used in the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention is not particularly limited as long as it is generally used in a two-phase mixed solvent reaction. quaternary salts such as halides and quaternary phosphonium halides; polyethers such as crown ethers and polyoxyalkylene glycols; aminoalcohols; Among these, quaternary salts are particularly preferred because they are present on the aqueous phase side after completion of the reaction and are easy to separate. Quaternary salts consist of a cation (positive ion) formed by bonding four carbon-containing substituents to a heteroatom such as a nitrogen atom and a phosphorus atom, and a counter anion (negative ion).

The heteroatom is not particularly limited as long as it is an atom of group 5B of the periodic table, but nitrogen and phosphorus atoms are preferable, and have good compatibility with hexafluoroisopropoxide ions formed in water, and yield the product. Nitrogen atoms are particularly preferred because they can improve the rate. Further, when an unsaturated carboxylic acid chloride is used as the raw material unsaturated carboxylic acid halide, a nitrogen atom is particularly preferable as the hetero atom because it is compatible with a chlorine atom.
The number of carbon atoms in the four carbon-containing substituents of the heteroatom is not particularly limited, but is usually 1 or more and 30 or less, preferably 1 or more and 20 or less. Such carbon-containing substituents are not particularly limited as long as they contain a carbon directly bonded to a heteroatom, and examples thereof include alkyl groups, aryl groups, aralkyl groups, alkenyl groups and alkynyl groups. These carbon-containing substituents include substituents that do not affect the reaction, such as alkoxy groups, halogen atoms, and alkylthio groups; A divalent substituent or the like may be included. Also, the carbon-containing substituents may be bonded to each other to form a ring. The carbon-containing substituents are preferably alkyl, aryl and aralkyl groups.

Specific examples of carbon-containing substituents include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, octyl group, lauryl group, and hexadecyl group; phenyl group, 2-methylphenyl group, 4-methylphenyl group, aryl groups such as 4-ethylphenyl group and naphthyl group; aralkyl groups such as benzyl group, 2-methylbenzyl group, 4-methylbenzyl group, 2-methoxybenzyl group and 4-methoxybenzyl group; The quaternary salts in which the carbon-containing substituents are bonded to each other to form a ring include pyridinium, picolinium, and the like in which the carbon-containing substituents are cyclic and bonded to a nitrogen atom. These carbon-containing substituents may have substituents that do not affect the reaction.

In the quaternary salts, three or more carbon-containing substituents preferably having 2 or more carbon atoms, more preferably 3 or more carbon atoms, preferably 7 or less carbon atoms, more preferably 5 or less carbon atoms are bonded to the heteroatom. It is preferable to be
A quaternary salt in which three or more carbon-containing substituents having the number of carbon atoms within the above range are bonded can improve the yield of unsaturated carboxylic acid hexafluoroisopropyl ester. Although the reason for this is not clear, it is presumed to be due to the interaction with hexafluoroisopropoxide ions formed in water, the solubility of the resulting cations in water-immiscible organic solvents, and the like.

Counter anions (negative ions) include, for example, halides, hydroxides, and hydrogen sulfate ions, preferably halides or hydrogen sulfate ions, and more preferably halides. Halides include, but are not particularly limited to, fluoride, bromide, chloride, and iodide, preferably bromide and chloride.

Specific examples of quaternary salts include quaternary ammonium halides, quaternary phosphonium halides, quaternary ammonium hydroxides, quaternary phosphonium hydroxides, quaternary ammonium hydrogensulfates, quaternary class phosphonium hydrogen sulfates, and the like. Among these, quaternary ammonium halides, quaternary ammonium hydrogensulfates, or quaternary phosphonium halides are preferable, and have good compatibility with hexafluoroisopropoxide ions formed in water, and unsaturated carboxylic acid hexa Quaternary ammonium halides or quaternary ammonium hydrogensulfates are more preferred, and quaternary ammonium halides are even more preferred, since they can improve the yield of fluoroisopropyl ester.

Specific quaternary ammonium halides include, for example, tetramethylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, cetyltrimethylammonium bromide, benzyltriethyl ammonium chloride, trioctylmethylammonium chloride and the like.
Examples of quaternary ammonium hydrogensulfates include tetramethylammonium hydrogensulfate and tetrabutylammonium hydrogensulfate.
The quaternary phosphonium halides include tetrabutylphosphonium bromide, benzyltriphenylphosphonium chloride, butyltriphenylphosphonium bromide and the like.
Among those listed above, tetrabutylammonium bromide, tetrabutylammonium chloride, cetyltrimethylammonium bromide, benzyltriethylammonium chloride, trimethylbenzylammonium bromide, tetrabutylammonium hydrogensulfate are preferred, and tetrabutylammonium bromide, tetrabutylammonium hydrogensulfate Salt is more preferred.

Examples of crown ethers include crown ethers such as 15-crown-5, 18-crown-6, dibenzo-18-crown-6, dibenzo-24-crown-8 and dicyclohexyl-18-crown-6. be done.
Examples of polyoxyalkylene glycols include polyethylene glycol, polypropylene glycol, polyethylene glycol monomethyl ether, and the like.
Examples of aminoalcohols include tris[2-(2-methoxyethoxy)ethyl]amine, cryptate and the like.

The phase transfer catalysts described above may be used alone or in combination of two or more.

The amount of the phase transfer catalyst used can be appropriately selected depending on the reaction conditions, but it is usually 0.001 mol or more, preferably 0.01 mol or more, more preferably 0.03 mol, usually 1 mol or less per 1 mol of hexafluoroisopropanol as a raw material. , preferably 0.1 mol or less, more preferably 0.07 mol or less.

<Additive>
In the method for producing hexafluoroisopropyl ester of unsaturated carboxylic acid of the present invention, additives may be used as long as they do not contradict the purpose. Additives include polymerization inhibitors and the like.

In the method for producing unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention, a polymerization inhibitor may be added to the reaction system as necessary in order to prevent unexpected side reactions (polymerization) during the reaction. . Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, tert-butyl-catechol, 2, 6-di-tert-butyl-4-methylphenol, pentaerythritol, tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 2-sec-butyl-4,6-dinitrophenol and the like Phenolic compounds; N,N'-diisopropylparaphenylenediamine, N,N'-di-2-naphthylparaphenylenediamine, N-phenylene-N'-(1,3-dimethylbutyl)paraphenylenediamine, N,N Amine compounds such as '-bis(1,4-dimethylphenyl)-paraphenylenediamine, N-(1,4-dimethylphenyl)-N'-phenyl-paraphenylenediamine; 4-hydroxy-2,2,6 ,6-tetramethylpiperidine-N-oxyl, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl, bis(1-oxyl-2,2,6,6-tetramethylpiperidine- 4-yl) N-oxyl compounds such as sebacate; metal compounds such as copper, copper (II) chloride and iron (III) chloride;

The amount of the polymerization inhibitor used can be determined as appropriate, but it is preferably 10 ppm or more, more preferably 50 ppm or more, with respect to hexafluoroisopropanol as a raw material, since good effects can be exhibited.

<Reaction conditions>
In the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention, the contact between hexafluoroisopropanol and the unsaturated carboxylic acid halide is not particularly limited as long as it is carried out in the above mixed solvent. It can be carried out by adding hexafluoroisopropanol to the containing aqueous solution, then adding a water-immiscible organic solvent and a phase transfer catalyst, and further dropping the unsaturated carboxylic acid halide there.

The temperature at which hexafluoroisopropanol and the unsaturated carboxylic acid halide are brought into contact (reaction temperature) is a temperature at which the aqueous alkali metal salt solution does not solidify and the reaction does not proceed excessively, and is preferably 0° C. or higher. It is more preferably 10° C. or higher, preferably 40° C. or lower, and more preferably 30° C. or lower.
When the reaction temperature is at least the above lower limit, the reaction rate can be efficiently advanced, and the time required to complete the reaction can be shortened. On the other hand, if the reaction temperature is equal to or lower than the above upper limit, polymerization of raw materials, products, and the like can be suppressed.

The reaction time can be appropriately determined depending on the reaction temperature and the like, and is preferably 0.5 hours or longer, more preferably 1 hour or longer, preferably 20 hours or shorter, and preferably 10 hours or shorter. more preferred.
When the reaction time is at least the above lower limit, the reaction can be completed and the yield can be improved. On the other hand, when the reaction time is equal to or less than the above upper limit, polymerization of raw materials, products, etc. can be suppressed.

After completion of the reaction, for example, in order to phase-separate the water-immiscible organic solvent phase and the aqueous phase, a step of allowing the mixed solvent containing the product to stand, the water-immiscible organic solvent phase and the aqueous phase A step of phase separation, a step of removing the aqueous phase from the phase-separated mixed solvent, a step of washing the remaining water-immiscible organic solvent phase with a dilute acid such as dilute hydrochloric acid, saturated aqueous sodium bicarbonate and saturated brine, after washing An arbitrary step such as a step of drying (dehydrating) the water-immiscible organic solvent phase with a drying agent such as magnesium sulfate and a step of distilling the dried water-immiscible organic solvent phase may be performed.
The progress of the reaction can be tracked by gas chromatography or the like. Completion of the reaction can be confirmed by disappearance of the raw material hexafluoroisopropanol.

<Unsaturated Carboxylic Acid Hexafluoroisopropyl Ester>
The unsaturated carboxylic acid hexafluoroisopropyl ester obtained by the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention is a compound represented by the following formula (1).

In addition, in Formula (1), X represents a hydrogen atom, a halogen atom, or a methyl group.
That is, the unsaturated carboxylic acid hexafluoroisopropyl ester represented by formula (1) includes, for example, hexafluoroisopropyl acrylate, hexafluoroisopropyl methacrylate, α-fluoroacrylate hexafluoroisopropyl ester, α-chloro Examples include hexafluoroisopropyl acrylate, α-bromoacrylate hexafluoroisopropyl ester, and α-iodoacrylate hexafluoroisopropyl ester.
X in formula (1) is preferably a hydrogen atom, a chlorine atom, or a methyl group, since it has good stability and can be used more advantageously as a monomer for polymer production. That is, the unsaturated carboxylic acid hexafluoroisopropyl ester represented by formula (1) is preferably acrylate hexafluoroisopropyl ester, α-chloroacrylate hexafluoroisopropyl ester or methacrylate hexafluoroisopropyl ester.

EXAMPLES The present invention will be described in more detail below with reference to examples, but the scope of the present invention is not limited by the following examples. In addition, "%" represents "% by mass" unless otherwise specified.

Analysis conditions for gas chromatography analysis (GC analysis) performed in Examples and Comparative Examples are as follows.

<Analysis conditions>
Apparatus: Agilent-7890 (manufactured by Agilent)
Column: Inert Cap-1 (manufactured by GL Sciences, length 60 m, inner diameter 0.25 mm, film thickness 1.5 μm)
Column temperature: Hold at 60°C for 10 minutes, then heat up to 260°C at a heating rate of 20°C/min, then hold at 260°C for 10 minutes Injection temperature: 250°C
Detector temperature: 250°C
carrier gas: nitrogen split ratio: 100/1
Detector: FID

[Synthesis Example 1] Synthesis of α-chloroacrylic acid chloride In a 1 L three-necked flask equipped with a condenser and a dropping funnel, 53.3 g (0.5 mol) of 2-chloroacrylic acid, 2 g of p-methoxyphenol and chloride were added. 300 ml of methylene was added and dissolved. The flask (reactor) was immersed in a water bath, the contents were stirred at room temperature, and 10 drops of N,N-dimethylformamide were added thereto. A solution prepared by dissolving 82.5 g (0.65 mol) of oxalyl chloride in 100 ml of methylene chloride was dropped from the dropping funnel into the reactor over 2 hours. During this time, the gas generated during the reaction was introduced from the top of the cooling tube into a gas washing bottle containing 500 ml of water. After the dropwise addition of oxalyl chloride was completed, the contents were stirred as they were for 1.5 hours, and then heated to 35°C in a water bath. About 40 minutes after the start of heating, the heating was stopped when the generation of gas stopped and the pressure in the system became negative. Most of the methylene chloride and unreacted oxalyl chloride were distilled off from the reactor contents while warming to 35° C. using a rotary evaporator. 1 g of p-methoxyphenol was added to the obtained residual liquid, and distillation was carried out under a reduced pressure of 10 kPa. Fractions having a boiling point of 47 to 49° C. were collected to obtain 36 g of α-chloroacrylic acid chloride. (Yield: 57%).

[Synthesis Example 2] Production of α-bromoacrylic acid chloride 25 g (0.1 mol) of 2,3-dibromopropionyl chloride and 120 ml of methylene chloride were placed in a 300 ml three-necked flask equipped with a condenser and a dropping funnel. . The flask (reactor) was immersed in an ice water bath, and 15.2 g (0.15 mol) of triethylamine was added dropwise from the dropping funnel over 25 minutes while stirring the contents. Thirty minutes after the completion of the dropwise addition, the reactor was lifted from the ice water bath and stirred at room temperature for 1 hour. Salts produced by the reaction were removed by filtration under reduced pressure. Most of the methylene chloride was distilled off from the resulting filtrate while warming to 35° C. using a rotary evaporator. Using the resulting residual liquid, distillation was performed under a reduced pressure of 2 kPa, and a fraction having a boiling point of 39 to 40° C. was collected to obtain 12.5 g of α-bromoacrylic acid chloride (yield 74%). ).

[Example 1]
10.36 g (0.075 mol) of potassium carbonate and 30 ml of water were placed in a 200 ml round bottom flask equipped with a dropping funnel and a stirrer, and the potassium carbonate was dissolved by stirring. A round bottom flask was immersed in an ice water bath and 8.4 g (0.05 mol) of 1,1,1,3,3,3-hexafluoroisopropanol was added. After stirring for about 10 minutes, 30 ml of toluene and 0.8 g (0.0025 mol) of tetrabutylammonium bromide as a phase transfer catalyst were added and vigorously stirred. Then, 6.8 g (0.075 mol) of acrylic acid chloride was dropped from the dropping funnel over about 20 minutes. After the contents were stirred as such for 30 minutes, the stirring was continued for an additional 6 hours at 20°C. The contents are transferred to a separating funnel, and after separating the aqueous phase, the remaining water-immiscible organic solvent phase is washed with 20 ml each of hydrochloric acid (concentration: 5% by mass), saturated aqueous sodium bicarbonate, and saturated brine, It was dried with magnesium sulfate. The magnesium sulfate was removed while washing with a small amount of toluene to obtain 29.52 g of a toluene solution containing the product. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 8.19 g of hexafluoroisopropyl acrylate (yield: 73.7%).

[Example 2]
Various operations were carried out in the same manner as in Example 1, except that the water-immiscible organic solvent toluene was changed to cyclopentylmethyl ether to obtain 26.67 g of a cyclopentylmethyl solution containing the product. rice field. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 7.12 g of hexafluoroisopropyl acrylate (yield: 64.1%).

[Example 3]
In Example 1, various Work-up yielded 28.46 g of a toluene solution containing the product. This solution was analyzed by gas chromatography and found to contain 7.92 g of hexafluoroisopropyl acrylate (yield: 71.3%).

[Example 4]
In Example 1, the same procedure as in Example 1 was performed except that 0.8 g (0.0025 mol) of tetrabutylammonium bromide as a phase transfer catalyst was changed to 0.43 g (0.0025 mol) of tetramethylammonium hydrogensulfate. Various operations were carried out with a 24.81-g toluene solution containing the product was obtained. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 7.87 g of hexafluoroisopropyl acrylate (yield: 70.9%).

[Example 5]
In Example 1, in the same manner as in Example 1, except that 0.8 g (0.0025 mol) of tetrabutylammonium bromide as a phase transfer catalyst was changed to 1.01 g (0.0025 mol) of triocrylmethylammonium chloride. Various operations were performed to obtain 25.85 g of a toluene solution containing the product. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 6.73 g of hexafluoroisopropyl acrylate (yield: 60.6%).

[Example 6]
In Example 1, the same procedure as in Example 1 was performed except that 0.8 g (0.0025 mol) of tetrabutylammonium bromide as a phase transfer catalyst was changed to 0.85 g (0.0025) of tetrabutylammonium hydrogensulfate. Various operations were carried out with a 27.37-g toluene solution containing the product was obtained. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 8.38 g of hexafluoroisopropyl acrylate (yield: 75.5%).

[Example 7]
In Example 1, various Work-up yielded 25.96 g of a toluene solution containing the product. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 6.64 g of hexafluoroisopropyl acrylate (yield: 59.8%).

[Example 8]
In Example 6, various operations were performed in the same manner as in Example 6, except that 10.36 g (0.075 mol) of potassium carbonate was changed to 5.83 g (0.075 mol) of sodium carbonate. .75 g of toluene solution was obtained. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 7.49 g of hexafluoroisopropyl acrylate (yield: 67.5%).

[Example 9]
In Example 6, various operations were performed in the same manner as in Example 6, except that 10.36 g (0.075 mol) of potassium carbonate was changed to 7.51 g (0.075 mol) of potassium hydrogen carbonate. 29.24 g of toluene solution was obtained. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 6.92 g of hexafluoroisopropyl acrylate (yield: 62.3%).

[Example 10]
In Example 6, various operations were performed in the same manner as in Example 6, except that 10.36 g (0.075 mol) of potassium carbonate was changed to 13.06 g (0.075 mol) of dipotassium hydrogen phosphate. 24.34 g of a toluene solution containing This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 7.18 g of hexafluoroisopropyl acrylate (yield: 64.6%).

[Example 11]
In Example 6, various operations were performed in the same manner as in Example 6, except that 10.36 g (0.075 mol) of potassium carbonate was changed to 10.65 g (0.075 mol) of disodium hydrogen phosphate. 25.86 g of a toluene solution containing This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 7.02 g of hexafluoroisopropyl acrylate (yield: 63.2%).

[Example 12]
In Example 6, various operations were performed in the same manner as in Example 6, except that 10.36 g (0.075 mol) of potassium carbonate was changed to 10.61 g (0.05 mol) of tripotassium phosphate, and the product was 30.05 g of a toluene solution containing This solution was analyzed by gas chromatography and found to contain 7.48 g of hexafluoroisopropyl acrylate (yield: 67.3%).

[Example 13]
In Example 6, 6.8 g (0.075 mol) of acrylic acid chloride was changed to 7.8 g (0.075 mol) of methacrylic acid chloride, and all toluene of the water-immiscible organic solvent was changed to p-xylene. performed various operations in the same manner as in Example 6 to obtain 30.70 g of p-xylene solution containing the product. When this solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard substance, it contained 9.826 g of hexafluoroisopropyl methacrylate (yield: 83.2%).

[Example 14]
In Example 13, except that 7.8 g (0.075 mol) of methacrylic acid chloride was changed to 9.38 g (0.075 mol) of 2-chloroacrylic acid chloride obtained in Synthesis Example 1. Various operations were carried out in the same manner to obtain 29.44 g of p-xylene solution containing the product. This solution was analyzed by gas chromatography using α-chloroacrylic acid hexafluoroisopropyl ester as a standard substance and found to contain 8.78 g of α-chloroacrylic acid hexafluoroisopropyl ester (yield: 68 .5%).

[Example 15]
In Example 13, except that 7.8 g (0.075 mol) of methacrylic acid chloride was changed to 12.76 g (0.075 mol) of 2-bromoacrylic acid chloride obtained in Synthesis Example 2. Various operations were carried out in the same manner to obtain 30.29 g of p-xylene solution containing the product. This solution was analyzed by gas chromatography using α-bromoacrylic acid hexafluoroisopropyl ester as a standard and contained 9.54 g of α-bromoacrylic acid hexafluoroisopropyl ester (yield: 63 .2%).

[Comparative Example 1]
8.4 g (0.05 mol) of 1,1,1,3,3,3-hexafluoroisopropanol and 6.8 g (0.075 mol) of acrylic acid chloride were added to a 100-ml round-bottomed flask equipped with a dropping funnel and a stirrer. ), and 70 ml of dry cyclopentyl methyl ether were added and stirred. The reactor was cooled with ice water, 6.0 g (0.075 mol) of pyridine was added with a dropping funnel over about 15 minutes, and the mixture was stirred for about 1 hour. After that, the temperature of the reactor was raised to 25° C., and stirring was continued for 7 hours. The content was transferred to a separating funnel, washed with 40 ml of water, 30 ml of 5% by mass hydrochloric acid, 30 ml of saturated aqueous sodium bicarbonate and 30 ml of saturated brine in that order, and the organic phase was dried over magnesium sulfate. Magnesium sulfate was removed while washing with a small amount of cyclopentyl methyl ether to obtain 55.01 g of cyclopentyl methyl ether solution containing the product. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 0.89 g of hexafluoroisopropyl acrylate (yield: 8.0%).

[Comparative Example 2]
Various operations were carried out in the same manner as in Example 1, except that the phase transfer catalyst tetrabutylammonium bromide was not added, to obtain 27.29 g of a toluene solution containing the product. This solution was analyzed by gas chromatography using hexafluoroisopropyl acrylate as a standard and contained 5.38 g of hexafluoroisopropyl acrylate (yield: 34.7%).

As is clear from the results of the above Examples and Comparative Examples, the method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester of the present invention produces an unsaturated carboxylic acid hexafluoroisopropyl ester in a simple operation with a high yield, and It can be seen that this is an economically advantageous method for industrial production.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester in a simple operation, in a high yield, and economically and industrially advantageous.

Claims (4)

Formula (1) below:

[In formula (1), X represents a hydrogen atom, a halogen atom, or a methyl group. ]
A method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester represented by
1,1,1,3,3,3-hexafluoroisopropanol;
Formula (2) below:

[In Formula (2), X is the same as X in Formula (1), and Y represents a halogen atom selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. ]
A step of contacting an unsaturated carboxylic acid halide represented by in a mixed solvent containing a water-immiscible organic solvent and water,
The mixed solvent contains at least one alkali metal salt selected from the group consisting of alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal phosphates and alkali metal hydrogen phosphates, and a phase transfer catalyst. , a method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester. 2. The method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester according to claim 1, wherein the phase transfer catalyst is at least one salt selected from the group consisting of alkylammonium halide salts and alkylammonium sulfates. The unsaturated carboxylic acid halide represented by the formula (2) is at least one compound selected from the group consisting of acrylic acid chloride, α-chloroacrylic acid chloride and α-bromoacrylic acid chloride. 3. A method for producing the unsaturated carboxylic acid hexafluoroisopropyl ester according to 1 or 2. The method for producing an unsaturated carboxylic acid hexafluoroisopropyl ester according to any one of claims 1 to 3, wherein X in the formula (1) is a hydrogen atom, a chlorine atom or a methyl group.