JP2005104907A - Fluorine-containing fullerenol derivative and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorine-containing fullerenol having a higher fluorine content than the fluorinated fullerene of the conventional product. <P>SOLUTION: The fluorine-containing fullerenol derivative is represented by formula (1) [wherein A is (1) a perfluoroalkenyloxy group represented by the formula : C<SB>a</SB>F<SB>2a-1</SB>O- (provided that a is an integer of 6-10) or (2) a perfluoroalkenyl-containing group represented by the formula: C<SB>a</SB>F<SB>2a-1</SB>OXCOO- (provided that a is the same as defined above; and X is a phenyl group or a naphthyl group); B is a fullerene unit represented by C<SB>20+m</SB>(provided that m is an integer of 1-100); and n+p is a number of 1-30 (provided that 1≤n≤30, 0≤p≤29, and 1≤n+p≤20+m)], and its manufacturing method is described. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fluorine-containing fullerenol derivative and a method for producing the same.

  Conventionally, various methods have been developed as a method for fluorinating fullerenes. For example, Patent Document 1 discloses a method of reacting fullerene and fluorine gas in the presence of hydrogen fluoride. Patent Document 2 discloses a method of irradiating a mixture obtained by mixing a fullerene solution with a polytetrafluoroethylene dispersion in a nonpolar solvent. In addition, as a technique related to the technical field, for example, Patent Document 3 discloses a compound having a polyfluoroalkyl group as a conductivity-imparting agent. Patent Document 4 discloses a method of coating fullerene with a polytetrafluoroethylene resin.

Thus, fullerene can be fluorinated also by a conventional fluorination method. However, in the conventional method, a fluorinated fullerene has a low fluorination rate, and in many cases, a fluorination gas that requires careful handling is used for fluorination. In addition, strictly speaking, the coating obtained by the coating method disclosed in Patent Document 4 is hardly a fluorinated fullerene.
Japanese Patent Laid-Open No. 06-24720 JP 09-118509 A JP 2003-55418 A JP 09-89973 A

  The main object of the present invention is to provide a fluorinated fullerenol derivative having a higher fluorine content than conventional fluorinated fullerenes. In addition, another object is to provide an easy and safe method for producing the fluorine-containing fullerenol derivative.

  As a result of intensive studies to achieve the above object, the present inventors have found that a specific method for producing a fluorine-containing fullerenol derivative can achieve the above object, and have completed the present invention.

That is, the present invention relates to the following fluorine-containing fullerenol derivative and a method for producing the same.
1. The following general formula (1):

〔式中、ＢはＣ_20+m（但し、ｍは１〜１００の整数）で表わされるフラーレン単位を示す。ｎ+ｐは１〜３０の数（但し、１≦ｎ≦３０、０≦ｐ≦２９、及び１≦ｎ+ｐ≦２０＋ｍを満たす）を示す。〕
で表わされる含フッ素フラレノール誘導体であって、上記Ａが、
１）Ｃ_aＦ_2a-1Ｏ−（但し、ａは６〜１０の整数）で表わされるパーフルオロアルケニルオキシ基、又は
２）Ｃ_aＦ_2a-1ＯＸＣＯＯ−〔式中、ａは前記と同じである。Ｘはフェニル基又はナフチル基を示す。〕で表わされるパーフルオロアルケニルを含有する基
であることを特徴とする含フッ素フラレノール誘導体。
２．Ｂ（ＯＨ）_q〔式中、ＢはＣ_20+m（但し、ｍは１〜１００の整数）で表わされるフラーレン単位を示す。ｑは１〜３０の整数（但し、１≦ｑ≦２０＋ｍ）を示す。〕で表わされるフラレノールと、
１）Ｃ_aＦ_2a（但し、ａは６〜１０の整数）で表わされるパーフルオロアルケン、又は
２）Ｃ_aＦ_2a-1ＯＸＣＯＹ〔式中、ａは前記と同じである。Ｘはフェニル基又はナフチル基を示す。Ｙは脱離基を示す。〕で表わされるパーフルオロアルケニルを含有する基
とを反応させることを特徴とする含フッ素フラレノール誘導体の製造方法。
３．脱離基Ｙが、ヒドロキシル基又は塩素原子である上記項２記載の製造方法。
４．上記項２又は３記載の製造方法により製造される含フッ素フラレノール誘導体。

[Wherein B represents a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). n + p is a number from 1 to 30 (provided that 1 ≦ n ≦ 30, 0 ≦ p ≦ 29, and 1 ≦ n + p ≦ 20 + m are satisfied). ]
A fluorine-containing fullerenol derivative represented by:
1) C _a F _2a-1 O— (where a is an integer of 6 to 10), or 2) C _a F _2a-1 OXCOO— wherein a is the same as above. It is. X represents a phenyl group or a naphthyl group. ] The fluorine-containing fullerenol derivative characterized by being the group containing perfluoroalkenyl represented by these.
2. B (OH) _q [wherein B represents a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). q represents an integer of 1 to 30 (where 1 ≦ q ≦ 20 + m). ] Fullerenol represented by
1) Perfluoroalkene represented by C _a F _2a (where a is an integer of 6 to 10), or 2) C _a F _2a-1 OXCOY [wherein a is the same as defined above. X represents a phenyl group or a naphthyl group. Y represents a leaving group. ] The manufacturing method of the fluorine-containing fullerenol derivative characterized by making it react with the group containing perfluoroalkenyl represented by these.
3. Item 3. The method according to Item 2, wherein the leaving group Y is a hydroxyl group or a chlorine atom.
4). 4. A fluorinated fullerenol derivative produced by the production method according to item 2 or 3.

  The fluorine-containing fullerenol derivative of the present invention has a higher fluorine content than conventional fluorinated fullerenes. For this reason, when the fluorine-containing fullerenol derivative of the present invention is used as a water repellent, a lubricant, etc., like the conventional fluorinated fullerene, it exhibits high water repellency, lubricity and the like. The fluorine-containing fullerenol derivative of the present invention is also a material having an excellent low refractive index in that it has a high fluorine content.

  According to the production method of the present invention, the fluorine-containing fullerenol derivative of the present invention can be produced easily and safely.

Fluorine-containing fullerenol derivative The fluorine-containing fullerenol derivative of the present invention has the following general formula (1):

〔式中、ＢはＣ_20+m（但し、ｍは１〜１００の整数）で表わされるフラーレン単位を示す。ｎ+ｐは１〜３０の数（但し、１≦ｎ≦３０、０≦ｐ≦２９、及び１≦ｎ+ｐ≦２０＋ｍを満たす）を示す。〕
で表わされる含フッ素フラレノール誘導体であって、上記Ａが、
１）Ｃ_aＦ_2a-1Ｏ−（但し、ａは６〜１０の整数）で表わされるパーフルオロアルケニルオキシ基、又は
２）Ｃ_aＦ_2a-1ＯＸＣＯＯ−〔式中、ａは前記と同じである。Ｘはフェニル基又はナフチル基を示す。〕で表わされるパーフルオロアルケニルを含有する基
であることを特徴とする。

[Wherein B represents a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). n + p is a number from 1 to 30 (provided that 1 ≦ n ≦ 30, 0 ≦ p ≦ 29, and 1 ≦ n + p ≦ 20 + m are satisfied). ]
A fluorine-containing fullerenol derivative represented by:
1) C _a F _2a-1 O— (where a is an integer of 6 to 10), or 2) C _a F _2a-1 OXCOO— wherein a is the same as above. It is. X represents a phenyl group or a naphthyl group. A group containing perfluoroalkenyl represented by the formula:

Examples of the fluorine-containing fullerenol derivative of the present invention include the following.
C ₆₀ (OC ₆ F ₁₁ ) _n (OH) _p
C ₇₀ (OC ₆ F ₁₁ ) _n (OH) _p
C ₆₀ (OC ₉ F ₁₇ ) _n (OH) _p
C ₇₀ (OC ₉ F ₁₇ ) _n (OH) _p

含フッ素フラレノール誘導体の製造方法
本発明の含フッ素フラレノール誘導体の製造方法は特に限定的ではないが、例えば、
Ｂ（ＯＨ）_q〔式中、ＢはＣ_20+m（但し、ｍは１〜１００の整数）で表わされるフラーレン単位を示す。ｑは１〜３０の整数（但し、１≦ｑ≦２０＋ｍ）を示す。〕で表わされるフラレノールと、
１）Ｃ_aＦ_2a（但し、ａは６〜１０の整数）で表わされるパーフルオロアルケン、又は
２）Ｃ_aＦ_2a-1ＯＸＣＯＹ〔式中、ａは前記と同じである。Ｘはフェニル基又はナフチル基を示す。Ｙは脱離基を示す。〕で表わされるパーフルオロアルケニルを含有する基
とを反応させることにより好適に製造できる。

Method for producing fluorine-containing fullerenol derivative The method for producing the fluorine-containing fullerenol derivative of the present invention is not particularly limited.
B (OH) _q [wherein B represents a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). q represents an integer of 1 to 30 (where 1 ≦ q ≦ 20 + m). ] Fullerenol represented by
1) Perfluoroalkene represented by C _a F _2a (where a is an integer of 6 to 10), or 2) C _a F _2a-1 OXCOY [wherein a is the same as defined above. X represents a phenyl group or a naphthyl group. Y represents a leaving group. It can be suitably produced by reacting with a group containing perfluoroalkenyl represented by the formula:

Hereinafter, each raw material and reaction conditions will be described.
[Fullerenol]
In the fullerenol represented by B (OH) _q , B is a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). The number of carbon atoms (20 + m) is usually 36, 60, 70, 76, 78, 80, 82 and 84. Among these, 60 and 70 carbon atoms are preferable. q is the number of hydroxyl groups of fullerenol, and is usually 1-30, preferably 10-20. However, q is in the range of 1 ≦ q ≦ 20 + m.

The method for producing such fullerenol is not particularly limited, and for example, it can be produced by treating fullerene powder with fuming sulfuric acid and then hydrolyzing it. This manufacturing method is described in the following non-patent literature, for example.
(Chiang, LY; Wang, LY; et al., J.Org.Chem.1994,59,3960)
Moreover, after making a fullerene and a halogen atom react and obtaining a halogenated fullerene, it can manufacture by making it react with a metal hydroxide. This manufacturing method is described in, for example, JP-A-2002-193861.
[Perfluoroalkene]
The perfluoroalkene represented by C _a F _2a (where a is an integer of 6 to 10) is a perfluoroalkene having 6 to 10 carbon atoms. For example, tetrafluoroethylene, hexafluoropropene or an oligomer thereof can be used. Among these, the dimer or trimer of hexafluoropropene is particularly preferable. A polymer having a high degree of polymerization has a high viscosity, and is preferably about a trimer from the viewpoint of ease of handling.

  The method for obtaining the oligomer is not particularly limited. As a method for obtaining an oligomer, for example, a method of oligomerizing perfluoroolefin in the presence of a halo ion (US Pat. No. 3,403,191), a crown ether is used as a cation scavenger, and a halo ion is activated. And oligomerization in a non-aqueous solvent using a compound containing a polyoxyalkylene group in the presence of fluorine ions (Japanese Patent Laid-Open No. 53-144508). Gazette) and the like.

  The reaction conditions of fullerenol and perfluoroalkene are not particularly limited as long as a desired fluorine-containing fullerenol derivative is obtained. Usually, after fullerenol is dispersed or dissolved in a non-aqueous polar solvent, it may be reacted with perfluoroalkene under basic conditions.

  Examples of the non-aqueous solvent include acetonitrile, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, diethyl ether and the like. Of these, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone are particularly preferable. These nonaqueous polar solvents can be used alone or in admixture of two or more.

  Examples of the basic substance include sodium carbonate, potassium carbonate, trimethylamine, triethylamine, tripropylamine, N, N-dimethylaniline, pyridine and the like. Of these, triethylamine and tripropylamine are particularly preferable.

  The ratio of reacting fullerenol with perfluoroalkene is not particularly limited, but fullerenol: perfluoroalkene (molar ratio) is usually about 1: 1 to 1:30, preferably about 1: 5 to 1:20. However, perfluoroalkene exceeding 1 mol may be reacted with 1 mol of hydroxyl group of fullerenol, and is not necessarily limited to the above range. For example, in consideration of various conditions such as reaction rate, perfluoroalkene may be reacted in excess of 30 moles with respect to 1 mole of fullerenol.

Although reaction temperature is not specifically limited, Usually, 0-100 degreeC, Preferably it is 10-60 degreeC, More preferably, it is about 20-50 degreeC. Although reaction time is not specifically limited, Usually, 5 to 15 hours, Preferably it is 5 to 10 hours.
[Group containing perfluoroalkenyl]
In the group containing perfluoroalkenyl represented by C _a F _2a-1 OXCOY, the portion represented by C _a F _2a-1 is perfluoroalkenyl, and Y is a leaving group. The type of the leaving group Y is not limited, but for example, a hydroxyl group or a halogen atom is preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like, and a chlorine atom is particularly preferable. When the leaving group Y is a hydroxyl group, examples of the group containing perfluoroalkenyl include perfluorononenyloxybenzoic acid and perfluorononenyloxyisophthalic acid. Hereinafter, the leaving group Y which is a preferred embodiment is a hydroxyl group (hereinafter referred to as “perfluoroalkenyloxy group-containing carboxylic acid”) and a chlorine atom (hereinafter referred to as “acid chloride of a perfluoroalkenyl group-containing carboxylic acid”). The group containing perfluoroalkenyl which is) will be described as an example.

  Although the manufacturing method of perfluoroalkenyloxy group containing carboxylic acid is not specifically limited, For example, it can manufacture by making the oligomer of tetrafluoroethylene or hexafluoropropene, and p-hydroxybenzoic acid or its ester react. This manufacturing method is described in, for example, Japanese Patent Laid-Open No. 50-121243.

  A method for producing an acid chloride of a perfluoroalkenyl group-containing carboxylic acid is not particularly limited. For example, an acid chloride can be produced by reacting a perfluoroalkenyl group-containing carboxylic acid with thionyl chloride.

  The reaction conditions for the fullerenol and the perfluoroalkenyloxy group-containing carboxylic acid are not particularly limited as long as the desired fluorine-containing fullerenol derivative is obtained. Usually, it can carry out similarly to a well-known esterification reaction. That is, the raw material may be heated as it is, or may be heated in the absence of a solvent or in a solvent in the presence of an acid catalyst such as sulfuric acid or p-toluenesulfonic acid. The heating temperature is usually about 50 to 200 ° C, preferably about 80 to 150 ° C when a catalyst is used. When no catalyst is used, the temperature is usually 100 to 200 ° C, preferably about 150 to 200 ° C. As the solvent, for example, benzene, toluene, dioxane and the like can be used. The ratio of the reaction between the fullerenol and the perfluoroalkenyloxy group-containing carboxylic acid is not particularly limited, but the fullerenol: perfluoroalkenyloxy group-containing carboxylic acid (molar ratio) is usually 1: 1 to 1:30, preferably 1: It is about 5 to 1:20. However, the perfluoroalkenyloxy group-containing carboxylic acid exceeding 1 mol may be reacted with 1 mol of hydroxyl group of fullerenol, and is not necessarily limited to the above range. For example, considering various conditions such as the reaction rate, the perfluoroalkenyloxy group-containing carboxylic acid may be reacted in excess of 30 moles with respect to 1 mole of fullerenol. Although reaction time is not specifically limited, Usually, 5 to 20 hours, Preferably it is 5 to 15 hours.

  The reaction conditions of fullerenol and acid chloride of perfluoroalkenyloxy group-containing carboxylic acid are not particularly limited as long as a desired fluorine-containing fullerenol derivative is obtained. Usually, in the presence of a deoxidizing agent such as triethylamine or pyridine, in a solvent such as benzene, toluene, diethyl ether, tetrahydrofuran, acetone, dimethoxyethane, N, N-dimethylformamide, dioxane or the like, usually 20 to 150 ° C., preferably May be reacted at about 50 to 100 ° C. The ratio of reacting the fullerenol with the acid chloride of the perfluoroalkenyloxy group-containing carboxylic acid is not particularly limited, but the acid chloride (molar ratio) of the fullerenol: perfluoroalkenyloxy group-containing carboxylic acid is usually 1: 1 to 1. The ratio is about 1:30, preferably about 1: 5 to 1:20. However, the above acid chloride exceeding 1 mol may be reacted with 1 mol of hydroxyl group of fullerenol, and is not necessarily limited to the above range. For example, in consideration of various conditions such as reaction rate, the acid chloride may be reacted in excess of 30 moles per mole of fullerenol. Although reaction time is not specifically limited, Usually, 5 to 15 hours, Preferably it is 5 to 10 hours.

  By the production method as described above, for example, the following general formula (1):

〔式中、ＢはＣ_20+m（但し、ｍは１〜１００の整数）で表わされるフラーレン単位を示す。ｎ+ｐは１〜３０の数（但し、１≦ｎ≦３０、０≦ｐ≦２９、及び１≦ｎ+ｐ≦２０＋ｍを満たす）を示す。〕
で表わされる含フッ素フラレノール誘導体であって、上記Ａが、
１）Ｃ_aＦ_2a-1Ｏ−（但し、ａは６〜１０の整数）で表わされるパーフルオロアルケニルオキシ基、又は
２）Ｃ_aＦ_2a-1ＯＸＣＯＯ−〔式中、ａは前記と同じである。Ｘはフェニル基又はナフチル基を示す。〕で表わされるパーフルオロアルケニルを含有する基
である含フッ素フラレノール誘導体が得られる。

[Wherein B represents a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). n + p is a number from 1 to 30 (provided that 1 ≦ n ≦ 30, 0 ≦ p ≦ 29, and 1 ≦ n + p ≦ 20 + m are satisfied). ]
A fluorine-containing fullerenol derivative represented by:
1) C _a F _2a-1 O— (where a is an integer of 6 to 10), or 2) C _a F _2a-1 OXCOO— wherein a is the same as above. It is. X represents a phenyl group or a naphthyl group. ] The fluorine-containing fullerenol derivative which is the group containing perfluoroalkenyl represented by this is obtained.

Those having the group shown in the above 1) are obtained by bonding a fullerene unit and a perfluoroalkenyloxy group by an ether bond type reaction. For example,
C ₆₀ (OC ₆ F ₁₁ ) _n (OH) _p
C ₇₀ (OC ₆ F ₁₁ ) _n (OH) _p
C ₆₀ (OC ₉ F ₁₇ ) _n (OH) _p
C ₇₀ (OC ₉ F ₁₇ ) _n (OH) _p
And fluorine-containing fullerenol derivatives such as

  Those having the group shown in the above 2) are obtained by bonding a fullerene unit and a group containing perfluoroalkenyl by an ester bond type reaction. For example,

等の含フッ素フラレノール誘導体が例示される。

And fluorine-containing fullerenol derivatives such as

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
In a 100 ml three-necked flask equipped with a thermometer, a condenser tube and a dropping funnel, 0.5 g of fullerenol mixture (Honjo Chemical Co., Ltd., C ₆₀ (OH) ₁₀ to ₁₂ (90 wt%) and C ₇₀ (OH) mixtures of _10-12 (10 wt%)), triethylamine 1.0g and N, putting N- dimethylformamide 50 ml, warmed with stirring to 50 ° C. with a magnetic stirrer. While maintaining 50 ° C., 2.5 g of hexafluoropropene dimer was gradually dropped from the dropping funnel. After 8 hours, the mixture was allowed to cool to room temperature, acidified with hydrochloric acid, washed repeatedly with water, and then the solid was filtered and dried. The product yield was 1.8 g. The IR measurement results of the product are shown in Table 1 below. For reference, the IR measurement results of the raw material fullerenol are also shown in Table 1 below.

Example 2
The reaction was performed according to Example 1 except that 2.5 g of hexafluoropropene dimer was replaced with 3.5 g of hexafluoropropene trimer. The product yield was 1.0 g. The IR measurement results of the product are shown in Table 1 below.

Example 3
A 100 ml three-necked flask equipped with a thermometer, a condenser tube and a dropping funnel is charged with 0.5 g of the fullerenol mixture used in Example 1, 1.0 g of triethylamine and 50 ml of toluene and stirred at 50 ° C. with a magnetic stirrer. Until warmed. While maintaining the temperature at 50 ° C., 3.8 g of 4- (perfluorononenyloxy) -benzoic acid chloride represented by the following structural formula was gradually dropped from the dropping funnel. After 8 hours, the mixture was allowed to cool to room temperature, acidified with hydrochloric acid, washed repeatedly with water, and then the solid was filtered and dried. The product yield was 0.9 g. The NMR and IR measurement results of the product are shown in Table 2 below. For reference, the IR measurement results of 4- (perfluorononenyloxy) -benzoic acid chloride represented by the following structural formula are shown in Table 3 below.

Claims (4)

The following general formula (1):

[Wherein B represents a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). n + p is a number from 1 to 30 (provided that 1 ≦ n ≦ 30, 0 ≦ p ≦ 29, and 1 ≦ n + p ≦ 20 + m are satisfied). ]
A fluorine-containing fullerenol derivative represented by:
1) C _a F _2a-1 O— (where a is an integer of 6 to 10), or 2) C _a F _2a-1 OXCOO— wherein a is the same as above. It is. X represents a phenyl group or a naphthyl group. ] The fluorine-containing fullerenol derivative characterized by being the group containing perfluoroalkenyl represented by these. B (OH) _q [wherein B represents a fullerene unit represented by C _{20 + m} (where m is an integer of 1 to 100). q represents an integer of 1 to 30 (where 1 ≦ q ≦ 20 + m). ] Fullerenol represented by
1) Perfluoroalkene represented by C _a F _2a (where a is an integer of 6 to 10), or 2) C _a F _2a-1 OXCOY [wherein a is the same as defined above. X represents a phenyl group or a naphthyl group. Y represents a leaving group. ] The manufacturing method of the fluorine-containing fullerenol derivative characterized by making it react with the group containing perfluoroalkenyl represented by these.   The production method according to claim 2, wherein the leaving group Y is a hydroxyl group or a chlorine atom.   A fluorine-containing fullerenol derivative produced by the production method according to claim 2 or 3.