JP5612960B2 - Fluorine-containing compound - Google Patents

Description

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

  A material having a heat resistance of 150 ° C. or higher is required as a material for covering a semiconductor element in a semiconductor device having a high heat resistance and a high withstand voltage. In particular, a material for coating an optical material such as an LED element is required to have physical properties such as flexibility, transparency, heat yellowing resistance, light yellowing resistance, and high refractive index in addition to heat resistance.

  As a material having high heat resistance and good heat dissipation, at least one first organosilicon polymer having a crosslinked structure with siloxane (Si—O—Si bond) and at least one having a linear connection structure with siloxane are used. A synthetic polymer compound containing at least one kind of a third organosilicon polymer having a molecular weight of 20,000 to 800,000, which is formed by linking a second organosilicon polymer of a kind with a siloxane bond has been reported ( Patent Document 1). However, the physical properties of these materials are not yet satisfactory.

JP 2006-206721 A

An object of the present invention is to provide a novel fluorine-containing compound into which an addition-curable crosslinking functional group capable of hydrosilylation reaction is introduced.
Another object of the present invention is to provide a method for producing the above fluorine-containing compound.

  When the fluorine-containing compound into which an addition-curable crosslinking functional group capable of hydrosilylation reaction is introduced is cured, the present inventors have high temperature heat resistance, flexibility, low Tg, transparency, heat yellowing, etc. The present inventors have found that these physical properties are possessed, and have reached the present invention.

［式中、Ｒ ^f' は、ｎ価のフッ素化炭化水素基であって、その炭化水素基が炭素数３〜１０の２〜３価の直鎖状の脂肪族炭化水素基、炭素数４〜１０の２〜３価の分枝鎖状の脂肪族炭化水素基、炭素数５〜１０の２〜３価の脂環式炭化水素基、又はこれらの基の２以上が結合した２〜３価の基であり、フッ素化前の炭化水素基の水素原子の２０〜１００％がフッ素原子で置換されているフッ素化炭化水素基であるか、又は
下記式（３）

（式中、ｎ１は１〜４の整数、ｎ２は１〜１０の整数、ｎ３は１〜４の整数を示す。）
で表される２価のフッ素化炭化水素基である。ｎ個の括弧内の基は、同一であっても異なっていてもよい。Ｒ¹〜Ｒ³は、同一又は異なって、水素原子、炭素数１〜４のアルキル基、アリール基又は下記式（２）

（式中、Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^eは、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す。ｍは、０〜３の整数を示す。）
で表される基を示す。但し、Ｒ¹〜Ｒ³の少なくとも１つは、水素原子又は上記式（２）で表される基である。］
で表されることを特徴とするフッ素含有化合物を提供する。
上記フッ素含有化合物において、ｎ１＝１、ｎ２＝３、ｎ３＝１、ｍ＝０であることが好ましい。好ましくは、上記フッ素含有化合物は、０〜９０℃のいずれかの温度において液体である。
また、本発明は、塩基の存在下、下記式（４’）

［式中、Ｒ ^f' は、ｎ価のフッ素化炭化水素基であって、その炭化水素基が炭素数３〜１０の２〜３価の直鎖状の脂肪族炭化水素基、炭素数４〜１０の２〜３価の分枝鎖状の脂肪族炭化水素基、炭素数５〜１０の２〜３価の脂環式炭化水素基、又はこれらの基の２以上が結合した２〜３価の基であり、フッ素化前の炭化水素基の水素原子の２０〜１００％がフッ素原子で置換されているフッ素化炭化水素基であるか、又は
下記式（３）

（式中、ｎ１は１〜４の整数、ｎ２は１〜１０の整数、ｎ３は１〜４の整数を示す。）
で表される２価のフッ素化炭化水素基である。］
で表されるヒドロキシ化合物と、下記式（５）

［式中、Ｘはハロゲン原子を示す。Ｒ¹〜Ｒ³は、同一又は異なって、水素原子、炭素数１〜４のアルキル基、アリール基又は下記式（２）

（式中、Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^eは、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す。ｍは、０〜３の整数を示す。）
で表される基を示す。但し、Ｒ¹〜Ｒ³の少なくとも１つは、水素原子又は上記式（２）で表される基である。］
で表されるシラン化合物とを反応させて、下記式（１’）

（式中、Ｒ ^f' は、ｎ価のフッ素化炭化水素基であって、その炭化水素基が炭素数３〜１０の２〜３価の直鎖状の脂肪族炭化水素基、炭素数４〜１０の２〜３価の分枝鎖状の脂肪族炭化水素基、炭素数５〜１０の２〜３価の脂環式炭化水素基、又はこれらの基の２以上が結合した２〜３価の基であり、フッ素化前の炭化水素基の水素原子の２０〜１００％がフッ素原子で置換されているフッ素化炭化水素基であるか、又は
下記式（３）

（式中、ｎ１は１〜４の整数、ｎ２は１〜１０の整数、ｎ３は１〜４の整数を示す。）
で表される２価のフッ素化炭化水素基である。ｎ、Ｒ¹〜Ｒ³は上記と同じ。ｎ個の括弧内の基は、同一であっても異なっていてもよい。）
で表されるフッ素含有化合物を得ることを特徴とする、フッ素含有化合物の製造方法を提供する。
上記製造方法において、ｎ１＝１、ｎ２＝３、ｎ３＝１、ｍ＝０であることが好ましい。また、好ましくは、塩基が有機塩基である。
また、本発明は、下記式（１）

［式中、Ｒ ^f はｎ価のフッ素化炭化水素基、ｎは１以上の整数を示し、ｎが２以上の場合、ｎ個の括弧内の基は、同一であっても異なっていてもよい。Ｒ ¹ 〜Ｒ ³ は、同一又は異なって、水素原子、炭素数１〜４のアルキル基、アリール基又は下記式（２）

（式中、Ｒ ^a 、Ｒ ^b 、Ｒ ^c 、Ｒ ^d 、Ｒ ^e は、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す。ｍは、０〜３の整数を示す。）
で表される基を示す。但し、Ｒ ¹ 〜Ｒ ³ の少なくとも１つは、水素原子又は上記式（２）で表される基である。］
で表されることを特徴とするフッ素含有化合物についても説明する。
さらに、本発明は、塩基の存在下、下記式（４）

（式中、Ｒ ^f はｎ価のフッ素化炭化水素基、ｎは１以上の整数を示す。）
で表されるヒドロキシ化合物と、下記式（５）

［式中、Ｘはハロゲン原子を示す。Ｒ ¹ 〜Ｒ ³ は、同一又は異なって、水素原子、炭素数１〜４のアルキル基、アリール基又は下記式（２）

（式中、Ｒ ^a 、Ｒ ^b 、Ｒ ^c 、Ｒ ^d 、Ｒ ^e は、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す。ｍは、０〜３の整数を示す。）
で表される基を示す。但し、Ｒ ¹ 〜Ｒ ³ の少なくとも１つは、水素原子又は上記式（２）で表される基である。］
で表されるシラン化合物とを反応させて、下記式（１）

（式中、Ｒ ^f 、ｎ、Ｒ ¹ 〜Ｒ ³ は上記と同じ。ｎが２以上の場合、ｎ個の括弧内の基は、同一であっても異なっていてもよい。）
で表されるフッ素含有化合物を得ることを特徴とする、フッ素含有化合物の製造方法についても説明する。 That is, the present invention provides the following formula (1 ′)

[ Wherein , R ^{f ′} is an n-valent fluorinated hydrocarbon group, and the hydrocarbon group is a C 2-10 trivalent linear aliphatic hydrocarbon group, C 4 10 to 2-3 trivalent branched aliphatic hydrocarbon groups, C 5 to 10 divalent or trivalent alicyclic hydrocarbon groups, or two or more of these groups bonded to each other. Or a fluorinated hydrocarbon group in which 20 to 100% of the hydrogen atoms of the hydrocarbon group before fluorination are substituted with fluorine atoms, or
Following formula (3)

(In the formula, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 4.)
It is a bivalent fluorinated hydrocarbon group represented by these. The groups in n parentheses may be the same or different. R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or the following formula (2)

^{(Wherein, R a, R b, R} c, R d, R e are the same or different, .m represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3. )
The group represented by these is shown. However, at least one of R ^{1 to} R ³ is a hydrogen atom or a group represented by the above formula (2). ]
The fluorine-containing compound characterized by these is provided.
In the above fluorine-containing compound, it is preferable that n 1 = 1 , n 2 = 3, n 3 = 1, and m = 0. Preferably, the fluorine-containing compound is liquid at any temperature of 0 to 90 ° C.
Further, the present invention provides the following formula (4 ′) in the presence of a base.

[ Wherein , R ^{f ′} is an n-valent fluorinated hydrocarbon group, and the hydrocarbon group is a C 2-10 trivalent linear aliphatic hydrocarbon group, C 4 10 to 2-3 trivalent branched aliphatic hydrocarbon groups, C 5 to 10 divalent or trivalent alicyclic hydrocarbon groups, or two or more of these groups bonded to each other. Or a fluorinated hydrocarbon group in which 20 to 100% of the hydrogen atoms of the hydrocarbon group before fluorination are substituted with fluorine atoms, or
Following formula (3)

(In the formula, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 4.)
It is a bivalent fluorinated hydrocarbon group represented by these. ]
And a hydroxy compound represented by the following formula (5):

[Wherein X represents a halogen atom. R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or the following formula (2)

^{(Wherein, R a, R b, R} c, R d, R e are the same or different, .m represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3. )
The group represented by these is shown. However, at least one of R ^{1 to} R ³ is a hydrogen atom or a group represented by the above formula (2). ]
Is reacted with a silane compound represented by the following formula (1 ′)

(In the formula, R ^{f ′} is an n-valent fluorinated hydrocarbon group, and the hydrocarbon group is a C 3-10 divalent linear aliphatic hydrocarbon group, carbon number 4 10 to 2-3 trivalent branched aliphatic hydrocarbon groups, C 5 to 10 divalent or trivalent alicyclic hydrocarbon groups, or two or more of these groups bonded to each other. Or a fluorinated hydrocarbon group in which 20 to 100% of the hydrogen atoms of the hydrocarbon group before fluorination are substituted with fluorine atoms, or
Following formula (3)

(In the formula, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 4.)
It is a bivalent fluorinated hydrocarbon group represented by these . n and R ^{1 to} R ³ are the same as above. The groups in n parentheses may be the same or different. )
A method for producing a fluorine-containing compound is provided.
In the above production method, it is preferable that n 1 = 1 , n 2 = 3, n 3 = 1, and m = 0. Preferably, the base is an organic base.
Further, the present invention provides the following formula (1):

[Wherein, R ^f represents an n-valent fluorinated hydrocarbon group, n represents an integer of 1 or more, and when n is 2 or more, the groups in n parentheses may be the same or different. Good. R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or the following formula (2)

^{(Wherein, R a, R b, R} c, R d, R e are the same or different, .m represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3. )
The group represented by these is shown. However, at least one of R ^{1 to} R ³ is a hydrogen atom or a group represented by the above formula (2). ]
A fluorine-containing compound characterized by the following is also described.
Furthermore, the present invention provides the following formula (4) in the presence of a base.

(In the formula, R ^f represents an n-valent fluorinated hydrocarbon group, and n represents an integer of 1 or more.)
And a hydroxy compound represented by the following formula (5):

[Wherein X represents a halogen atom. R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or the following formula (2)

^{(Wherein, R a, R b, R} c, R d, R e are the same or different, .m represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3. )
The group represented by these is shown. However, at least one of R ^{1 to} R ³ is a hydrogen atom or a group represented by the above formula (2). ]
Is reacted with a silane compound represented by the following formula (1):

(In the formula, R ^f , n and R ^{1 to} R ³ are the same as above. When n is 2 or more, the groups in n parentheses may be the same or different.)
A method for producing a fluorine-containing compound, characterized in that a fluorine-containing compound represented by the formula:

Since the novel fluorine-containing compound of the present invention has an addition-curing crosslinking functional group capable of hydrosilylation reaction, the variation of the compound having fluorine and silicon-containing crosslinking functional group is expanded and changed to its application. Can be caused. According to the novel fluorine-containing compound of the present invention, a cured product having physical properties such as high temperature heat resistance, flexibility, low Tg, transparency, and heat yellowing can be obtained. The fluorine-containing compound of the present invention can be used as a sealing material for semiconductor elements such as LEDs having physical properties such as high temperature heat resistance, flexibility, low Tg, transparency and heat yellowing.
Moreover, according to the manufacturing method of the fluorine-containing compound of this invention, the said novel fluorine-containing compound can be obtained.

で表されることを特徴とする。上記式（１）中、Ｒ^fはｎ価のフッ素化炭化水素基、ｎは１以上（例えば１〜６）の整数を示し、ｎが２以上の場合、ｎ個の括弧内の基は同一であっても異なっていてもよい。本発明のフッ素含有化合物は、ヒドロシリル化反応が可能となる付加硬化型架橋官能基が導入され、固体、液体、気体の状態をとることが考えられるが、好ましくは、常圧で、０〜９０℃のいずれかの温度において液状を呈している。さらに好ましくは、常圧で、１０〜４０℃のいずれかの温度において液状を呈し、特に、常温常圧（１ａｔｍ、２５±５℃）にて液状を呈することが好ましい。融点としては、９０℃以下が好ましく、４０℃以下がさらに好ましく、０℃以下が特に好ましい。ヒドロシリル化反応が可能となる付加硬化型架橋官能基とは、エチレン性不飽和二重結合を有する基、またはＳｉ−Ｈ結合を有する基を指す。 [Fluorine-containing compound]
The fluorine-containing compound of the present invention has the following formula (1)

It is represented by. In the above formula (1), R ^f represents an n-valent fluorinated hydrocarbon group, n represents an integer of 1 or more (for example, 1 to 6), and when n is 2 or more, the groups in n parentheses are the same. Or different. The fluorine-containing compound of the present invention may be in a solid, liquid, or gaseous state by introducing an addition-curing crosslinking functional group that enables a hydrosilylation reaction, and is preferably 0 to 90 at normal pressure. It is liquid at any temperature of ° C. More preferably, it is liquid at normal pressure and at any temperature of 10 to 40 ° C., and particularly preferably liquid at normal temperature and normal pressure (1 atm, 25 ± 5 ° C.). The melting point is preferably 90 ° C. or lower, more preferably 40 ° C. or lower, and particularly preferably 0 ° C. or lower. The addition-curable crosslinking functional group capable of hydrosilylation refers to a group having an ethylenically unsaturated double bond or a group having a Si—H bond.

で表される基を示す。上記式（２）中、Ｒ^a、Ｒ^b、Ｒ^c、Ｒ^d、Ｒ^eは、同一又は異なって、水素原子又は炭素数１〜４のアルキル基を示す。ｍは０〜３の整数を示し、ｍ＝０の場合は単結合を表す。ｍは０又は１が好ましく、特に好ましくは１である。Ｒ¹〜Ｒ³の少なくとも１つは、水素原子又は上記式（２）で表される基である。 <R ^{1 to} R ³ >
R < ¹ > -R < ³ > in the said Formula (1) is the same or different, and is a hydrogen atom, a C1-C4 alkyl group, an aryl group, or following formula (2)

The group represented by these is shown. In said formula (2), R ^<a> , R ^<b> , R ^<c> , R ^<d> , ^Re is the same or different and shows a hydrogen atom or a C1-C4 alkyl group. m represents an integer of 0 to 3, and when m = 0, it represents a single bond. m is preferably 0 or 1, particularly preferably 1. At least one of R ^{1 to} R ³ is a hydrogen atom or a group represented by the above formula (2).

Examples of the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ³ , R ^a , R ^b , R ^c , R ^d , and R ^e include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and t-butyl groups. Can be mentioned. Examples of the aryl group in R ^{1 to} R ³ include a substituted or unsubstituted phenyl group and naphthyl group. As R ^{1 to} R ³ , a group other than a hydrogen atom or a group represented by the above formula (2) is preferably a methyl group or a phenyl group. R ^a , R ^b , R ^c , R ^d , and R ^e are preferably a hydrogen atom or a methyl group.

<R ^f >
Examples of the hydrocarbon group in the fluorinated hydrocarbon group represented by R ^f include a monovalent or polyvalent aliphatic hydrocarbon group, a monovalent or polyvalent alicyclic hydrocarbon group, a monovalent or polyvalent hydrocarbon group. An aromatic hydrocarbon group, and a monovalent or polyvalent group in which two or more of these are bonded, and the like, preferably a C1-C20 linear monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, carbon 1 to 4 valent branched aliphatic hydrocarbon group having 2 to 20 carbon atoms, 1 to 4 carbon alicyclic hydrocarbon group having 3 to 20 carbon atoms, 1 to 4 carbon atoms having 6 to 20 carbon atoms Examples thereof include aromatic hydrocarbon groups and 1 to 4 valent groups having a total carbon number of 4 to 22 in which two or more of these groups are bonded via or without oxygen atoms or sulfur atoms. More preferably, it is a C2-C10 divalent trivalent linear aliphatic hydrocarbon group, a C4-C10 divalent trivalent branched aliphatic hydrocarbon group, and C5. 10 to 2 to 3 valent alicyclic hydrocarbon groups, C 8 to 2 to 3 valent aromatic hydrocarbon groups, and two or more of these groups through or through an oxygen atom or a sulfur atom. Examples thereof include a divalent or trivalent group that is bonded without any problem.

  Examples of the monovalent linear hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, undecyl, pentadecyl, octadecyl group, etc .; 1 having 2 to 20 carbon atoms As the branched branched hydrocarbon group, methylethyl, dimethylmethyl, 2-methylpropyl, 2,2-dimethylpropyl, 2-methylbutyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl, 2-ethyl- 2-methylpropyl, 2-methylpentyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 2,3,4-trimethylpentyl, 2-ethyl-2-methylpentyl, etc. As a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, cyclopentyl, 1-methylcyclopentyl, cyclohexyl, 1-methyl Cyclohexyl, 1,4-dimethylcyclohexyl group and the like; examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include phenyl, 1-methylphenyl, 1,4-dimethylphenyl, naphthyl group and the like. It is done.

  Examples of the divalent linear hydrocarbon group having 1 to 20 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene group, etc .; As branched chain hydrocarbon groups, methylmethylene, methylethylene, dimethylmethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, 2-methyltetramethylene, 2,3-dimethyltetramethylene, 2,2-dimethyl Tetramethylene, 2-ethyl-2-methyltrimethylene, 2-methylpentamethylene, 2,2-dimethylpentamethylene, 2,3-dimethylpentamethylene, 2,4-dimethylpentamethylene, 2,3,4-trimethyl Pentamethylene, 2-ethyl-2-methylpentamethylene group, etc .; C 3-20 divalent As the alicyclic hydrocarbon group, 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohex Xylene, cyclohexylidene group, etc .; C6-C20 divalent aromatic hydrocarbon group such as phenylene, naphthylene group, etc .; 1,4-cyclohexylenebis (methylene), 1,4-phenylenebis (methylene) Etc.

  Examples of polyvalent hydrocarbon groups other than those described above include 1,2,3-propanetriyl, 1,2,3-butyltriyl, 1,2,4-butyltriyl, 1,2,3,4-butyltetra. 1,2,3-pentanetriyl, 1,2,4-pentanetriyl, 1,2,5-pentanetriyl, 1,2,3,4-pentanetetrayl, 1,2,4,5 -Pentanetetrayl, 1,2,3-cyclohexanetriyl and the like.

Of the hydrocarbon groups in the fluorinated hydrocarbon group represented by R ^f , a divalent aliphatic hydrocarbon group is preferable, and tetramethylene, pentamethylene, hexamethylene, 2-methyltetramethylene, 2-methyltrimethylene. 2-methylpentamethylene and 3-methylpentamethylene are particularly preferred.

In the fluorinated hydrocarbon group represented by R ^f , for example, 20 to 100% of the hydrogen atoms of the hydrocarbon group before fluorination are substituted with fluorine atoms, and 30 to 90% are substituted. Preferably, 50 to 70% is more preferably substituted. In the fluorinated hydrocarbon group represented by R ^f , it is preferable that the hydrogen atoms bonded to the carbon atoms at both ends are not substituted with fluorine atoms. The fluorinated hydrocarbon group represented by R ^f of the present invention preferably has 3 to 8 carbon atoms, 2 to 14 fluorine atoms, and 1 to 6 —CF ₂ — groups. Furthermore, it is preferable that the number of carbon atoms is 3 to 6, the number of fluorine atoms is 2 to 8, and 1 to 4 —CF ₂ — groups are included. When there are two or more —CF ₂ — groups, they are preferably continuous. By setting it as such a structure, the compound which exhibits the said liquid state is obtained. Moreover, when cured, a cured product having excellent heat resistance and transparency can be obtained. If the number of carbon atoms is larger than the above range, the cured product tends to become cloudy.

  Examples of the fluorinated hydrocarbon group include, for example, 2,2-difluoropropanediyl, 2,2,3,3-tetrafluorobutanediyl, 2,2,3,3,4,4-hexafluoropentane. Diyl, 2,2,3,3,4,4,5,5-octafluorohexanediyl, 2,2,3,3,4,4,5,5,6,6-decafluoroheptanediyl, 2, 2,3,3,4,4,5,5,6,6,7,7-dodecafluorooctanediyl, 2,2,3,3,4,4,5,5,6,6,7,7 , 8,8-tetradecafluorononanediyl and 2,2,3,3,4,4,5,5,6,7,7,8,8,9,9-heptadecafluorodecanediyl, 2-Fluoro-2-perfluoromethyl-1,3-propanediyl and 2-fluoro-2-perfur Such Roechiru 1,3-propanediyl can be exemplified.

で表される２価のフッ素化炭化水素基であることが特に好ましい。なお、式中、ｎ１は１〜４の整数、ｎ２は１〜１０の整数、ｎ３は１〜４の整数を示す。なかでも、ｎ１＝ｎ３＝１、ｎ２＝１〜７が好ましく、ｎ２＝１〜４が特に好ましい。すなわち、１〜４個の−ＣＦ₂−基を連続して構造中に有し、両末端がメチレン基である、２，２−ジフルオロプロパンジイル、２，２，３，３−テトラフルオロブタンジイル、２，２，３，３，４，４−ヘキサフルオロペンタンジイル、２，２，３，３，４，４，５，５−オクタフルオロヘキサンジイルが好ましい。 As the fluorinated hydrocarbon group represented by R ^f of the present invention, the following formula (3)

The divalent fluorinated hydrocarbon group represented by the formula is particularly preferred. In the formula, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 4. Especially, n1 = n3 = 1 and n2 = 1-7 are preferable, and n2 = 1-4 are especially preferable. That is, 2,2-difluoropropanediyl, 2,2,3,3-tetrafluorobutanediyl having 1 to 4 —CF ₂ — groups in the structure in succession and both ends being methylene groups 2,2,3,3,4,4-hexafluoropentanediyl and 2,2,3,3,4,4,5,5-octafluorohexanediyl are preferred.

Specific examples of the compound represented by the above formula (1) include the following compounds.

で表されるヒドロキシ化合物と、下記式（５）

で表されるシラン化合物とを反応させて、上記式（１）で表されるフッ素含有化合物を得ることを特徴とする。上記式（４）（５）中、Ｒ^f、ｎ、Ｒ¹〜Ｒ³は上記と同じである。上記式（５）中、Ｘは塩素、臭素などのハロゲン原子及びアルコキシを示す。アルコキシ基には、例えば、メトキシ、エトキシ、イソプロポキシ、ブトキシ、ｔ−ブトキシ、ヘキシルオキシ、オクチルオキシ、デシルオキシ、ドデシルオキシ、テトラデシルオキシ、オクタデシルオキシ基などの炭素数１〜３０程度（特に、炭素数１〜２０程度）のアルコキシ基が含まれる。 [Production of fluorine-containing compounds]
The method for producing a fluorine-containing compound of the present invention comprises the following formula (4) in the presence of a base.

And a hydroxy compound represented by the following formula (5):

A fluorine-containing compound represented by the above formula (1) is obtained by reacting with a silane compound represented by formula (1). In the above formulas (4) and (5), R ^f , n and R ^{1 to} R ³ are the same as described above. In said formula (5), X shows halogen atoms, such as chlorine and a bromine, and alkoxy. The alkoxy group includes, for example, about 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy, octadecyloxy groups (particularly carbon An alkoxy group of about 1 to 20).

<Hydroxy compound>
As the hydroxy compound represented by the formula (4), a monovalent or polyhydric alcohol having the above R ^f can be used, and the hydroxy compound corresponding to the target fluorine-containing compound represented by the formula (1) is used. it can. The hydroxy compound represented by Formula (4) can be manufactured by a well-known method, and a commercial item can also be used for it. Specifically, 2,2-difluoropropanediol, 2,2,3,3-tetrafluorobutanediol, 2,2,3,3,4,4-hexafluoropentanediol, 2,2,3,3 4,4,5,5-octafluorohexanediol can be preferably exemplified.

<Silane compound>
Specific examples of the silane compound represented by the formula (5) include monohalogenated vinyl silane, monohalogenated allyl silane, 3-butenyl monohalogenated silane, 4-pentenyl monohalogenated silane, and monohalogen having a hydrogen atom. And monohalogenated silane compounds such as a silane compound; monoalkoxyvinylsilane compounds such as monoalkoxyvinylsilane, monoalkoxyallylsilane, 3-butenylmonoalkoxysilane, 4-pentenylmonoalkoxysilane, and the like.

  Representative examples of the monohalogenated silane compound having a hydrogen atom include chlorodimethylsilane, chloromethylphenylsilane, chlorodiethylsilane, chloroethylphenylsilane, chlorodi-n-propylsilane, chloro-n-propylphenylsilane, chlorodi- t-butylsilane, chloro-t-butylphenylsilane, chlorodiphenylsilane, bromodimethylsilane, bromomethylphenylsilane, bromodiethylsilane, bromoethylphenylsilane, bromodi-n-propylsilane, bromon-propylphenylsilane, bromodi- Examples include t-butylsilane, bromo t-butylphenylsilane, bromodiphenylsilane, and the like.

  Representative examples of monohalogenated vinyl silanes include chlorodimethyl vinyl silane, chloromethyl phenyl vinyl silane, chloro diethyl vinyl silane, chloro ethyl phenyl vinyl silane, chloro di-n-propyl vinyl silane, chloro n-propyl phenyl vinyl silane, chloro di-t-butyl vinyl silane, Chloro-t-butylphenylvinylsilane, chlorodiphenylvinylsilane, bromodimethylvinylsilane, bromomethylphenylvinylsilane, bromodiethylvinylsilane, bromoethylphenylvinylsilane, bromodi-n-propylvinylsilane, bromon-propylphenylvinylsilane, bromodi-t-butylvinylsilane Bromo t-butylphenyl vinyl silane, bromodiphenyl vinyl silane, etc.

  Representative examples of monohalogenated allylsilane include chlorodimethylallylsilane, chloromethylphenylallylsilane, chlorodiethylallylsilane, chloroethylphenylallylsilane, chlorodi-n-propylallylsilane, chloro-n-propylphenylallylsilane, chlorodi-t-butylallylsilane, Chloro-t-butylphenylallylsilane, chlorodiphenylallylsilane, bromodimethylallylsilane, bromomethylphenylallylsilane, bromodiethylallylsilane, bromoethylphenylallylsilane, bromodi-n-propylallylsilane, bromon-propylphenylallylsilane, bromodi-t-butylallylsilane Bromo t-butylphenylallylsilane, bromodiphenylallylsilane, etc.

  Typical examples of 3-butenyl monohalogenated silane include chlorodimethyl-3-butenyl silane, chloromethylphenyl-3-butenyl silane, chlorodiethyl-3-butenyl silane, chloroethylphenyl-3-butenyl silane, chlorodiphenyl-3-butenyl silane Bromodimethyl-3-butenylsilane, bromomethylphenyl-3-butenylsilane, bromodiethyl-3-butenylsilane, bromoethylphenyl-3-butenylsilane, bromodiphenyl-3-butenylsilane, and the like.

  Representative examples of 4-pentenyl monohalogenated silane include chlorodimethyl-4-pentenyl silane, chloromethylphenyl-4-pentenyl silane, chlorodiethyl-4-pentenyl silane, chloroethylphenyl-4-pentenyl silane, chlorodiphenyl- 4-pentenylsilane, bromodimethyl-4-pentenylsilane, bromomethylphenyl-4-pentenylsilane, bromodiethyl-4-pentenylsilane, bromoethylphenyl-4-pentenylsilane, bromodiphenyl-4-pentenylsilane, etc. .

  Representative examples of monoalkoxy vinyl silane include methoxy dimethyl vinyl silane, methoxy methyl phenyl vinyl silane, methoxy diethyl vinyl silane, methoxy ethyl phenyl vinyl silane, methoxy di-n-propyl vinyl silane, methoxy n-propyl phenyl vinyl silane, methoxy di-t-butyl vinyl silane, methoxy t -Butylphenylvinylsilane, methoxydiphenylvinylsilane, ethoxydimethylvinylsilane, ethoxymethylphenylvinylsilane, ethoxydiethylvinylsilane, ethoxyethylphenylvinylsilane, ethoxydi-n-propylvinylsilane, ethoxyn-propylphenylvinylsilane, ethoxydi-t-butylvinylsilane, ethoxyt -Butylphenylvinylsilane, ethoxydiphe Rubinirushiran and the like.

  Representative examples of monoalkoxyallylsilane include methoxydimethylallylsilane, methoxymethylphenylallylsilane, methoxydiethylallylsilane, methoxyethylphenylallylsilane, methoxydi-n-propylallylsilane, methoxyn-propylphenylallylsilane, methoxydi-t-butylallylsilane, methoxyt -Butylphenylallylsilane, methoxydiphenylallylsilane, ethoxydimethylallylsilane, ethoxymethylphenylallylsilane, ethoxydiethylallylsilane, ethoxyethylphenylallylsilane, ethoxydi-n-propylallylsilane, ethoxyn-propylphenylallylsilane, ethoxydi-t-butylallylsilane, ethoxyt -Butylphenylallylsilane, ethoxydiphe Ruarirushiran and the like.

  Representative examples of 3-butenyl monoalkoxysilane include methoxydimethyl-3-butenylsilane, methoxymethylphenyl-3-butenylsilane, methoxydiethyl-3-butenylsilane, methoxyethylphenyl-3-butenylsilane, methoxydiphenyl-3-butenylsilane, Examples include ethoxydimethyl-3-butenylsilane, ethoxymethylphenyl-3-butenylsilane, ethoxydiethyl-3-butenylsilane, ethoxyethylphenyl-3-butenylsilane, and ethoxydiphenyl-3-butenylsilane.

  Representative examples of 4-pentenyl monoalkoxysilane include methoxydimethyl-4-pentenylsilane, methoxymethylphenyl-4-pentenylsilane, methoxydiethyl-4-pentenylsilane, methoxyethylphenyl-4-pentenylsilane, methoxydiphenyl-4 -Pentenylsilane, ethoxydimethyl-4-pentenylsilane, ethoxymethylphenyl-4-pentenylsilane, ethoxydiethyl-4-pentenylsilane, ethoxyethylphenyl-4-pentenylsilane, ethoxydiphenyl-4-pentenylsilane and the like. The silane compound represented by Formula (5) can be manufactured by a well-known method, and a commercial item can also be used for it.

<Solvent>
The reaction between the hydroxy compound represented by the formula (4) and the silane compound represented by the formula (5) is performed in the presence or absence of a solvent. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane, 1,2- Halogenated hydrocarbons such as dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate, ethyl acetate, isopropyl acetate and butyl acetate; N, N-dimethylformamide; Amides such as N, N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile. These solvents are used alone or in admixture of two or more.

  The usage-amount of the silane compound represented by Formula (5) is 1.0-2 mol with respect to 1 mol of hydroxyl groups which should be attached | subjected to reaction of the hydroxy compound represented by Formula (4), Preferably 1. It is about 0 to 1.3 mol, more preferably about 1.0 to 1.2 mol.

<Base>
The method for producing a fluorine-containing compound of the present invention is carried out in the presence of a base. The presence of a base in the reaction system generally increases the reaction rate significantly. Bases include inorganic and organic bases. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide, and barium hydroxide. Alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate Examples thereof include hydrogen salt.

  Examples of the organic base include alkali metal organic acid salts (particularly alkali metal acetate) such as lithium acetate, sodium acetate, potassium acetate, and cesium acetate; alkaline earth metal organic acid salts such as magnesium acetate; methyllithium, butyl Alkyllithium such as lithium (n-butyllithium, s-butyllithium, t-butyllithium, etc.); alkali metal alkoxide such as lithium methoxide, sodium methoxide, sodium ethoxide, sodium isopropoxide, potassium ethoxide (formula (5) or alkali metal alkoxide corresponding to the hydroxy compound represented by (6)); alkali metal phenoxide such as sodium phenoxide; triethylamine, N-methylpiperidine, 4-dimethylaminopyridine (DMAP) 1,8-diazabicyclo [5.4.0] -7-undecene (DBU), triethylenediamine (1,4-diazabicyclo [2.2.2] octane; DABCO), 1,5-diazabicyclo [4.3. 0] -5-nonene (DBN), hexamethylenetetramine, tetramethylethylenediamine, trioctylamine, dimethylaniline, N-methylpyrrolidine, N-methylpiperidine, 4-methylmorpholine, and other amines (tertiary amines, etc. ); Nitrogen-containing aromatic heterocyclic compounds such as pyridine, lutidine, picoline, imidazole, 2,2′-bipyridyl and 1,10-phenanthroline. These bases can be used alone or in combination of two or more. Of these, tertiary amines such as triethylamine and 4-dimethylaminopyridine; nitrogen-containing aromatic heterocyclic compounds such as pyridine, lutidine and picoline are preferable.

  The usage-amount of a base is 1-300 mol with respect to 1 mol of hydroxyl groups in the hydroxy compound represented by Formula (4), Preferably it is about 1-1.5 mol.

  The reaction may be performed in the presence of a polymerization inhibitor. The reaction temperature can be appropriately selected according to the reaction components and the type of catalyst. For example, in the case of vinyl silane, the reaction temperature is 20 to 200 ° C, preferably 20 to 100 ° C, and more preferably about 40 to 60 ° C. In the case of hydrosilane, the reaction temperature can be appropriately selected according to the reaction components and the type of catalyst, and is, for example, -78 to 110 ° C, preferably -30 to 40 ° C, more preferably about -10 to 10 ° C. is there. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  In the above method, at least one hydroxyl group of the hydroxy compound represented by the formula (4) is silylated by the reaction to produce a corresponding fluorine-containing compound represented by the formula (1). After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these. You may wash by adding aqueous solvents, such as water, 1-7% dilute hydrochloric acid, and 1-7% sodium hydrogen carbonate solution, to the liquid mixture after reaction.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The reaction product was identified by GC-MS and ¹ H-NMR.

Example 1
Hexafluoropentanediol derivatization (derivatization to divinylsilane _CV )
In a 300 ml four-necked flask, 2,2,3,3,4,4-hexafluoropentanediol (20 g, manufactured by Tokyo Chemical Industry Co., Ltd.), pyridine (22.3 g) and toluene (160 g) were charged. While stirring with a magnetic stirrer at room temperature, chlorodimethylvinylsilane (25.0 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped with a dropping funnel over 30 minutes. After completion of dropping, the mixture was heated to 50 ° C. in an oil bath and aged for 1 hour.
Water (100 g) was added and stirred, and then allowed to stand to extract the lower layer (aqueous layer). Further, 5% HC1 (60 ml) was added to the upper layer, stirred, and allowed to stand to extract the lower layer. 30 ml of 5% aqueous sodium bicarbonate solution was added to the upper layer, stirred, allowed to stand, and the lower layer was extracted.
After concentrating the upper layer with an evaporator and then reducing the pressure with a vacuum pump, 27 g of a fluorine-containing compound (divinylsilane derivative) represented by the above formula (11) was obtained.
H NMR δ0.25 ppm (s, 12H), δ4.04 ppm (s, 4H), δ5.80 ppm (dd, 4H) δ6.12 ppm (t, 2H)

Example 2
Derivatization of hexafluoro-pentanediol (derivatized to H-type body C _H)
In a 300 ml four-necked flask, 2,2,3,3,4,4-hexafluoropentanediol (20 g, manufactured by Tokyo Chemical Industry Co., Ltd.), pyridine (22.3 g) and toluene (160 g) were charged. While cooling with ice at 0 ° C. and stirring with a magnetic stirrer, chlorodimethylsilane (19.9 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 30 minutes using a dropping funnel. After completion of dropping, the mixture was further aged at 0 ° C. for 1 hour.
The precipitated pyridine hydrochloride was removed by filtration.
When the filtrate was concentrated with an evaporator and then reduced in pressure with a vacuum pump, 20 g of a fluorine-containing compound (disilane derivative) represented by the above formula (12) was obtained.
H NMR δ0.25 ppm (s, 12H), δ4.01 ppm (s, 4H), δ4.20 ppm (s, 2H)

Example 3
The fluorine-containing compound (0.400 g) obtained in Example 1 and methyl H siloxane (0.100 g, molecular weight 1900-2000, distributor: Azumax) were weighed into a 6 ml screw tube and stirred for 1 hour at room temperature. However, a compatible and transparent and uniform solution was obtained. To the obtained mixed solution, 1.0 μl of platinum vinylmethylsiloxane complex (manufactured by Wako Pure Chemicals; platinum 1.6 wt%) was added and stirred again to obtain a heat-curable composition.
When the obtained heat-curable composition was applied to a glass plate and heated on a hot plate at 60 ° C. for 10 minutes, a colorless and transparent cured product was obtained.

Example 4
In Example 3, a heat-curable composition was obtained in the same manner as in Example 3 except that the fluorine-containing compound obtained in Example 1 was replaced with the fluorine-containing compound obtained in Example 2.
When the obtained heat-curable composition was applied to a glass plate and heated on a hot plate at 60 ° C. for 10 minutes, a colorless and transparent cured product was obtained.

Claims (6)

Following formula (1 ')

[ Wherein , R ^{f ′} is an n-valent fluorinated hydrocarbon group, and the hydrocarbon group is a C 2-10 trivalent linear aliphatic hydrocarbon group, C 4 10 to 2-3 trivalent branched aliphatic hydrocarbon groups, C 5 to 10 divalent or trivalent alicyclic hydrocarbon groups, or two or more of these groups bonded to each other. Or a fluorinated hydrocarbon group in which 20 to 100% of the hydrogen atoms of the hydrocarbon group before fluorination are substituted with fluorine atoms, or
Following formula (3)

(In the formula, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 4.)
It is a bivalent fluorinated hydrocarbon group represented by these. The groups in n parentheses may be the same or different. R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or the following formula (2)

^{(Wherein, R a, R b, R} c, R d, R e are the same or different, .m represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3. )
The group represented by these is shown. However, at least one of R ^{1 to} R ³ is a hydrogen atom or a group represented by the above formula (2). ]
A fluorine-containing compound represented by the formula: The fluorine-containing compound according to claim 1, wherein n1 = 1, n2 = 3, n3 = 1, and m = 0. The fluorine-containing compound according to claim 1 or 2 , which is liquid at any temperature of 0 to 90 ° C. In the presence of a base, the following formula (4 ′)

[ Wherein , R ^{f ′} is an n-valent fluorinated hydrocarbon group, and the hydrocarbon group is a C 2-10 trivalent linear aliphatic hydrocarbon group, C 4 10 to 2-3 trivalent branched aliphatic hydrocarbon groups, C 5 to 10 divalent or trivalent alicyclic hydrocarbon groups, or two or more of these groups bonded to each other. Or a fluorinated hydrocarbon group in which 20 to 100% of the hydrogen atoms of the hydrocarbon group before fluorination are substituted with fluorine atoms, or
Following formula (3)

(In the formula, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 4.)
It is a bivalent fluorinated hydrocarbon group represented by these. ]
And a hydroxy compound represented by the following formula (5):

[Wherein X represents a halogen atom. R ^{1 to} R ³ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or the following formula (2)

^{(Wherein, R a, R b, R} c, R d, R e are the same or different, .m represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, an integer of 0 to 3. )
The group represented by these is shown. However, at least one of R ^{1 to} R ³ is a hydrogen atom or a group represented by the above formula (2). ]
Is reacted with a silane compound represented by the following formula (1 ′)

(In the formula, R ^{f ′} is an n-valent fluorinated hydrocarbon group, and the hydrocarbon group is a C 3-10 divalent linear aliphatic hydrocarbon group, carbon number 4 10 to 2-3 trivalent branched aliphatic hydrocarbon groups, C 5 to 10 divalent or trivalent alicyclic hydrocarbon groups, or two or more of these groups bonded to each other. Or a fluorinated hydrocarbon group in which 20 to 100% of the hydrogen atoms of the hydrocarbon group before fluorination are substituted with fluorine atoms, or
Following formula (3)

(In the formula, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 10, and n3 represents an integer of 1 to 4.)
It is a bivalent fluorinated hydrocarbon group represented by these . n and R ^{1 to} R ³ are the same as above. The groups in n parentheses may be the same or different. )
A method for producing a fluorine-containing compound, comprising obtaining a fluorine-containing compound represented by the formula: The method for producing a fluorine-containing compound according to claim 4, wherein n1 = 1, n2 = 3, n3 = 1, and m = 0. The method for producing a fluorine-containing compound according to claim 4 or 5, wherein the base is an organic base.