JP2009256305A - Method for producing fluorocarboxylic acid ester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an objective fluorocarboxylic acid ester within a relatively short time by using a 2-fluoroalkylethyl chloride and a carboxylate as raw materials. <P>SOLUTION: The method for producing a fluorocarboxylic acid ester represented by formula (III) comprises reacting a carboxylate represented by formula (I) with a 2-fluoroalkylethylchloride represented by formula (II): RfCH<SB>2</SB>CH<SB>2</SB>Cl in the presence of a phase transfer catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

（a）
（式中、Ｘはフッ素原子または−ＣＨ_２ＣＨ_２Ｙ、Ｙは臭素またはヨウ素）
で表される２−含フッ素アルキルエチルハロゲン化物とを反応させる方法が広く知られている（特許文献１）。この製造方法に使用される２−含フッ素アルキルエチルハロゲン化物としては製造、入手の容易性から２−パーフルオロアルキルエチルアイオダイドが一般的に使用されるが、ヨウ素は高価な資源であるために使用後に回収、再利用を行わない場合には得られた製品の採算性が悪化する原因となり得る。従って特許文献１の方法で含フッ素カルボン酸エステルを製造する場合には反応後に副生したヨウ化物塩からヨウ素を回収する必要性が生じるが、この場合は原料の一つであるカルボン酸金属塩由来の不純物が混入することによって高純度でのヨウ素の回収が困難である。 As a manufacturing method of fluorine-containing carboxylic acid ester, carboxylic acid metal salt and the following general formula (a):

(A)
(Wherein X is a fluorine atom or —CH ₂ CH ₂ Y, Y is bromine or iodine)
The method of making it react with 2-fluorine-containing alkyl ethyl halide represented by these is widely known (patent document 1). As 2-fluorinated alkylethyl halides used in this production method, 2-perfluoroalkylethyl iodide is generally used because of its ease of production and availability, but iodine is an expensive resource. If the product is not collected and reused after use, the profitability of the obtained product may deteriorate. Therefore, when producing a fluorine-containing carboxylic acid ester by the method of Patent Document 1, it is necessary to recover iodine from the iodide salt by-produced after the reaction. In this case, the carboxylic acid metal salt which is one of the raw materials It is difficult to recover iodine with high purity by mixing impurities derived from it.

  On the other hand, in carrying out the production method similar to Patent Document 1, a quaternary compound is used for the purpose of carrying out the reaction at a lower temperature by using a solvent cheaper than the monohydric alcohol shown as an effective solvent in Patent Document 1. A method using an ammonium salt or a quaternary phosphonium salt is known (Patent Document 2). According to this method, it is possible to use milder conditions for the selection of the solvent and the temperature in carrying out the reaction than in the production method of Patent Document 1, but the halide (iodide) to be recovered or reused. Or, when a quaternary salt is mixed in the bromide salt, it is very difficult to recover iodine or bromine with high purity.

In order to solve this problem, 2-perfluoroalkylethyl iodide is reacted with bromine or chlorine alone to form 2-perfluoroalkylethyl bromide or 2-perfluoroalkylethyl chloride by a halogen exchange reaction in advance. In the case where iodine is to be collected in advance, chlorine is superior to bromine in that it is relatively easy to handle and inexpensive, and the halogen exchange reaction easily proceeds. However, 2-perfluoroalkylethyl chloride is poor in reactivity with carboxylic acid metal salts, and fluorinated carboxylic acid esters compared to the case where 2-perfluoroalkylethyl iodide or 2-perfluoroalkylethyl bromide is used as a raw material. Productivity is greatly reduced.
Japanese Examined Patent Publication No. 39-18112 (US Pat. No. 3,329,557) Shoko 48-30611

  The main object of the present invention is to provide a method for producing a target fluorinated carboxylic acid ester in a relatively short time using 2-fluorinated alkylethyl chloride and a carboxylate as raw materials.

  As a result of intensive studies to achieve the above object, the present inventor has achieved a relatively short time according to the method of reacting 2-fluorinated alkylethyl chloride with a carboxylate in the presence of a phase transfer catalyst. The present inventors have found that a fluorine-containing carboxylic acid ester can be obtained, and have completed the present invention.

（Ｉ）
（式中、Ｒ^１、Ｒ^２およびＲ³は、同一又は異なって、それぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のパーフルオロアルキル基、一般式：Ｃ_ｍＨ_ｎＦ_ｐ（式中、ｍは１〜１０の整数、ｎは、１〜２ｍの整数、ｐは２ｍ＋１−ｎである）で表される炭素数１〜１０のポリフルオロアルキル基、炭素数６〜１８のアリール基、炭素数６〜１８のパーフルオロアリール基、炭素数６〜１８のポリフルオロアリール基又は炭素数７〜１９のアラルキル基、Ｍはアルカリ金属、ｑは０〜８の整数である）
で表されるカルボン酸塩と、下記一般式（II）：
ＲｆＣＨ_２ＣＨ_２Ｃｌ (II)
（式中、Ｒｆは、炭素数１〜１３のパーフルオロアルキル基、一般式：Ｃ_ｍＨ_ｎＦ_ｐ（式中、ｍは１〜１３の整数、ｎは、１〜２ｍの整数、ｐは２ｍ＋１−ｎである）で表される炭素数１〜１３であるポリフルオロアルキル基である）
で表される２−含フッ素アルキルエチルクロリドとを反応させる事を特徴とする、下記一般式（III）：

（III）
（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒｆおよびｑは上記に同じ）
で表される含フッ素カルボン酸エステルの製造方法。 That is, this invention provides the manufacturing method of the following fluorine-containing carboxylic acid ester.
In the presence of a phase transfer catalyst, the following general formula (I):

(I)
(In formula, R < ¹ >, R < ² > and R < ³ > are the same or different, respectively, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C1-C10 alkyl group, and C1-C10 perfluoroalkyl group, the general _formula: C _m (where, m is an integer of from 1 to 10, n is an integer of 1 to 2 m, p is a is 2m + 1-n) H n F p carbon atoms represented by 1-10 polyfluoroalkyl groups, C6-C18 aryl groups, C6-C18 perfluoroaryl groups, C6-C18 polyfluoroaryl groups, or C7-C19 aralkyl groups, M Is an alkali metal, q is an integer of 0-8)
And the following general formula (II):
RfCH ₂ CH ₂ Cl (II)
(In the formula, Rf is a C 1-13 perfluoroalkyl group, general formula: C _m H _n F _p (where m is an integer of 1-13, n is an integer of 1-2 m, p is 2m + 1-n) and a polyfluoroalkyl group having 1 to 13 carbon atoms.
The following general formula (III), characterized in that it is reacted with 2-fluorinated alkylethyl chloride represented by the following formula:

(III)
(Wherein R ¹ , R ² , R ³ , Rf and q are the same as above)
The manufacturing method of fluorine-containing carboxylic acid ester represented by these.

  It is preferable that the phase transfer catalyst is at least one selected from the group consisting of a quaternary ammonium salt, a phosphonium salt, a pyridinium salt, and a polyether.

  According to the present invention, the intended fluorine-containing carboxylic acid ester can be obtained in a relatively short time. Further, according to the present invention, since no iodine compound is used, it is not necessary to recover iodine. The obtained fluorine-containing carboxylic acid ester can be effectively used for various applications such as a polymer material raw material and an organic synthetic intermediate.

（式中、Ｒ^１、Ｒ^２およびＲ³は、同一又は異なって、それぞれ、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子、炭素数１〜１０のアルキル基、炭素数１〜１０のパーフルオロアルキル基、一般式：Ｃ_ｍＨ_ｎＦ_ｐ（式中、ｍは１〜１０の整数、ｎは、１〜２ｍの整数、ｐは２ｍ＋１−ｎである）で表される炭素数１〜１０のポリフルオロアルキル基、炭素数６〜１８のアリール基、炭素数６〜１８のパーフルオロアリール基、炭素数６〜１８のポリフルオロアリール基又は炭素数７〜１９のアラルキル基、Ｍはアルカリ金属、ｑは０〜８の整数である）
で表されるものである。 The carboxylate used as a raw material in the method of the present invention is represented by the following general formula (I):

(In formula, R < ¹ >, R < ² > and R < ³ > are the same or different, respectively, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C1-C10 alkyl group, and C1-C10 perfluoroalkyl group, the general _formula: C _m (where, m is an integer of from 1 to 10, n is an integer of 1 to 2 m, p is a is 2m + 1-n) H n F p carbon atoms represented by 1-10 polyfluoroalkyl groups, C6-C18 aryl groups, C6-C18 perfluoroaryl groups, C6-C18 polyfluoroaryl groups, or C7-C19 aralkyl groups, M Is an alkali metal, q is an integer of 0-8)
It is represented by

In the general formula (I), q is preferably 0 to 5, and particularly preferably 0 to 3. R ¹ , R ² and R ³ are preferably a hydrogen atom, a methyl group or a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom).
As specific examples of the carboxylate, any compound represented by the general formula (I) can be used without particular limitation. However, in view of availability, acrylic acid, α-chloroacrylic acid, methacrylic acid, croton Preference is given to alkali metal salts of acids, 3-butenoic acid, 2-pentenoic acid, 3-pentenoic acid and 4-pentenoic acid. Examples of alkali metals are lithium, sodium and potassium. As the carboxylate, sodium or potassium salts of acrylic acid and methacrylic acid are particularly preferable.
The amount of the carboxylate represented by the general formula (I) is not particularly limited, but in consideration of economy, it is 1.0 to 2.0 with respect to 1 mol of 2-fluorinated alkylethyl chloride. It is preferable to set it as about a mole, and it is more preferable to set it as about 1.0-1.3 mole.

2-Fluorine-containing alkyl ethyl chloride which is the other raw material of the present invention has the following general formula (II):
RfCH ₂ CH ₂ Cl (II)
(In the formula, Rf is a C 1-13 perfluoroalkyl group, general formula: C _m H _n F _p (where m is an integer of 1-13, n is an integer of 1-2 m, p is 2m + 1-n) and a polyfluoroalkyl group having 1 to 13 carbon atoms.
It is represented by

  In the general formula (II), the Rf group (particularly, the perfluoroalkyl group having 1 to 13 carbon atoms) may be either linear or branched. The Rf group preferably has 1 to 10 carbon atoms, particularly 2 to 8 carbon atoms.

  Preferred functional groups for Rf include trifluoromethyl, pentafluoroethyl, heptafluoro-n-propyl, 1,1,1,2,3,3,3-heptafluoro-2-propyl, nonafluoro Butyl group, undecafluoropentyl group, 1,1,2,2,3,4,4,4-octafluoro-3-trifluoromethylbutyl group, tridecafluorohexyl group, pentadecafluoroheptyl group, 1, 1,2,2,3,3,4,4,5,6,6,6-dodecafluoro-5-trifluoromethylhexyl group, heptadecafluorooctyl group, nonadecafluorononyl group, 1,1,2, 2,3,3,4,4,5,5,6,6,7,8,8,8-hexadecafluoro-7-trifluoromethyloctyl group, henicosafluorodecyl group, tricho Fluoroundecyl group, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,10,10,10-icosafluoro-9-tri Fluoromethyldecyl group, pentacosafluorododecyl group, heptacosafluorotridecyl group, 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8, Examples include 9, 9, 10, 10, 11, 12, 12, 12-tetracosafluoro-11-trifluoromethyldodecyl group.

  Among these, pentafluoroethyl group, 1,1,1,2,3,3,3-heptafluoro-2-propyl group, nonafluorobutyl group, 1,1,2,2,3,4,4,4 -Octafluoro-3-trifluoromethylbutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, 1,1,2,2,3,3,4,4,5,5,6,6,7, 8,8,8-hexadecafluoro-7-trifluoromethyloctyl group, henicosafluorodecyl group, 1,1,2,2,3,3,4,4,5,5,6,6,7 , 7,8,8,9,10,10,10-icosafluoro-9-trifluoromethyldecyl group is more preferred, pentafluoroethyl group, 1,1,1,2,3,3,3-heptafluoro- 2-propyl group, nonafluorobutyl group, 1,1 2,2,3,4,4,4-octafluoro-3-trifluoromethylbutyl group, tridecafluorohexyl group, 1,1,2,2,3,3,4,4,5,6,6 The 6,6-dodecafluoro-5-trifluoromethylhexyl group is particularly preferred.

  An important feature of the process of the present invention is that the carboxylate is reacted with 2-fluorinated alkylethyl chloride in the presence of a phase transfer catalyst. As a result, the reaction rate is greatly accelerated, and the target fluorine-containing carboxylic acid ester can be obtained in a relatively short time.

  Examples of the phase transfer catalyst include quaternary ammonium salts, phosphonium salts, pyridinium salts, calixarene, and polyether compounds such as crown ethers, cryptands, and polyalkylene glycol ethers.

（IV）
（式中：Ｒ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、それぞれ、同一または異なって、水素原子、炭素数１〜３０のアルキル基、炭素数７〜１３のアラルキル基または炭素数６〜３０のアリール基であり、Ａ⁺は窒素原子またはリン原子、Ｂ^-は1価の陰イオンである。ただしＲ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷のうちの３つが水素原子である場合、他の１つは水素原子ではない）
で表される第４級アンモニウム塩、ホスホニウム塩を用いることができる。 Although it does not specifically limit as a quaternary ammonium salt and a phosphonium salt, For example, following general formula (IV)

(IV)
(In the formula: R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same or different and are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or 6 to 30 carbon atoms. A ⁺ is a nitrogen atom or a phosphorus atom, B ^- is a monovalent anion, provided that when three of R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen atoms, Is not a hydrogen atom)
The quaternary ammonium salt and phosphonium salt represented by these can be used.

  In the general formula (IV), the alkyl group having 1 to 30 carbon atoms may be either linear or branched. As the aryl group having 6 to 30 carbon atoms, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthranyl group and the like are preferable. The aralkyl group having 7 to 13 carbon atoms is preferably a benzyl group, a phenethyl group, a naphthylmethyl group, or the like. In the aryl group and aralkyl group, part or all of the hydrogen atoms bonded to the aryl skeleton may be substituted with other elements or functional groups.

  In particular, as the quaternary ammonium salt, the cation is tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tributylmethylammonium, trioctylmethylammonium, trilaurylmethylammonium, di-cured tallow alkyldimethylammonium, Benzyltrimethylammonium, benzyltriethylammonium, benzyltripropylammonium, benzyltributylammonium, phenyltrimethylammonium, etc., where the anion is a halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), Hydrogen sulfate ion, hydroxide ion, carboxylate ion, sulfonate ion, tetrafluoroborate ion, tetrapheny Borate ion, hexafluorophosphate ion, is preferred a hexafluoroantimonate ion or the like.

  Similarly, as a quaternary phosphonium salt, the cation is tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, tributylmethylphosphonium, trioctylmethylphosphonium, trilaurylmethylphosphonium, di-cured tallow alkyldimethylphosphonium, Benzyltrimethylphosphonium, benzyltriethylphosphonium, benzyltripropylphosphonium, benzyltributylphosphonium, phenyltrimethylphosphonium, etc., where the anion is a halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), Hydrogen sulfate ion, hydroxide ion, carboxylate ion, sulfonate ion, tetrafluoroborate ion, tetrapheny Borate ion, hexafluorophosphate ion, is preferred a hexafluoroantimonate ion or the like.

(V)
（式中：Ｒ⁸は水素原子、炭素数１〜３０のアルキル基、炭素数７〜１３のアラルキル基、炭素数６〜３０のアリール基またはアミノ基であり、Ｃ^-はハロゲン化物イオン（フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオンなど）、硫酸水素イオン、カルボン酸イオン、スルホン酸イオン、テトラフルオロホウ酸イオン、テトラフェニルホウ酸イオン、ヘキサフルオロリン酸イオン、ヘキサフルオロアンチモン酸イオン）
で表されるピリジニウム塩を用いることができる。 The pyridinium salt is not particularly limited, but for example, the following general formula (V)

(V)
(Wherein R ⁸ is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, an aryl group or an amino group having 6 to 30 carbon atoms, and C ⁻ is a halide ion (fluorine ion). Chloride ion, chloride ion, bromide ion, iodide ion, etc.), hydrogen sulfate ion, carboxylate ion, sulfonate ion, tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, hexafluoroantimonic acid ion)
The pyridinium salt represented by these can be used.

In the above general formula (V), in particular, R ⁸ in the formula is a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group. Eicosanyl group, and the anion is halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), hydrogen sulfate ion, carboxylate ion, sulfonate ion, tetrafluoroborate ion, tetra Those which are phenylborate ion, hexafluorophosphate ion, hexafluoroantimonate ion and the like are preferable.

As the crown ether, for example, 12-crown 4-ether, 15-crown 5-ether, 18-crown 6-ether, 24-crown 8-ether and the like are preferable.
As the cryptand, for example, [1,1,1] cryptand, [2,1,1] cryptand, [2,2,1] cryptand, [2,2,2] cryptand and the like are preferable.
As the calixarene, for example, calix [4] arene, calix [5] arene, calix [6] arene and the like are preferable.

Polyether compounds other than cyclic ethers such as the above-mentioned crown ethers and cryptands can be used as the polyether compound without limitation, but among them, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether Diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether and the like are preferable.
These phase transfer catalysts may be used alone or as a solution, or may be used by being fixed on a polymer. A phase transfer catalyst can be used individually by 1 type or in mixture of 2 or more types.

  The amount of the phase transfer catalyst used is not particularly limited, but it is preferably about 0.0005 to 2 moles per mole of 2-fluorinated alkylethyl chloride in consideration of reaction rate, economy and the like. , And more preferably about 0.005 to 0.2 mol.

  In carrying out the production method of the present invention, a polymerization inhibitor may be used in order to prevent polymerization of the carboxylate which is a raw material.

The polymerization inhibitor can be used without any particular limitation, but hydroquinone, methoquinone, 4-methoxy-1-naphthol and phenothiazine are preferable from the viewpoint of availability.
The amount of the polymerization inhibitor used is not particularly limited. However, in consideration of economy and the like, the amount is preferably about 0.00001 to 1 mol with respect to 1 mol of 2-fluorinated alkylethyl chloride. More preferably, it is about 0001 to 0.05 mol. A polymerization inhibitor can be used individually by 1 type or in mixture of 2 or more types.

The production method of the present invention may not use a solvent, but may be carried out in the presence of a solvent. When using a solvent, 2-methyl-2-butanol, 3-methyl-1-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 1-heptanol 2-heptanol, 3-heptanol, 4-heptanol, 1-pentanol, 2-pentanol, 3-pentanol, 3-methylpentanol, 1-hexanol, cyclohexanol, 3-ethyl-3-pentanol, 2-methyl-1-cyclohexanol, 3-methyl-1-cyclohexanol, 4-methyl-1-cyclohexanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-nonanol, 1-decanol 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetra Decanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 4-methyl-1-heptanol, 5-methyl-1-heptanol, 6-methyl-1-heptanol, 2-methyl-4-heptanol, 3-methyl-4-heptanol, 4-methyl-4-heptanol, 1,2,3,4-tetrahydro- 2-naphthol, 2-ethyl-1-hexanol, n-amyl alcohol, 1-phenylethanol and 2-phenylethanol are preferred. Of these, 2-methyl-2-propanol and 2-methyl-2-butanol are particularly preferable.
The solvent can be used alone or in combination of two or more.
The amount of the solvent is not limited, but may be 3000 parts by weight or less, for example, 5 to 1000 parts by weight with respect to a total of 100 parts by weight of the carboxylate and the 2-fluorinated alkylethyl chloride.

  The specific method for carrying out the production method of the present invention is not particularly limited, but an example of the production method is as follows.

First, a carboxylate, 2-fluorinated alkylethyl chloride, and a phase transfer catalyst are introduced into a pressurizable reaction apparatus such as an autoclave, and the inside of the apparatus is replaced with an inert gas. Reduce the pressure to about 09 MPa. At this time, the reaction apparatus may be cooled with an appropriate cryogen in order to prevent loss of raw materials due to reduced pressure.
Next, the temperature of the reactor after depressurization is raised, and the reaction is carried out while maintaining a predetermined temperature. Although the reaction temperature is not particularly limited, it is usually about 0 to 250 ° C., preferably about 100 to 200 ° C. in consideration of the reaction rate, the safety of the apparatus, and the economy.

  The obtained fluorine-containing carboxylic acid ester may be further purified by a known method such as extraction, distillation, recrystallization, column chromatography, liquid separation, or washing according to a conventional method, if necessary.

  Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples.

Example 1
In a 200 mL autoclave, 38.30 g (0.100 mol) of 2- (tridecafluorohexyl) ethyl chloride, 11.69 g (0.106 mol) of potassium acrylate, 74.30 g (1.002 mol) of tert-butyl alcohol, hydroquinone 115.9 mg (1.053 mmol), 1-4.0 mg (0.113 mmol) of p-methoxyphenol and 1.40 g (5.037 mmol) of tetrabutylammonium chloride as a catalyst were charged and the container was sealed and heated to 180 ° C. Stir for 4 hours. The vessel was then cooled to room temperature and the contents analyzed by gas chromatography. The conversion of 2- (tridecafluorohexyl) ethyl chloride was 53.2 mol%.

Example 2
In an autoclave with a volume of 200 mL, 38.28 g (0.100 mol) of 2- (tridecafluorohexyl) ethyl chloride, 11.69 g (0.106 mol) of potassium acrylate, 74.13 g (1.000 mol) of tert-butyl alcohol, hydroquinone Charge 116.1 mg (1.054 mmol), 13.7 mg (0.110 mmol) of p-methoxyphenol and 1.70 g (5.010 mmol) of tetrabutylphosphonium bromide as a catalyst, and seal the container and heat to 180 ° C. Stir for 4 hours. The vessel was then cooled to room temperature and the contents analyzed by gas chromatography. The conversion of 2- (tridecafluorohexyl) ethyl chloride was 92.5 mol%.

Example 3
In a 200 mL autoclave, 38.27 g (0.100 mol) 2- (tridecafluorohexyl) ethyl chloride, 11.80 g (0.107 mol) potassium acrylate, 74.12 g (1.002 mol) tert-butyl alcohol, hydroquinone 116.4 mg (1.057 mmol), p-methoxyphenol 13.8 mg (0.111 mmol) and 1.35 g (5.761 mmol) of 18-crown-6 ether as a catalyst were charged and the vessel was sealed and heated to 180 ° C. The mixture was stirred for 4 hours. The vessel was then cooled to room temperature and the contents analyzed by gas chromatography. The conversion of 2- (tridecafluorohexyl) ethyl chloride was 90.8 mol%.

Example 4
In a 200 mL autoclave, 38.28 g (0.100 mol) of 2- (tridecafluorohexyl) ethyl chloride, 11.68 g (0.106 mol) of potassium acrylate, 74.16 g (1.001 mol) of tert-butyl alcohol, hydroquinone 115.6 mg (1.050 mmol), p-methoxyphenol 14.3 mg (0.115 mmol) and cetylpyridinium bromide 1.92 g (4.994 mmol) as a catalyst were charged, and the container was sealed and heated to 180 ° C. Stir for hours. The container was then cooled to room temperature and the contents were analyzed by gas chromatography. The conversion of 2- (tridecafluorohexyl) ethyl chloride was 69.2 mol%.

Comparative Example 1
In an autoclave with a volume of 200 mL, 38.31 g (0.100 mol) of 2- (tridecafluorohexyl) ethyl chloride, 11.68 g (0.106 mol) of potassium acrylate, 74.35 g (1.003 mol) of tert-butyl alcohol, hydroquinone 115.9 mg (1.053 mmol) and p-methoxyphenol 13.9 mg (0.112 mmol) were added, and the container was sealed, heated to 180 ° C. and stirred for 4 hours. The vessel was then cooled to room temperature and the contents analyzed by gas chromatography. The conversion of 2- (tridecafluorohexyl) ethyl chloride was 13.3 mol%. When the heating was further continued, the conversion rate was 49.0 mol% even after 20 hours.

  From the above Examples and Comparative Examples, it can be confirmed that the reaction is greatly accelerated by adding the phase transfer catalyst.

  The polymer of the present invention is useful as a soil release agent having excellent water absorption, antifouling properties and soil release properties.

Claims (2)

In the presence of a phase transfer catalyst, the following general formula (I):

(In formula, R < ¹ >, R < ² > and R < ³ > are the same or different, respectively, a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a C1-C10 alkyl group, and C1-C10 perfluoroalkyl group, the general _formula: C _m (where, m is an integer of from 1 to 10, n is an integer of 1 to 2 m, p is a is 2m + 1-n) H n F p carbon atoms represented by 1-10 polyfluoroalkyl groups, C6-C18 aryl groups, C6-C18 perfluoroaryl groups, C6-C18 polyfluoroaryl groups, or C7-C19 aralkyl groups, M Is an alkali metal, q is an integer of 0-8)
And the following general formula (II):
RfCH ₂ CH ₂ Cl (II)
(In the formula, Rf is a C 1-13 perfluoroalkyl group, general formula: C _m H _n F _p (where m is an integer of 1-13, n is an integer of 1-2 m, p is 2m + 1-n) and a polyfluoroalkyl group having 1 to 13 carbon atoms.
The following general formula (III), characterized in that it is reacted with 2-fluorinated alkylethyl chloride represented by the following formula:

(Wherein R ¹ , R ² , R ³ , Rf and q are the same as above)
The manufacturing method of fluorine-containing carboxylic acid ester represented by these. The method according to claim 1, wherein the phase transfer catalyst is at least one selected from the group consisting of a quaternary ammonium salt, a phosphonium salt, a pyridinium salt, and a polyether.