JP2019203038A - Fluorine-containing organosilicon compound, and method of producing the same, room-temperature curable fluorine-containing rubber composition, and cured product of the same and article - Google Patents

Abstract

To provide a new fluorine-containing organosilicon compound suitable for obtaining an elastomer excellent in releasability, water repellency, and low moisture permeability, and in particular heightened in chemical resistance, acid resistance, and amine resistance, and to provide: a method of producing the new fluorine-containing organosilicon compound; and a room-temperature curable fluorine-containing rubber composition containing the compound, and the like.SOLUTION: The fluorine-containing organosilicon compound is provided that is represented by the following formula (1) where A is an unsubstituted or substituted aliphatic bivalent hydrocarbon group, R, and Rare unsubstituted or substituted monovalent hydrocarbon groups, Ris an unsubstituted or substituted saturated aliphatic bivalent hydrocarbon group, Rf is a perfluoroalkylene group or a bivalent perfluoropolyether group, X is a hydrolysable group, Ph is a phenyl group, and Q is a N coupling group containing an unsubstituted or substituted bivalent hydrocarbon group which may be interposed by a specific element in a bond.SELECTED DRAWING: None

Description

  The present invention is, for example, a fluorine-containing organosilicon compound that can be suitably applied as a base polymer of a fluorine-containing elastomer (fluorine-containing rubber cured product) that is useful as a rubber material or a mold release agent and that is excellent in acid resistance and amine resistance. The present invention relates to a method, a room temperature-curable fluorine-containing rubber composition containing the fluorine-containing organosilicon compound, a cured product thereof (fluorine-containing rubber cured product), and articles and uses using the same.

  Organofluorine compounds are used in various fields. For example, a fluorine-containing elastomer (fluorinated rubber cured product) obtained by mixing an organic fluorine compound with a crosslinking agent and crosslinking at a high temperature of 150 ° C. or higher is used as a rubber material or a release agent. However, the above thermosetting material is not suitable for non-heatable applications such as large parts due to the property that high temperature conditions are required. In addition, many elastomers obtained from conventional organic fluorine compounds are insufficient in chemical resistance such as solvent resistance, acid resistance and base resistance. In particular, an elastomer used for a sealant, a molded part or the like is preferably an elastomer that is excellent in releasability, water repellency, low moisture permeability, and cures at room temperature in addition to the above-mentioned chemical resistance. An organic fluorine compound capable of obtaining an elastomer satisfying such properties and a composition containing the same have been reported in Patent Document 1 (Japanese Patent No. 3121245) and the like. Since the base polymer is a perfluoropolyether compound having a bonded phenylene structure in the molecule, the cured product (fluorinated elastomer) obtained from the composition is resistant to chemicals, particularly high concentrations of acids and amine compounds. The durability for a long time is not enough.

Japanese Patent No. 3121245

  The present invention has been made in view of the above circumstances, and includes a novel inclusion suitable for obtaining an elastomer having excellent releasability, water repellency and low moisture permeability, and further improved chemical resistance, particularly acid resistance and amine resistance. It is an object of the present invention to provide a fluorinated organosilicon compound, a production method thereof, a room temperature curable fluorinated rubber composition containing the fluorinated organosilicon compound, and the like.

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ¹及びＲ²は独立に非置換又は置換の１価炭化水素基であり、Ｒ³は独立に非置換又は置換の飽和脂肪族２価炭化水素基であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｘは独立に加水分解性基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは０以上の整数であり、ｂは１、２又は３である。］
で表される含フッ素有機ケイ素化合物をベースポリマーとして用いた室温硬化性含フッ素ゴム組成物が、離型性、撥水性、低透湿性に優れ、耐薬品性、特に耐酸性及び耐アミン性をさらに高めたエラストマーとなり得ることを見出し、本発明をなすに至った。 As a result of extensive studies to achieve the above object, the present inventor has found that the following general formula (1):

[Wherein, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently an unsubstituted or substituted monovalent hydrocarbon group, and R ³ is independently not A substituted or substituted saturated aliphatic divalent hydrocarbon group, Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, and Ph is a phenyl group Q is the following general formula (2) or the following general formula (3):

(In the formula, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding, and Ph is a phenyl group. .)

(In the formula, R ⁵ and R ⁶ are each independently an unsubstituted or substituted divalent hydrocarbon group.)
A is an integer of 0 or more, and b is 1, 2 or 3. ]
The room temperature-curing fluorine-containing rubber composition using a fluorine-containing organosilicon compound represented by the formula as a base polymer is excellent in releasability, water repellency and low moisture permeability, and has chemical resistance, particularly acid resistance and amine resistance. The inventors have found that the elastomer can be further enhanced, and have reached the present invention.

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ¹及びＲ²は独立に非置換又は置換の１価炭化水素基であり、Ｒ³は独立に非置換又は置換の飽和脂肪族２価炭化水素基であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｘは独立に加水分解性基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは０以上の整数であり、ｂは１、２又は３である。］
で表される含フッ素有機ケイ素化合物。
２．
下記一般式（４）：

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ²は独立に非置換又は置換の１価炭化水素基であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｒ¹²は独立に脂肪族不飽和結合を有する非置換又は置換の１価炭化水素基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは０以上の整数である。］
で表される脂肪族不飽和結合を有する含フッ素有機ケイ素化合物と、下記一般式（５）：

（式中、Ｒ¹は非置換又は置換の１価炭化水素基であり、Ｘは加水分解性基であり、ｂは１、２又は３である。）
で表される（オルガノ）ハイドロジェンシラン化合物とを触媒の存在下でヒドロシリル化付加反応させる工程を含む１に記載の含フッ素有機ケイ素化合物の製造方法。
３．
１に記載の含フッ素有機ケイ素化合物及び硬化触媒を含有する室温硬化性含フッ素ゴム組成物。
４．
更に、架橋剤、充填剤、接着助剤、耐熱性付与剤及び着色剤から選ばれる少なくとも一種を含有する３に記載の室温硬化性含フッ素ゴム組成物。
５．
３又は４に記載の室温硬化性含フッ素ゴム組成物の硬化物からなる含フッ素ゴム。
６．
３又は４に記載の室温硬化性含フッ素ゴム組成物を室温で硬化して含フッ素ゴム硬化物を得る工程を含む含フッ素ゴム硬化物の耐熱性、耐薬品性、耐溶剤性、撥水性及び／又は低透湿性を向上させる方法。
７．
３又は４に記載の室温硬化性含フッ素ゴム組成物の硬化物層を有する物品。 Accordingly, the present invention provides the following fluorine-containing organosilicon compound and a method for producing the same, a room temperature-curable fluorine-containing rubber composition, and a cured product thereof.
1.
The following general formula (1):

[Wherein, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently an unsubstituted or substituted monovalent hydrocarbon group, and R ³ is independently not A substituted or substituted saturated aliphatic divalent hydrocarbon group, Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, and Ph is a phenyl group Q is the following general formula (2) or the following general formula (3):

(In the formula, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding, and Ph is a phenyl group. .)

(In the formula, R ⁵ and R ⁶ are each independently an unsubstituted or substituted divalent hydrocarbon group.)
A is an integer of 0 or more, and b is 1, 2 or 3. ]
The fluorine-containing organosilicon compound represented by these.
2.
The following general formula (4):

[Wherein, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group, and Rf is independently a perfluoroalkylene group or A divalent perfluoropolyether group, R ¹² independently represents an unsubstituted or substituted monovalent hydrocarbon group having an aliphatic unsaturated bond, Ph represents a phenyl group, and Q represents the following general formula (2 ) Or the following general formula (3):

(In the formula, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding, and Ph is a phenyl group. .)

(In the formula, R ⁵ and R ⁶ are each independently an unsubstituted or substituted divalent hydrocarbon group.)
A is an integer of 0 or more. ]
A fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the following general formula (5):

(In the formula, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and b is 1, 2 or 3.)
2. The method for producing a fluorine-containing organosilicon compound according to 1, which comprises a step of hydrosilylation addition reaction with an (organo) hydrogensilane compound represented by the formula:
3.
A room temperature-curable fluorine-containing rubber composition comprising the fluorine-containing organosilicon compound according to 1 and a curing catalyst.
4).
4. The room temperature curable fluorinated rubber composition according to 3, further comprising at least one selected from a crosslinking agent, a filler, an adhesion aid, a heat resistance imparting agent, and a colorant.
5.
5. A fluorine-containing rubber comprising a cured product of the room temperature-curable fluorine-containing rubber composition according to 3 or 4.
6).
Heat resistance, chemical resistance, solvent resistance, water repellency of the fluorinated rubber cured product comprising a step of curing the room temperature curable fluorinated rubber composition according to 3 or 4 at room temperature to obtain a fluorinated rubber cured product A method for improving low moisture permeability.
7).
An article having a cured layer of the room temperature curable fluorine-containing rubber composition according to 3 or 4.

  Since the fluorine-containing organosilicon compound of the present invention has a hydrolyzable silyl group at the terminal, it can be cross-linked by reacting with moisture (water) in the air, for example, to become a fluorine-containing elastomer (fluorine-containing rubber cured product). Further, since the fluorine-containing organosilicon compound of the present invention has a high fluorine content, the room temperature curable fluorine-containing rubber composition containing the fluorine-containing organic silicon compound is excellent in solvent resistance, chemical resistance, particularly acid resistance and amine resistance. Furthermore, it is possible to obtain building materials, industrial plant members, sealants, molded parts, extruded parts, coating materials, mold release agents and the like that are also excellent in releasability, water repellency and low moisture permeability. The fluorine-containing rubber composition of the present invention can be used to coat the surface of a specific substrate such as metal, rubber, resin, or fiber. Thereby, it is possible to give the above properties derived from the fluorinated rubber composition and its cured product (fluorinated rubber cured product) to the target substrate, or to improve the above properties of the target substrate. . As the first application, the surface of general-purpose rubber such as nitrile rubber, polyurethane, silicone rubber, butyl rubber, etc., which has poor solvent resistance or water resistance, is coated with solvent resistance and chemical resistance (acid resistance and amine resistance). Moreover, low moisture permeability and water repellency can be imparted to the target substrate, and the above properties can be improved. This approach is effective for all other rubber and elastomer substrates. Furthermore, since the cured product obtained from the fluorine-containing rubber composition is rubbery, there is also an advantage that flexibility, stretchability and other functionality derived from the target rubber substrate and elastomer substrate are not impaired. .

［式中、Ａは独立に非置換又は置換の脂肪族２価炭化水素基であり、Ｒ¹及びＲ²は独立に非置換又は置換の１価炭化水素基であり、Ｒ³は独立に非置換又は置換の飽和脂肪族２価炭化水素基であり、Ｒｆは独立にパーフルオロアルキレン基又は２価のパーフルオロポリエーテル基であり、Ｘは独立に加水分解性基であり、Ｐｈはフェニル基であり、Ｑは下記一般式（２）又は下記一般式（３）：

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基と同じである。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。）
で表される基であり、ａは０以上の整数であり、ｂは１、２又は３である。］ Hereinafter, the present invention will be described in detail.
[Fluorine-containing organosilicon compound]
The fluorine-containing organosilicon compound of the present invention is represented by the following general formula (1).

[Wherein, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently an unsubstituted or substituted monovalent hydrocarbon group, and R ³ is independently not A substituted or substituted saturated aliphatic divalent hydrocarbon group, Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, and Ph is a phenyl group Q is the following general formula (2) or the following general formula (3):

(In the formula, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding, and Ph is a phenyl group. Is the same.)

(In the formula, R ⁵ and R ⁶ are each independently an unsubstituted or substituted divalent hydrocarbon group.)
A is an integer of 0 or more, and b is 1, 2 or 3. ]

In the general formula (1), R ¹ and R ² are each independently an unsubstituted or substituted monovalent hydrocarbon group, preferably an unsubstituted or substituted saturated or unsubstituted group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms. Saturated monovalent hydrocarbon group, and the unsubstituted saturated or unsaturated monovalent hydrocarbon group represented by R ¹ and R ² includes, for example, saturated aliphatic monovalent hydrocarbon such as alkyl group and cycloalkyl group Groups, aromatic monovalent hydrocarbon groups such as an aryl group and aralkyl groups, and unsaturated aliphatic monovalent hydrocarbon groups such as an alkenyl group.
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, and octyl. Group, 2-ethylhexyl group, nonyl group, decyl group and the like, linear or branched alkyl groups having 1 to 10 carbon atoms are mentioned, and more representative examples are methyl group, ethyl group, propyl group, butyl group Group, tert-butyl group, hexyl group and octyl group, particularly preferably a lower alkyl group having 1 to 3 carbon atoms such as methyl group, ethyl group and propyl group.
Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group, and more representative examples include carbon atoms such as a cyclopentyl group and a cyclohexyl group. It is a cycloalkyl group of the number 5 or 6.
Examples of the aryl group include aryl groups having 6 to 15 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a biphenylyl group, and more representative examples include a phenyl group, a tolyl group, An aryl group having 6 to 8 carbon atoms such as a xylyl group.
Examples of the aralkyl group include aralkyl groups having 7 to 10 carbon atoms such as a benzyl group, a phenylethyl group, a phenylpropyl group, and a methylbenzyl group, and more representative examples include a benzyl group and a phenylethyl group. An aralkyl group having 7 or 8 carbon atoms, such as
Examples of the alkenyl group include alkenyl groups having 2 to 10 carbon atoms such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, hexenyl group, cyclohexenyl group, and the like. Typical examples are alkenyl groups having 2 to 4 carbon atoms such as vinyl, allyl and butenyl groups.
As the substituted saturated or unsaturated monovalent hydrocarbon group represented by R ¹ and R ² , at least a part of the hydrogen atoms of the unsubstituted saturated or unsaturated monovalent hydrocarbon group is a fluorine atom, chlorine A group substituted with a halogen atom such as an atom, bromine atom or iodine atom, and typical ones are, for example, chloromethyl group, 2-bromoethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl Group, a halogen-substituted alkyl group having 1 to 8 carbon atoms such as 3,3,4,4,5,5,6,6,6-nonafluorohexyl group and the like. , 3-trifluoropropyl group, 3,3,4,4,5,5,6,6,6-nonafluorohexyl group and the like, are halogen-substituted alkyl groups having 3 to 8 carbon atoms.
Among these, R ¹ is preferably a methyl group, an ethyl group, or a propyl group, and R ² is preferably a methyl group, an ethyl group, or a propyl group.

  In the general formula (1), A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group. Examples of the unsubstituted or substituted aliphatic divalent hydrocarbon group include 1 to 20 carbon atoms. In particular, 2 to 10 unsubstituted or substituted saturated or unsaturated aliphatic divalent hydrocarbon groups may be mentioned. Typical examples include methylene group, ethylene group, propylene group (trimethylene group), and methylethylene group. A linear, branched or cyclic alkylene group having 1 to 10 carbon atoms such as butylene group (tetramethylene group) or hexamethylene group, and more typically carbon such as methylene group, ethylene group or propylene group A linear alkylene group having 1 to 4 atoms; a saturated aliphatic divalent hydrocarbon group such as a cycloalkylene group having 3 to 7 carbon atoms such as a cyclohexylene group; a 1-butenylene group, and 3-heptenylene. A linear or branched alkenylene group having 4 to 10 carbon atoms, or the like; or a combination of these unsubstituted or substituted alkylene groups or cycloalkylene groups; or a part or all of the hydrogen atoms of these groups is fluorine. Examples include groups substituted with halogen atoms such as atoms, chlorine atoms, bromine atoms and iodine atoms. Among these, a linear alkylene group such as an ethylene group or a propylene group is preferable from the viewpoint of ease of synthesis and stability of the compound.

In the general formula (1), R ³ is independently an unsubstituted or substituted saturated aliphatic divalent hydrocarbon group. Examples of the unsubstituted or substituted saturated aliphatic divalent hydrocarbon group for R ³ include, for example, Examples thereof include linear, branched or cyclic saturated aliphatic divalent hydrocarbon groups having 1 to 20 carbon atoms, particularly 2 to 10 carbon atoms. Typical examples include methylene group, ethylene group, propylene. Linear (branched or cyclic) alkylene groups having 1 to 10 carbon atoms, such as a group (trimethylene group), methylethylene group, butylene group, hexamethylene group, and more typically methylene group, ethylene group, propylene A linear alkylene group having 1 to 4 carbon atoms such as a group (trimethylene group); a saturated aliphatic divalent hydrocarbon group such as a cycloalkylene group having 3 to 7 carbon atoms such as a cyclohexylene group; or these Base Examples include groups in which part or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms. Among these, an ethylene group and a propylene group are preferable from the viewpoint of easiness of synthesis and stability of the compound.

In the general formula (1), Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, and among these Rf, the perfluoroalkylene group is a linear or branched group represented by the following general formula. belongs to.
−C _m F _2m −
(In the formula, m is an integer of 1 to 10, preferably an integer of 1 to 6.)

（式中、Ｙは独立にフッ素原子又はトリフルオロメチル基であり、ｐ、ｑ及びｒは、ｐ≧１、ｑ≧１、２≦ｐ＋ｑ≦２００を満足する整数であり、好ましくは３≦ｐ＋ｑ≦１１０、０≦ｒ≦６を満足する整数である。）

（式中、ｒは前記と同じであり、ｓ及びｔは、ｓ≧０、ｔ≧０、２≦ｓ＋ｔ≦２００を満足する整数であり、好ましくは３≦ｓ＋ｔ≦１１０を満足する整数である。）

（式中、Ｙは前記と同じであり、ｕ及びｖは１≦ｕ≦１００、１≦ｖ≦１００を満足する整数である。）

（式中、ｗは１≦ｗ≦１００を満足する整数である。） In addition, examples of the divalent perfluoropolyether group in Rf include those represented by the following general formula.

Wherein Y is independently a fluorine atom or a trifluoromethyl group, and p, q and r are integers satisfying p ≧ 1, q ≧ 1, 2 ≦ p + q ≦ 200, preferably 3 ≦ p + q ≦ 110, 0 ≦ r ≦ 6.)

(Wherein, r is the same as described above, and s and t are integers satisfying s ≧ 0, t ≧ 0, 2 ≦ s + t ≦ 200, preferably 3 ≦ s + t ≦ 110) .)

(In the formula, Y is the same as described above, and u and v are integers satisfying 1 ≦ u ≦ 100 and 1 ≦ v ≦ 100.)

(In the formula, w is an integer satisfying 1 ≦ w ≦ 100.)

（式中、ｐ１は平均で１〜１００、ｑ１は平均で１〜１００、ｐ１＋ｑ１は平均で２〜２００、好ましくは３０〜１１０である。）

（式中、ｐ２は平均で１〜１００、ｑ２は平均で１〜１００、ｐ２＋ｑ２は平均で２０〜１１０、例えば３０である。）

（式中、ｕ１は平均で５〜５０、例えば８であり、ｖ１は平均で１〜１０、例えば２である。）

（式中、ｕ２は平均で５〜５０、例えば１５であり、ｖ２は平均で１〜１０、例えば２である。）

（式中、ｗ１は５〜１００の整数、例えば１０である。） Specific examples of such Rf include those shown below.

(In the formula, p1 is 1 to 100 on average, q1 is 1 to 100 on average, and p1 + q1 is 2 to 200 on average, preferably 30 to 110.)

(Wherein p2 is 1 to 100 on average, q2 is 1 to 100 on average, and p2 + q2 is 20 to 110 on average, for example 30,)

(In the formula, u1 is 5 to 50, for example, 8 on average, and v1 is 1 to 10, for example, 2 on average.)

(Wherein u2 is 5 to 50, for example, 15 on average, and v2 is 1 to 10, for example 2, on average)

(W1 is an integer of 5 to 100, for example 10, in the formula.)

  In the present invention, the polymerization degree (or molecular weight) of the perfluoroalkylene group or divalent perfluoropolyether group as Rf is, for example, in terms of polystyrene in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. The number average degree of polymerization (or the number average molecular weight) can be obtained.

  In the general formula (1), X is independently a hydrolyzable group, and examples of the hydrolyzable group represented by X include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; Examples include groups represented by general formulas.

（式中、Ｒ⁷及びＲ⁸はそれぞれ水素原子又は非置換もしくは置換の１価炭化水素基である。）

(In the formula, R ⁷ and R ⁸ are each a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group.)

Here, examples of the unsubstituted or substituted monovalent hydrocarbon group represented by R ⁷ and R ⁸ include carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. An alkyl group having 1 to 10 carbon atoms, typically, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or an isobutyl group; a cycloalkyl group having 3 to 7 carbon atoms such as a cyclohexyl group; An alkyl group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, and an isobutenyl group, and typically, a carbon atom such as a vinyl group or an isopropenyl group An alkenyl group having 2 to 4 carbon atoms; an aryl group having 6 to 10 carbon atoms such as a phenyl group; or a group in which the hydrogen atoms of these groups are partially substituted with alkoxy groups, etc. For example, an alkoxy-substituted alkyl group having 2 to 4 carbon atoms such as a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, and an ethoxyethyl group.

Ｘとしては、これらの中でもメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基等のアルコキシ基が好ましい。 Specific examples of X include those shown below.

Among these, X is preferably an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, or an isopropoxy group.

（式中、Ｒ⁴は結合途中に酸素原子、窒素原子及びケイ素原子からなる群より選ばれる少なくとも１種を介在させてもよい非置換又は置換の２価炭化水素基であり、Ｐｈはフェニル基である。）

（式中、Ｒ⁵及びＲ⁶は独立に非置換又は置換の２価炭化水素基である。） In the general formula (1), Q is a group represented by the following general formula (2) or the following general formula (3).

(In the formula, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding, and Ph is a phenyl group. .)

(In the formula, R ⁵ and R ⁶ are each independently an unsubstituted or substituted divalent hydrocarbon group.)

(I) Group represented by general formula (2) In general formula (2), R ⁴ may intervene at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding. A substituted or substituted divalent hydrocarbon group, and as R ⁴ , the above-mentioned unsubstituted or substituted aliphatic divalent hydrocarbon group (for example, (cyclo) alkylene group) exemplified as A, aromatic 2 An unsubstituted hydrocarbon group (for example, an arylene group), a combination thereof (for example, an alkylene / arylene group), and at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a silicon atom in the middle of the bond, Substituted aliphatic or aromatic divalent hydrocarbon groups may be mentioned. In the aliphatic or aromatic divalent hydrocarbon group represented by R ⁴ , the oxygen atom may be present as —O— (ether bond), and the nitrogen atom may be —NR ⁹ — (provided that R ⁹ Is a hydrogen atom, an alkyl group or an aryl group), and the silicon atom is a divalent group containing a linear or cyclic organosiloxane structure, or a divalent group. It can intervene as an organosilylene group.

Here, as the alkyl group of R ⁹ , for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, An octyl group etc. are mentioned, and particularly typical ones are the number of carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, etc. 1 to 6 alkyl groups. Examples of the aryl group represented by R ⁹ include aryl groups having 6 to 8 carbon atoms such as a phenyl group, a tolyl group, and a xylyl group. Of these, methyl group, ethyl group, propyl group, butyl group, and phenyl group are preferable as R ⁹ .

（式中、Ｒ¹⁰は独立にアルキル基又はアリール基であり、Ｒ¹¹は独立にアルキレン基であり、ｃは０〜１０の整数、代表的には０〜５の整数である。） Moreover, what is shown below can be illustrated as a bivalent group and diorgano silylene group containing the said linear or cyclic organosiloxane structure.

(Wherein R ¹⁰ is independently an alkyl group or an aryl group, R ¹¹ is independently an alkylene group, and c is an integer of 0 to 10, typically 0 to 5)

Here, examples of the alkyl group or aryl group of R ¹⁰ include the same as the alkyl group or aryl group of R ⁹ .
Examples of the alkylene group of R ¹¹ include alkylene having 1 to 10 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, and decylene group. Groups. Of these, R ¹¹ is preferably a lower alkylene group such as a methylene group, an ethylene group or a propylene group.

（式中、Ｒｆは上記と同じであり、Ｍｅはメチル基である。） Specific examples of the unsubstituted or substituted divalent hydrocarbon group in which at least one selected from the group consisting of an oxygen atom, a nitrogen atom, and a silicon atom may be interposed in the middle of the bond of R ⁴ include, for example, And those represented by the following formula.
- (CH _{2) 2} -,
- (CH _{2) 3} -,
- (CH _{2) 6} -,
_{- (CH 2) 2 -Rf- (} CH 2) 2 -,

(In the formula, Rf is the same as above, and Me is a methyl group.)

（式中、Ｍｅはメチル基であり、Ｐｈはフェニル基であり、Ｒｆは上記と同じである。） Specific examples of the group Q represented by the general formula (2) include the following.

(In the formula, Me is a methyl group, Ph is a phenyl group, and Rf is the same as above.)

(Ii) Group Represented by General Formula (3) In General Formula (3), R ⁵ and R ⁶ are independently an unsubstituted or substituted divalent hydrocarbon group, and this unsubstituted or substituted divalent carbon Examples of the hydrogen group include those exemplified as R ^{3 in the} general formula (1), and typical examples include a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, hexa An alkylene group having 1 to 20 carbon atoms such as a methylene group, particularly an alkylene group having 1 to 10 carbon atoms, and more typically, an alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group or a propylene group; Examples include groups in which some or all of the hydrogen atoms in the group are substituted with halogen atoms such as fluorine, chlorine, bromine and iodine atoms. Of these, ethylene group and propylene group are preferable as R ⁵ and R ⁶ .

（式中、Ｍｅはメチル基である。） Specific examples of the group Q represented by the general formula (3) include the following.

(In the formula, Me is a methyl group.)

In the general formula (1), a is an integer of 0 or more, typically an integer of 0 to 10, more typically an integer of 0 to 6. Therefore, at least one perfluoroalkylene group or divalent perfluoropolyether group is contained in one molecule of the fluorine-containing organosilicon compound of the general formula (1).
In the general formula (1), b is independently 1, 2 or 3, preferably 2 or 3, more preferably 3. Therefore, the fluorine-containing organosilicon compound of the general formula (1) contains 1 to 3 hydrolyzable groups X (that is, 2 to 6 in the molecule) at both ends of the molecular chain.

（式中、Ｒｆ、Ｑ及びａは前記と同じである。Ｍｅはメチル基であり、Ｐｈはフェニル基である。） Examples of the fluorine-containing organosilicon compound represented by the formula (1) include those shown below.

(In the formula, Rf, Q and a are the same as described above. Me is a methyl group and Ph is a phenyl group.)

  The fluorine-containing organosilicon compound represented by the general formula (1) of the present invention includes a low viscosity polymer of several tens of mPa · s to a solid raw rubber-like polymer. For example, for a heat vulcanized rubber, a raw rubber polymer may be used in consideration of ease of handling. For liquid rubber, those having a viscosity at 25 ° C. of about 100 to 100,000 mPa · s may be used. If the viscosity is too low, the resulting cured product loses elasticity and may become brittle. In the present invention, the viscosity can be measured with a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.).

［式中、Ａ、Ｒ²、Ｒｆ、Ｑ及びａは上記と同じであり、Ｐｈはフェニル基であり、Ｒ¹²は独立に脂肪族不飽和結合を有する非置換又は置換の１価炭化水素基である。］

（式中、Ｒ¹、Ｘ、ｂは上記と同じである。） [Method for producing fluorine-containing organosilicon compound]
The fluorine-containing organosilicon compound represented by the general formula (1) of the present invention includes a fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the following general formula (4) and the following general formula (5). It can be produced by subjecting the represented (organo) hydrogensilane compound to a hydrosilylation addition reaction in the presence of a catalyst.

Wherein A, R ² , Rf, Q and a are the same as above, Ph is a phenyl group, and R ¹² is an unsubstituted or substituted monovalent hydrocarbon group independently having an aliphatic unsaturated bond. It is. ]

(Wherein R ¹ , X and b are the same as above)

[Fluorine-containing organosilicon compound of general formula (4)]
In the general formula (4), R ¹² is an unsubstituted or substituted monovalent hydrocarbon group having an aliphatic unsaturated bond capable of hydrosilylation reaction independently with a hydrogen atom bonded to a silicon atom. Examples of R ¹² include 2 to 8 carbon atoms such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, and cyclohexenyl group, and more representative examples include carbon atoms. Aliphatic unsaturated monovalent hydrocarbon groups such as 2-6 alkenyl groups, or some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc. Groups and the like. R ¹² is particularly preferably a vinyl group.

（式中、Ｒｆ、Ｑ及びａは前記と同じである。Ｍｅはメチル基であり、Ｐｈはフェニル基である。） Examples of the fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the formula (4) include those shown below.

(In the formula, Rf, Q and a are the same as described above. Me is a methyl group and Ph is a phenyl group.)

（式中、Ａ、Ｒ²、Ｒ¹²及びＲｆは前記と同じである。Ｐｈはフェニル基である。） [Method for producing fluorine-containing organosilicon compound of general formula (4)]
(I) Production method of fluorine-containing organosilicon compound in which a is 0 in formula (4) The fluorine-containing organosilicon compound in which a in formula (4) is 0 [the following formula (4-1)] For example, as shown in the following reaction formula, a fluorine-containing compound having acid fluoride groups at both ends represented by the following general formula (6) and an aliphatic unsaturated group-containing silyl group represented by the following general formula (7) It can synthesize | combine by making the amine compound which has it react in presence of acid acceptors, such as a triethylamine.

(In the formula, A, R ² , R ¹² and Rf are the same as described above. Ph is a phenyl group.)

（式中、ｐ１は平均で１〜１００、ｑ１は平均で１〜１００、ｐ１＋ｑ１は平均で２〜２００、好ましくは３０〜１１０である。）

（式中、ｐ２は平均で１〜１００、ｑ２は平均で１〜１００、ｐ２＋ｑ２は平均で２０〜１１０、例えば３０である。）

（式中、ｕ１は平均で５〜５０、例えば８であり、ｖ１は平均で１〜１０、例えば２である。）

（式中、ｕ２は平均で５〜５０、例えば１５であり、ｖ２は平均で１〜１０、例えば２である。）

（式中、ｗ１は５〜１００の整数、例えば１０である。） Specific examples of the fluorine-containing compound having an acid fluoride group at both ends represented by the formula (6) are shown below.

(In the formula, p1 is 1 to 100 on average, q1 is 1 to 100 on average, and p1 + q1 is 2 to 200 on average, preferably 30 to 110.)

(Wherein p2 is 1 to 100 on average, q2 is 1 to 100 on average, and p2 + q2 is 20 to 110 on average, for example 30,)

(In the formula, u1 is 5 to 50, for example, 8 on average, and v1 is 1 to 10, for example, 2 on average.)

(Wherein u2 is 5 to 50, for example, 15 on average, and v2 is 1 to 10, for example 2, on average)

(W1 is an integer of 5 to 100, for example 10, in the formula.)

  The viscosity at 25 ° C. of a fluorine-containing compound having an acid fluoride group at both ends represented by the formula (6) at 25 ° C. is 300 to 15,000 mPa · s, particularly 400 to 7,500 mPa · s. Is preferred.

Specific examples of the amine compound having an aliphatic unsaturated group-containing silyl group represented by the formula (7) include those shown below.

  In the above reaction, the compounding ratio of the fluorine-containing compound of the general formula (6) and the amine compound of the general formula (7) is not particularly limited, but the amount of the fluorine-containing compound of the formula (6) used (A) / Amount (B) [molar ratio] of the amine compound of formula (7) is preferably 0.2 to 0.5, particularly preferably 0.4 to 0.5. If the molar ratio is too small, a colored product may be obtained. If the molar ratio is too large, some of the COF groups at both ends of the molecular chain of the fluorine-containing compound of the general formula (6) remain and the reaction is not completed. There is.

  Examples of the acid acceptor used in the above reaction include triethylamine, diisopropylethylamine, pyridine and the like. Although the usage-amount of an acid acceptor is not specifically limited, It is 1.1-1.5 equivalent (molar conversion) with respect to the quantity of the COF group of the molecular chain both ends of the fluorine-containing compound of General formula (6). Is preferred.

  The reaction conditions are not particularly limited, and may be about 20 to 100 ° C. for about 1 to 8 hours, preferably 20 to 50 ° C. for 2 to 4 hours.

（式中、Ａ、Ｒ²、Ｒ¹²、Ｑ、ａ及びＲｆは前記と同じである。Ｐｈはフェニル基である。） (Ii) Production method of fluorine-containing organosilicon compound in which a is 1 or more in formula (4) The fluorine-containing organosilicon compound in which a in formula (4) is 1 or more is, for example, as shown in the following reaction formula In addition, a fluorine-containing compound having an acid fluoride group at both ends represented by the following general formula (6) and a compound having an active hydrogen atom at both ends represented by the following general formula (8) are received by triethylamine or the like. After reacting in the presence of an acid agent, the resulting reaction product represented by the following general formula (9) has an amine compound having an aliphatic unsaturated group-containing silyl group represented by the following general formula (7) Can be synthesized by reacting.

(In the formula, A, R ² , R ¹² , Q, a and Rf are the same as above. Ph is a phenyl group.)

  Examples of the fluorine-containing compound having an acid fluoride group at both ends represented by the formula (6) and the amine compound having an aliphatic unsaturated group-containing silyl group represented by the formula (7) include those described above.

Specific examples of the compound having active hydrogen atoms at both ends represented by the formula (8) include those shown below.

  In the above reaction, the compounding ratio of the fluorine-containing compound of the general formula (6) and the active hydrogen atom-containing compound of the general formula (8) is the molar amount (A) of the fluorine-containing compound of the formula (6) in terms of mole. Although it is not particularly limited as long as it is not less than the molar amount (C) of the active hydrogen atom-containing compound (8), the molar amount ratio (A) / (C) is 1.0 to 3.0, In particular, 1.0 to 2.0 is preferable. In addition, a of General formula (4) can be made into the value according to the objective by adjusting this molar ratio (A) / (C). If (A) / (C) is increased, a polymer having a relatively small molecular weight can be synthesized, and if the value of (A) / (C) is made close to 1, a polymer having a large molecular weight can be synthesized.

  In the above reaction, the mixing ratio of the reaction product of the general formula (9) and the amine compound of the general formula (7) is not particularly limited, but the amount of the reaction product of the formula (9) used (D) / Amount (B) [molar ratio] of the amine compound of formula (7) is preferably 0.2 to 0.5, particularly 0.4 to 0.5. If the molar ratio is too small, a colored product may be obtained. If the molar ratio is too large, some of the COF groups at both ends of the molecular chain of the fluorine-containing compound of the general formula (9) remain and the reaction is not completed. There is a case.

  In addition, examples of the acid acceptor used in the above reaction include the same as those exemplified in the above (i). Although the usage-amount of an acid acceptor is not specifically limited, It is 1.1-1.5 equivalent (molar conversion) with respect to the quantity of the COF group of the molecular chain both ends of the fluorine-containing compound of General formula (9). Is preferred.

  The reaction conditions for the fluorine-containing compound of the formula (6) and the active hydrogen atom-containing compound of the formula (8) and the reaction conditions of the reaction product of the formula (9) and the amine compound of the formula (7) are the same as described above. The reaction conditions of (i) may be the same.

（式中、Ａ、Ｒ²、Ｒ¹²、ａ及びＲｆは上記と同じである。Ｐｈはフェニル基である。Ｐは末端にケイ素原子を有する２価の有機基であり、Ｒ¹³は独立に炭素原子数２〜８の非置換又は置換の２価炭化水素基である。） (Iii) Another method for producing a fluorine-containing organosilicon compound in which a is 1 or more in formula (4) As another method for producing a fluorine-containing organosilicon compound in which a in formula (4) is 1 or more, For example, first, a fluorine-containing organosilicon compound having an aliphatic unsaturated group-containing silyl group at the terminal represented by the formula (4-1) in which a is 0 in the formula (4) is synthesized by the method (i). As shown in the following reaction formula, the obtained fluorine-containing organosilicon compound having an aliphatic unsaturated group-containing silyl group at the end represented by the following general formula (4-1), and the following general formula (10) By reacting a compound having a silicon atom-bonded hydrogen atom at both ends shown in the presence of an addition reaction catalyst, the following general formula (4-2), ie, aliphatic unsaturation represented by general formula (4) Fluorine-containing organosilicon compound having a bond It can be synthesized.

(In the formula, A, R ² , R ¹² , a and Rf are the same as above. Ph is a phenyl group. P is a divalent organic group having a silicon atom at the terminal, and R ¹³ is independently (It is an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms.)

（式中、Ａ、Ｒ²、Ｒ¹³及びＰは上記と同じである。Ｐｈはフェニル基である。） In addition, the following structure in Formula (4-2) corresponds to Q of Formula (4), and the compound of Formula (4-2) is included in the fluorine-containing organosilicon compound of Formula (4). It is.

(In the formula, A, R ² , R ¹³ and P are the same as described above. Ph is a phenyl group.)

（式中、Ｒｆ及びＱは前記と同じである。Ｍｅはメチル基であり、Ｐｈはフェニル基である。） Examples of the fluorine-containing organosilicon compound having an aliphatic unsaturated group-containing silyl group at the terminal represented by the above formula (4-1) include those shown below.

(In the formula, Rf and Q are the same as described above. Me is a methyl group and Ph is a phenyl group.)

（式中、Ｍｅはメチル基である。） In the above formula (10), P is a divalent organic group having a silicon atom at the terminal, and preferably has a siloxane bond, and specific examples thereof are shown below.

(In the formula, Me is a methyl group.)

In the above formula (4-2), R ¹³ is independently an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, preferably unsubstituted or substituted. Saturated aliphatic divalent hydrocarbon group, specifically, a linear or branched alkylene group such as methylene group, ethylene group, propylene group (trimethylene group), methylethylene group, butylene group, hexamethylene group Or a group in which some or all of the hydrogen atoms of these groups are substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Of these, ethylene group and propylene group are preferable.

  In the above reaction, the compounding ratio of the fluorine-containing compound of the general formula (4-1) and the formula (10) is the molar amount (E) of the fluorine-containing compound of the formula (4-1) in terms of moles. The amount of the fluorine-containing organosilicon compound of the formula (4-1) / the amount of the compound of the formula (10) is not particularly limited as long as it is less than the molar amount (F) of the compound of 10). The amount that the used amount (F) [molar ratio] is 1.0 to 3.0, particularly 1.0 to 2.0 is preferable. If the molar ratio (E) / (F) is increased within the above range, a polymer having a relatively small molecular weight can be synthesized. If the value of (E) / (F) is close to 1, A polymer having a large molecular weight can be synthesized.

As the addition reaction catalyst used in the above reaction, a platinum group metal catalyst known as a catalyst used in the hydrosilylation reaction, for example, chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972) ), Complex of chloroplatinic acid and olefin (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452), platinum and alcohol And a complex with vinyl siloxane, platinum black or palladium supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), and the like. Among these, the complex type is preferably used by dissolving in an organic solvent such as alcohol, ketone, ether or toluene.
The use amount of the addition reaction catalyst may be a so-called catalytic amount. The fluorine-containing organosilicon compound having an aliphatic unsaturated group-containing silyl group at the terminal represented by the general formula (4-1) and the general formula (9) It is good to set it as the range of about 10-2,000 ppm in conversion of the mass of a platinum group metal with respect to the total mass with the compound which has a silicon atom bond hydrogen atom in the both terminals shown, More preferably, it is about 100-1,000 ppm.

  In the above reaction, the reaction temperature may be about 50 to 150 ° C, preferably 80 to 120 ° C. The reaction time may be about 2 to 4 hours, preferably about 2 to 3 hours.

（式中、Ｍｅはメチル基である。） [(Organo) hydrogensilane compound of general formula (5)]
Examples of the (organo) hydrogensilane compound represented by the formula (5) include trimethoxysilane, triethoxysilane, dimethoxymethylsilane, dimethoxyethylsilane, diethoxyethylsilane, and those shown below.

(In the formula, Me is a methyl group.)

The amount of the (organo) hydrogensilane compound of the general formula (5) is usually 2 to 10 mol, preferably 2 to 5 mol, per 1 mol of the fluorine-containing organosilicon compound of the general formula (4). If the amount of the (organo) hydrogensilane compound of the formula (5) is too much, too much fraction may be produced during stripping, which is a post-treatment step, and the time required for completion of stripping may become long. (Fluorine-containing organosilicon compound of general formula (4)) A part of terminal alkenyl groups such as Si—CH═CH ₂ group at the terminal may remain and the addition reaction may not be completed.

Examples of the catalyst include platinum group metal catalysts known as catalysts used in hydrosilylation reactions, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972), chloroplatinic acid. And olefin complex (see US Pat. Nos. 3,159,601, 3,159,662, and 3,775,452), platinum black or palladium, etc. Examples thereof include those supported on a carrier such as silica and carbon, rhodium-olefin complexes, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), and the like. Of these, the complex type is preferably used by dissolving in an organic solvent such as alcohol, ketone or ether.
The amount of the catalyst used may be a so-called catalyst amount. For example, the fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the formula (4) and the (organo) hydrogensilane represented by the formula (5) It is good to set it as the range of about 10-2,000 ppm in conversion of the mass of a platinum group metal with respect to the total mass with a compound, More preferably, it is about 100-1,000 ppm.

As described above, the fluorine-containing organosilicon compound represented by the general formula (1) of the present invention includes the fluorine-containing organosilicon compound represented by the general formula (4) and the (organo) hydrogensilane compound represented by the general formula (5). Can be obtained by a hydrosilylation addition reaction in the presence of the catalyst.
In this reaction, the reaction temperature may be about 50 to 150 ° C, preferably 70 to 120 ° C. The reaction time may be about 2 to 4 hours, preferably about 2 to 3 hours. After completion of the reaction, the compound of the formula (5) remaining in the reaction product can be removed by a vacuum strip.

  Since the fluorine-containing organosilicon compound of the present invention thus obtained has hydrolyzable groups (X in the formula (1)) at both ends of the molecular chain, for example, it is hydrolyzed by moisture in the atmosphere. While decomposing, it undergoes condensation polymerization to form a rubber-like cured product. Therefore, the fluorine-containing organosilicon compound of the present invention can be used as a base polymer of a room temperature curable fluorine-containing rubber composition.

[Room-temperature curable fluorine-containing rubber composition]
The room temperature curable fluorinated rubber composition of the present invention essentially contains the fluorinated organosilicon compound of the general formula (1) as a main agent (base polymer). In addition to the fluorinated organosilicon compound, A curing catalyst is included, and an adhesion assistant can be added to the composition.

などのグアニジル基含有シランもしくはシロキサン等のグアニジル化合物；を挙げることができ、これらは１種単独でも２種以上を組み合わせても使用することもできる。なお、上記のうち、特にグアニジル化合物は、硬化反応を良好に進行させると共に接着性向上機能を併せて有しているので好ましい。
これらの硬化触媒は、通常、前記一般式（１）で表される含フッ素有機ケイ素化合物１００質量部に対し、０．０１〜５質量部、特に０．０５〜５質量部程度の範囲が好適である。 The curing catalyst further accelerates the curing rate of the composition, such as lead-2-ethyl octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, butyltin tri-2-ethylhexoate, Iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, zinc-2-ethylhexoate, stannous caprylate, tin naphthenate, tin oleate, Metal salts of organic carboxylic acids such as tin butyrate, titanium naphthenate, zinc naphthenate, cobalt naphthenate, zinc stearate; tetrabutyl titanate, tetra-2-ethylhexyl titanate, triethanolamine titanate, tetra (isopropenyloxy) Organic titanate such as titanate Organic organo compounds such as organosiloxy titanium and β-carbonyl titanium; alkoxyaluminum compounds; aminoalkyl-substituted alkoxysilanes such as 3-aminopropyltriethoxysilane and N- (trimethoxysilylpropyl) ethylenediamine, hexylamine, phosphoric acid Amine compounds such as dodecylamine and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; lower fatty acids of alkali metals such as potassium acetate, sodium acetate and lithium oxalate; dialkylhydroxyls such as dimethylhydroxyamine and diethylhydroxylamine Amine; tetramethylguanidine, the following formula:

Guanidyl compounds such as guanidyl group-containing silanes or siloxanes such as, and the like. These can be used alone or in combination of two or more. Of the above, a guanidyl compound is particularly preferable because it allows the curing reaction to proceed satisfactorily and has a function of improving adhesion.
These curing catalysts are usually in the range of 0.01 to 5 parts by mass, particularly 0.05 to 5 parts by mass with respect to 100 parts by mass of the fluorine-containing organosilicon compound represented by the general formula (1). It is.

で表されるもの等が挙げられる。
これらの接着助剤は、通常、前記一般式（１）で表される含フッ素有機ケイ素化合物１００質量部に対し、０．１〜５．０質量部、特に１．０〜３．０質量部程度の範囲が好適である。 The adhesion aid further improves the adhesion between the cured product and various substrates when the composition is cured. Examples of such an adhesion assistant include vinyl chlorosilane, vinyl trimethoxy silane, vinyl tris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyl tri Ethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyl Trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, as well as partially fluorinated silanes such as 3,3,3-trifluoropropyltrimethoxysilane, and the following formula: CF ₃ (CF _{2) 7 CH 2 CH 2 -Si} (OCH 3) 3 and

The thing etc. which are represented by are mentioned.
These adhesion assistants are usually 0.1 to 5.0 parts by weight, particularly 1.0 to 3.0 parts by weight, based on 100 parts by weight of the fluorine-containing organosilicon compound represented by the general formula (1). A range of about is preferred.

  In addition, the room temperature curable fluorine-containing rubber composition of the present invention includes various additives conventionally used in this type of composition, for example, tetramethoxysilane, in addition to the above-described curing catalyst and adhesion aid. 2 or 3 alkoxy groups in a molecule such as tetraalkoxysilane such as tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane Crosslinkers such as hydrolyzable silane compounds such as (organo) alkoxysilanes having no functional group in the molecule other than hydrolyzable groups, such as alkylalkoxysilanes and arylalkoxysilanes having a group, fumed silica ( Dry silica), precipitated silica (wet silica), fused silica, calcined silica, In addition to silica-based fillers such as crystalline silica (quartz powder), sol-gel silica, and colloidal silica, reinforcing or non-reinforcing fillers such as titanium dioxide, aluminum oxide, carbon, talc and bentonite, asbestos, glass fibers and Fillers such as fibrous fillers such as organic fibers, colorants such as potassium methacrylate, dyes and pigments, heat resistance imparting agents such as bengara (iron oxide) and cerium oxide can also be blended. A predetermined amount of these may be added according to the purpose.

  Moreover, the room temperature curable fluorine-containing rubber composition of the present invention can be stored as a solution diluted with a non-aqueous organic solvent, if necessary, or can be used. In particular, the use as an organic solvent solution is suitable for forming a thin cured film. Examples of such organic solvents include hydrocarbon solvents such as n-hexane, cyclohexane, toluene, petroleum ether, and xylene, ether solvents such as diethyl ether, n-butyl ether, dioxane, and tetrahydrofuran, acetone, methyl ethyl ketone, and dibutyl. Ketone solvents such as ketone and ethyl acetate, chlorinated hydrocarbon solvents such as methylene chloride, chlorobenzene and chloroform, nitrile solvents such as acetonitrile, fluorinated solvents such as trifluorobenzene and metaxylene hexafluoride, methanol, Examples of the alcohol solvent include ethanol, isopropanol, and n-butanol, and these may be used as a mixture of two or more thereof as necessary.

  The room temperature curable fluorine-containing rubber composition of the present invention is a fluorine-containing elastomer (fluorine-containing elastomer) that is cured (crosslinked) by hydrolysis and condensation reaction with moisture (moisture) in the atmosphere at room temperature (25 ° C. ± 10 ° C.). In addition to the properties specific to solvent-resistant fluorine-containing coatings such as water repellency, oil repellency, chemical resistance, low moisture permeability, weather resistance, etc., various bases can be obtained. A cured film (fluorinated rubber cured product) having excellent properties such as adhesion to the material and strength can be formed. Therefore, the room temperature curable fluorine-containing rubber composition of the present invention is useful as a coating agent, a sealing agent, and a paint for the building field, industrial plant, various devices and the like. In addition, because it has excellent adhesion to various metals, resins, rubber, concrete and other base materials, especially when coated on exterior materials, it not only retains its aesthetics over a long period of time, but also has solvent resistance, chemical resistance, and repellent properties. Properties such as aqueous and low moisture permeability can be imparted to the substrate, or the properties of the substrate can be improved. Furthermore, the room temperature curable fluorine-containing rubber composition of the present invention can be applied to various powders, for example, surface treatment agents such as silica filler, quartz powder, ceramic powder, metal powder, and sand, and has water and oil repellency. There are effects such as being able to give.

  The room temperature curable fluorine-containing rubber composition of the present invention can be obtained as a one-pack type room temperature curable fluorine-containing rubber composition by uniformly mixing predetermined amounts of the respective components described above in a dry atmosphere. In this composition, for example, hydrolysis and polycondensation reaction proceed due to moisture in the air to form a cured rubber elastic body. The composition of the present invention is cured at room temperature, but can also be cured by heating. The resulting cured product has solvent resistance, chemical resistance, heat resistance, cold resistance, water repellency, low water content, in relation to the extremely high fluorine content of the fluorine-containing organosilicon compound that is the base component in the composition. It is excellent in any property of moisture permeability. This composition is suitable for a sealing agent, a coating material and the like in the construction and civil engineering industries, and is also very useful as an adhesive for electric and electronic parts, a sealing material and a FIPG material in the automobile industry.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In this example, “Me” represents a methyl group, “Ph” represents a phenyl group, and “PhN” represents a phenylene group. The viscosity is a value measured by a rotational viscometer at 25 ° C., and the degree of polymerization indicates a number average degree of polymerization in terms of polystyrene in gel permeation chromatography (GPC) analysis using a fluorine-based solvent as a developing solvent. The refractive index is a value measured by an Abbe refractometer DR-A1 (manufactured by Atago Co., Ltd.).

（式中、ｐ’＋ｑ’の平均は３８である。）
で示される両末端に酸フロライド基を有する化合物１８９．２ｇ（０．０３０モル、２５℃における粘度：４３０ｍＰａ・ｓ）を投入した。そしてこれを室温（２５℃、以下同じ）下に攪拌しながら滴下ロートより下記式：

で示される化合物１５．８ｇ（０．０７２モル）とトリエチルアミン６．５ｇ（０．０６４モル）との混合物を滴下した。滴下終了後、６０℃で２時間撹拌した。次に、反応混合物を加圧濾過して得られた濾液を、１２０℃／３ｍｍＨｇで減圧ストリップし、淡黄色がかった透明の液状化合物１９５．３ｇを得た。この液状化合物を前記と同様のフラスコに投入し、これにメタキシレンヘキサフロライド５０．０ｇを加え、撹拌しながら１００℃に昇温した後、塩化白金酸のイソプロピルアルコール２質量％溶液０．２ｇを添加した。次いで、これに滴下ロートから下記式：

で示されるシクロテトラシロキサン４．９ｇ（０．０１５モル）を滴下し、２時間反応を行った。滴下終了後、反応生成物を熟成させながらガスクロマトグラフで前記のシクロテトラシロキサンが消失するのを確認し、フラスコ内容物を室温まで冷却した。次に、フラスコ内に、活性炭１．５ｇを投入して２時間撹拌した後、反応混合物を加圧濾過し、得られた濾液を１２０℃／３ｍｍＨｇで減圧ストリップし、透明な液状化合物１９６．１ｇを得た。 [Example 1]
In a 300 ml four-necked flask equipped with a stir bar, thermometer, Jim funnel and dropping funnel, the following formula:

(In the formula, the average of p ′ + q ′ is 38.)
189.2 g (0.030 mol, viscosity at 25 ° C .: 430 mPa · s) having an acid fluoride group at both ends shown in FIG. While stirring this at room temperature (25 ° C., the same shall apply hereinafter), the following formula:

A mixture of 15.8 g (0.072 mol) of the compound represented by formula and 6.5 g (0.064 mol) of triethylamine was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours. Next, the filtrate obtained by pressure filtration of the reaction mixture was stripped under reduced pressure at 120 ° C./3 mmHg to obtain 195.3 g of a light yellowish transparent liquid compound. This liquid compound was put into a flask similar to the above, 50.0 g of metaxylene hexafluoride was added thereto, and the temperature was raised to 100 ° C. while stirring, and then 0.2 g of a 2% by mass solution of chloroplatinic acid in isopropyl alcohol. Was added. Next, from this dropping funnel, the following formula:

Then, 4.9 g (0.015 mol) of cyclotetrasiloxane represented by the formula was added dropwise and reacted for 2 hours. After completion of the dropwise addition, it was confirmed that the cyclotetrasiloxane had disappeared by gas chromatography while aging the reaction product, and the flask contents were cooled to room temperature. Next, 1.5 g of activated carbon was put into the flask and stirred for 2 hours, and then the reaction mixture was filtered under pressure. The obtained filtrate was stripped under reduced pressure at 120 ° C./3 mmHg to obtain 196.1 g of a transparent liquid compound. Got.

This liquid compound had a viscosity of 13,700 mPa · s (25 ° C.) and a refractive index of 1.335. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
¹ H-NMR (TMS standard)
δ = 3.4 to 3.9 ppm (m, N—C H ₂ —, 8H)
δ = 5.4 to 6.2 ppm (m, SiC H = C H ₂ , 6H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹は下記式：

（式中、ｐ’＋ｑ’は平均で３８である。）
で表される基であり、Ｑ¹は下記式：

で表される基であり、ａ１は平均で１である。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Moreover, when the vinyl group content of this compound was quantified, it was 0.014 mol / 100 g, and the obtained compound had the following structural formula (11):

(Where Rf ¹ is the following formula:

(Wherein p ′ + q ′ is 38 on average)
Q ¹ is a group represented by the following formula:

A1 is 1 on average. )
It was confirmed that it is a fluorine-containing organosilicon compound represented by.

In a 500 ml four-necked flask equipped with a stir bar, thermometer, Dim funnel and dropping funnel, 276.2 g of a fluorine-containing organosilicon compound having vinyl groups at both ends represented by the structural formula (11) obtained above. (0.020 mol) and 55 g of metaxylene hexafluoride were added and heated in an oil bath so that the temperature of the flask contents was 80 ° C. while stirring. Next, 0.3 g of a 2% by mass isopropyl alcohol solution of chloroplatinic acid was added to the flask, and then 7.3 g (0.06 mol) of trimethoxysilane was added dropwise from the dropping funnel to react for 2 hours. After completion of the dropwise addition, it was confirmed that the vinyl group (—CH═CH ₂ : δ = 5.4 to 6.2 ppm) of the compound of the formula (11) disappeared by ¹ H-NMR analysis while aging the reaction product. Then, stripped under reduced pressure at 100 ° C./10 mmHg to remove unreacted silane component, and 278.3 g of a light yellowish transparent liquid compound was obtained. The obtained liquid compound had a viscosity of 33,400 mPa · s (25 ° C.) and a refractive index of 1.338. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
¹ H-NMR (TMS standard)
δ = 3.4 to 3.9 ppm (m, N—C H ₂ —, 8H)
δ = 3.67 ppm (s, Si—OC H ₃ , 18H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹、Ｑ¹及びａ１は前記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Moreover, when this liquid compound was hydrolyzed and the amount of desorbed methanol was quantified, it was 0.044 mol / 100 g, and the following structural formula (12):

(In the formula, Rf ¹ , Q ¹ and a1 are the same as described above.)
It was confirmed that it was a fluorine-containing organosilicon compound represented by

で示されるシラン化合物７．９ｇ（０．０５０モル）を用いた以外は、実施例１と同様に反応、後処理を行い、淡黄色がかった透明のオイル状化合物２７９．３ｇを得た。得られたオイル状化合物は粘度が３４，７００ｍＰａ・ｓ（２５℃）であり、屈折率が１．３４０（２５℃）であった。この液状化合物を¹Ｈ−ＮＭＲ測定した結果、以下に示す吸収が認められた。
¹Ｈ−ＮＭＲ（ＴＭＳ標準）
δ＝３．３〜３．８ｐｐｍ（ｍ，Ｎ−ＣＨ ₂−，８Ｈ）
δ＝４．１〜４．２ｐｐｍ（ｍ，ＯＣ＝ＣＨ ₂，８Ｈ）
δ＝６．９〜７．４ｐｐｍ（ｍ，Ｎ−Ｐｈ，２０Ｈ） [Example 2]
In Example 1, instead of 7.3 g of trimethoxysilane, the following formula (13):

The reaction and post-treatment were performed in the same manner as in Example 1 except that 7.9 g (0.050 mol) of the silane compound represented by the formula (1) was used to obtain 279.3 g of a pale yellowish transparent oily compound. The oily compound thus obtained had a viscosity of 34,700 mPa · s (25 ° C.) and a refractive index of 1.340 (25 ° C.). As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
¹ H-NMR (TMS standard)
δ = 3.3 to 3.8 ppm (m, N—C H ₂ —, 8H)
δ = 4.1-4.2 ppm (m, OC = C H ₂ , 8H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹、Ｑ¹及びａ１は前記と同じである。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Moreover, when this compound was hydrolyzed and the amount of acetone removed was quantified, it was 0.028 mol / 100 g, and the following structural formula (14):

(In the formula, Rf ¹ , Q ¹ and a1 are the same as described above.)
It was confirmed that it is a fluorine-containing organosilicon compound represented by.

で示されるシラン化合物８．１ｇ（０．０５０モル）を用いた以外は実施例２と同様に反応、後処理を行い、淡黄色がかった透明の液状化合物２８０．４ｇを得た。得られた液状化合物は、粘度が３５，２００ｍＰａ・ｓ（２５℃）であり、屈折率が１．３４１（２５℃）であった。この液状化合物を¹Ｈ−ＮＭＲ測定した結果、以下に示す吸収が認められた。
¹Ｈ−ＮＭＲ（ＴＭＳ標準）
δ＝１．９４ｐｐｍ（ｓ，ＳｉＯＣＣＨ ₃，１２Ｈ）
δ＝３．３〜３．８ｐｐｍ（ｍ，Ｎ−ＣＨ ₂−，８Ｈ）
δ＝６．９〜７．４ｐｐｍ（ｍ，Ｎ−Ｐｈ，２０Ｈ） [Example 3]
In Example 2, instead of 7.9 g of the silane compound represented by the formula (13), the following formula (15):

The reaction and post-treatment were performed in the same manner as in Example 2 except that 8.1 g (0.050 mol) of the silane compound represented by the formula (1) was used to obtain 280.4 g of a pale yellowish transparent liquid compound. The obtained liquid compound had a viscosity of 35,200 mPa · s (25 ° C.) and a refractive index of 1.341 (25 ° C.). As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
¹ H-NMR (TMS standard)
δ = 1.94 ppm (s, SiOCC H ₃ , 12H)
δ = 3.3 to 3.8 ppm (m, N—C H ₂ —, 8H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 20H)

（式中、Ｒｆ¹、Ｑ¹及びａ１は前記と同じである。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Further, when this compound was hydrolyzed and the amount of acetic acid released was quantified, it was 0.028 mol / 100 g, and the following structural formula (16):

(In the formula, Rf ¹ , Q ¹ and a1 are the same as described above.)
It was confirmed that it is a fluorine-containing organosilicon compound represented by.

（式中、ｐ’＋ｑ’の平均は３８である。）
で示される両末端に酸フロライド基を有する化合物１８９．２ｇ（０．０３０モル、２５℃における粘度：４３０ｍＰａ・ｓ）を投入した。そしてこれを室温下に攪拌しながら滴下ロートより下記式：

で示される化合物２．３ｇ（０．０２モル）とトリエチルアミン６．５ｇ（０．０６４モル）との混合物を滴下した。滴下終了後、６０℃で２時間撹拌した。次に、これに滴下ロートから下記式：

で示される化合物５．３ｇ（０．０２４モル）を滴下し、反応を行った。滴下終了後、反応生成物を熟成させながら¹⁹Ｆ−ＮＭＲで前記の両末端に酸フロライド基を有する化合物のＣＯＦ由来のシグナルの消失を確認し、フラスコ内容物を室温まで冷却した。次に、フラスコ内に、活性炭１．５ｇを投入して２時間撹拌した後、反応混合物を加圧濾過し、得られた濾液を１２０℃／３ｍｍＨｇで減圧ストリップし、薄黄色の液状化合物１８４．９ｇを得た。 [Example 4]
In a 300 ml four-necked flask equipped with a stir bar, thermometer, Jim funnel and dropping funnel, the following formula:

(In the formula, the average of p ′ + q ′ is 38.)
189.2 g (0.030 mol, viscosity at 25 ° C .: 430 mPa · s) having an acid fluoride group at both ends shown in FIG. And while stirring this at room temperature, the following formula:

A mixture of 2.3 g (0.02 mol) of the compound represented by formula and 6.5 g (0.064 mol) of triethylamine was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours. Next, from this dropping funnel, the following formula:

Then, 5.3 g (0.024 mol) of the compound represented by the formula was added dropwise to carry out the reaction. After completion of the dropping, the reaction product was aged, and the disappearance of the COF-derived signal of the compound having an acid fluoride group at both ends was confirmed by ¹⁹ F-NMR, and the flask contents were cooled to room temperature. Next, 1.5 g of activated carbon was put into the flask and stirred for 2 hours, and then the reaction mixture was subjected to pressure filtration. The obtained filtrate was stripped under reduced pressure at 120 ° C./3 mmHg to obtain a pale yellow liquid compound 184. 9 g was obtained.

This liquid compound had a viscosity of 35,300 mPa · s (25 ° C.) and a refractive index of 1.346. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
¹ H-NMR (TMS standard)
δ = 0.45 ppm (s, Si—C H ₃ , 12H)
δ = 1.1 to 1.5 ppm (m, C—C H ₃ , 12H)
δ = 3.3~3.8ppm (m, CON- C H 2 -, 4H)
δ = 5.4 to 6.2 ppm (m, SiC H = C H ₂ , 6H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 10H)

（式中、Ｒｆ¹は上記と同じであり、Ｑ²は下記式：

で表される基であり、ａ２は平均で２である。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Moreover, when the vinyl group content of this compound was quantified, it was 0.01 mol / 100 g, and the obtained compound had the following structural formula (17):

(Wherein Rf ¹ is the same as above, and Q ² is the following formula:

A2 is 2 on average. )
It was confirmed that it is a fluorine-containing organosilicon compound represented by.

  In a 500 ml four-necked flask equipped with a stir bar, thermometer, Dim funnel and dropping funnel, 393.9 g of a fluorine-containing organosilicon compound having vinyl groups at both ends represented by the structural formula (17) obtained above. (0.020 mol) and 64.8 g of metaxylene hexafluoride were added, and the mixture was heated in an oil bath so that the temperature of the flask content was 70 ° C. while stirring. Next, 0.3 g of a 2% by mass isopropyl alcohol solution of chloroplatinic acid was added to the flask, and then 9.5 g (0.078 mol) of trimethoxysilane was added dropwise from the dropping funnel to react for 2 hours. Thereafter, the reaction and the post-treatment were performed in the same manner as in Example 1. As a result, 397.0 g of a light yellowish transparent liquid compound was obtained.

The obtained compound had a viscosity of 84,200 mPa · s (25 ° C.) and a refractive index of 1.324 (25 ° C.). As a result of ¹ H-NMR measurement, the following absorption was confirmed.
¹ H-NMR (TMS standard)
δ = 0.45 ppm (s, Si—C H ₃ , 12H)
δ = 1.1 to 1.5 ppm (m, C—C H ₃ , 12H)
δ = 3.3~3.8ppm (m, CON- C H 2 -, 4H)
δ = 3.63 ppm (s, SiO—C H ₃ , 18H)
δ = 6.9 to 7.4 ppm (m, N- Ph , 10H)

（式中、Ｒｆ¹、Ｑ²、ａ２は上記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Moreover, when this compound was hydrolyzed and the amount of methanol released was quantified, it was 0.031 mol / 100 g, and the following structural formula (18):

(In the formula, Rf ¹ , Q ² and a2 are the same as above.)
It was confirmed that it was a fluorine-containing organosilicon compound represented by

［式中、Ｒｆ²は下記式：

（式中、ｐ’＋ｑ’は平均で９４である。）
で表される基である。］
で表される化合物３２０．２ｇ（０．０２０モル）を用い、メタキシレンヘキサフロライドの使用量を６０．０ｇにした以外は実施例１と同様に反応、後処理を行い、淡黄色がかった透明の液状化合物３２４．１ｇを得た。 [Comparative Example 1]
In Example 1, in place of 276.2 g of the compound of formula (11), the following formula (19):

[Wherein Rf ² represents the following formula:

(Wherein p ′ + q ′ is 94 on average)
It is group represented by these. ]
The reaction and post-treatment were performed in the same manner as in Example 1 except that 320.2 g (0.020 mol) of the compound represented by formula (1) was used and the amount of metaxylene hexafluoride was changed to 60.0 g. 324.1 g of a transparent liquid compound was obtained.

The obtained liquid compound had a viscosity of 18,300 mPa · s (25 ° C.) and a refractive index of 1.320 (25 ° C.). As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was confirmed.
¹ H-NMR (TMS standard)
δ = 0.42 ppm (s, Si—C H ₃ , 12H)
δ = 3.56 ppm (s, Si—OC H ₃ , 18H)

（式中、Ｒｆ²は上記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Further, when this compound was hydrolyzed and the amount of desorbed methanol was quantified, it was 0.039 mol / 100 g, and the following structural formula (20):

(In the formula, Rf ² is the same as above.)
It was confirmed that it was a fluorine-containing organosilicon compound represented by

（式中、ｐ’＋ｑ’の平均は３８である。）
で示される両末端に酸フロライド基を有する化合物１８９．２ｇ（０．０３０モル、２５℃における粘度：４３０ｍＰａ・ｓ）を投入した。そしてこれを室温下に攪拌しながら滴下ロートより下記式：

で示される化合物１３．８ｇ（０．０７２モル）とトリエチルアミン６．５ｇ（０．０６４モル）との混合物を滴下した。滴下終了後、６０℃で２時間撹拌した。次に、反応混合物を加圧濾過して得られた濾液を、１２０℃／３ｍｍＨｇで減圧ストリップし、淡黄色がかった透明の液状化合物１９５．３ｇを得た。この液状化合物を前記と同様のフラスコに投入し、これにメタキシレンヘキサフロライド５０．０ｇを加え、撹拌しながら１００℃に昇温した後、塩化白金酸のイソプロピルアルコール２質量％溶液０．２ｇを添加した。次いで、これに滴下ロートから下記式：

で示されるシクロテトラシロキサン４．９ｇ（０．０１５モル）を滴下し、２時間反応を行った。滴下終了後、反応生成物を熟成させながらガスクロマトグラフで前記のシクロテトラシロキサンが消失するのを確認し、フラスコ内容物を室温まで冷却した。次に、フラスコ内に、活性炭１．５ｇを投入して２時間撹拌した後、反応混合物を加圧濾過し、得られた濾液を１２０℃／３ｍｍＨｇで減圧ストリップし、透明な液状化合物１９７．４ｇを得た。 [Comparative Example 2]
In a 300 ml four-necked flask equipped with a stir bar, thermometer, Jim funnel and dropping funnel, the following formula:

(In the formula, the average of p ′ + q ′ is 38.)
189.2 g (0.030 mol, viscosity at 25 ° C .: 430 mPa · s) having an acid fluoride group at both ends shown in FIG. And while stirring this at room temperature, the following formula:

A mixture of 13.8 g (0.072 mol) of the compound shown below and 6.5 g (0.064 mol) of triethylamine was added dropwise. After completion of dropping, the mixture was stirred at 60 ° C. for 2 hours. Next, the filtrate obtained by pressure filtration of the reaction mixture was stripped under reduced pressure at 120 ° C./3 mmHg to obtain 195.3 g of a light yellowish transparent liquid compound. This liquid compound was put into a flask similar to the above, 50.0 g of metaxylene hexafluoride was added thereto, and the temperature was raised to 100 ° C. while stirring, and then 0.2 g of a 2% by mass solution of chloroplatinic acid in isopropyl alcohol. Was added. Next, from this dropping funnel, the following formula:

Then, 4.9 g (0.015 mol) of cyclotetrasiloxane represented by the formula was added dropwise and reacted for 2 hours. After completion of the dropwise addition, it was confirmed that the cyclotetrasiloxane had disappeared by gas chromatography while aging the reaction product, and the flask contents were cooled to room temperature. Next, 1.5 g of activated carbon was put into the flask and stirred for 2 hours, and then the reaction mixture was filtered under pressure. The obtained filtrate was stripped under reduced pressure at 120 ° C./3 mmHg to obtain 197.4 g of a transparent liquid compound. Got.

This liquid compound had a viscosity of 15,200 mPa · s (25 ° C.) and a refractive index of 1.335. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
¹ H-NMR (TMS standard)
δ = 3.42 ppm (S, N—C H ₃ , 12H)
δ = 5.5 to 6.3 ppm (m, SiC H = C H ₂ , 6H)
δ = 7.1-7.8 ppm (m, PhN , 16H)

（式中、Ｒｆ¹は下記式：

（式中、ｐ’＋ｑ’は平均で３８である。）
で表される基であり、Ｑ³は下記式：

で表される基であり、ａ１は平均で１である。）
で表される含フッ素有機ケイ素化合物であることが確認された。 Moreover, when the vinyl group content of this compound was quantified, it was 0.014 mol / 100 g, and the obtained compound had the following structural formula (21):

(Where Rf ¹ is the following formula:

(Wherein p ′ + q ′ is 38 on average)
Q ³ is a group represented by the following formula:

A1 is 1 on average. )
It was confirmed that it is a fluorine-containing organosilicon compound represented by.

In a 500 ml four-necked flask equipped with a stir bar, thermometer, Dim funnel and dropping funnel, 276.2 g (0.020) of a compound having vinyl groups at both ends represented by the structural formula (21) obtained above was obtained. Mol) and 55 g of metaxylene hexafluoride were added and heated in an oil bath with stirring so that the temperature of the flask contents reached 80 ° C. Next, 0.3 g of a 2% by mass solution of chloroplatinic acid in isopropyl alcohol was added to the flask, and then 7.3 g (0.060 mol) of trimethoxysilane was added dropwise from the dropping funnel to react for 2 hours. After completion of the dropwise addition, it was confirmed that the vinyl group (—CH═CH ₂ : δ = 5.5 to 6.3 ppm) of the compound of the formula (21) disappeared by ¹ H-NMR analysis while aging the reaction product. Then, stripped under reduced pressure at 100 ° C./10 mmHg to remove unreacted silane component, and 278.3 g of a light yellowish transparent liquid compound was obtained. The obtained liquid compound had a viscosity of 34,200 mPa · s (25 ° C.) and a refractive index of 1.103. As a result of ¹ H-NMR measurement of this liquid compound, the following absorption was observed.
¹ H-NMR (TMS standard)
δ = 3.44 ppm (S, N—C H ₃ , 12H)
δ = 3.67 ppm (S, Si—OC H ₃ , 18H)
δ = 7.1-7.8 ppm (m, PhN , 16H)

（式中、Ｒｆ¹、Ｑ³及びａ１は前記と同じである。）
で示される含フッ素有機ケイ素化合物であることが確認された。 Moreover, when this liquid compound was hydrolyzed and the amount of desorbed methanol was quantified, it was 0.044 mol / 100 g, and the following structural formula (22):

(In the formula, Rf ¹ , Q ³ and a1 are the same as described above.)
It was confirmed that it was a fluorine-containing organosilicon compound represented by

[Example 5]
100 g of the fluorine-containing organosilicon compound of the formula (12) obtained in Example 1 and 20 g of MT carbon (medium-sized pyrolytic carbon, manufactured by Denka Co., Ltd., the same applies hereinafter) are mixed, and this mixture is mixed into three rolls. A composition I was obtained by mixing once and then mixing 0.1 g of dibutyltin dioctoate. This composition I was formed into a sheet having a thickness of 2 mm, and the sheet was allowed to stand for 14 days in an atmosphere having a temperature of 20 ° C. and a relative humidity of 55% to be cured. Rubber properties (hardness, tensile strength, elongation at break) of the obtained sheet-like rubber elastic body (hereinafter referred to as elastic body I) were measured according to JIS C 2123. The results are shown in Table 1.
The composition I was stored in a sealed state at room temperature. Composition I was stable for over 6 months. A sheet-like rubber elastic body (hereinafter referred to as an elastic body I ′) was prepared from the composition I after the lapse of 6 months in the same manner as described above, and the rubber physical properties of the rubber elastic body were measured in the same manner as described above. Table 1 shows the results.
In addition, the hardness in a table | surface is the value measured using the spring type hardness tester (A type) (hereinafter, the same).

[Comparative Example 3]
By mixing 100 g of the fluorine-containing organosilicon compound of the formula (22) obtained in Comparative Example 2 and 20 g of MT carbon, this mixture was passed once through three rolls, and then 0.1 g of dibutyltin dioctoate was mixed. Composition II was obtained. This composition II was formed into a sheet having a thickness of 2 mm, and the sheet was cured by leaving it for 14 days in an atmosphere of a temperature of 20 ° C. and a relative humidity of 55%. The rubber physical properties of the obtained sheet-like rubber elastic body (hereinafter referred to as elastic body II) were measured according to JIS C2123. The results are shown in Table 1.
The composition II was stored in a sealed state at room temperature. Composition II was stable for over 6 months. A sheet-like rubber elastic body (hereinafter referred to as elastic body II ′) was prepared from Composition II after 6 months in the same manner as described above, and the rubber physical properties of this rubber elastic body were measured in the same manner as described above. Table 1 shows the results.

  Next, the elastic bodies I and II were evaluated for the following solvent resistance, acid resistance, heat resistance, cold resistance, moisture permeability, and amine resistance.

Solvent Resistance The elastic body was immersed in each solvent at 25 ° C. shown in Table 2 for 7 days, and the solvent resistance was evaluated by the volume change rate. The results are shown in Table 2. The fluoro rubber in Table 2 is Viton E-60C manufactured by DuPont, which was used for comparison.

Acid resistance The elastic body is immersed for 1 week in 40 ° C. acid (98% by mass sulfuric acid and 60% by mass nitric acid) shown in Table 3, and the acid resistance is determined by the rate of change in hardness and the rate of change in mass (weight loss on heating: mass%). Evaluated. The results are shown in Table 3. In addition, the hardness in a table | surface is the value measured using the spring type hardness tester (A type). The elastic body I obtained from the composition I of Example 5 was compared with the elastic body II obtained from the composition II of Comparative Example 3, and the hardness change rate when immersed in 98 mass% sulfuric acid and 60 mass% nitric acid and The mass change rate tended to be small. In particular, when immersed in 98 mass% sulfuric acid, the elastic body I maintained its shape, while the elastic body II decomposed. In addition, the silicone rubber of Table 3 is a cured product of a condensation curable room temperature curable silicone rubber composition manufactured by Shin-Etsu Chemical Co., Ltd .; used for comparison; KE-951.

Rubber properties (based on JIS C 2123) before and after heating the heat-resistant elastic body at 250 ° C. for 120 hours were measured and evaluated. The results are shown in Table 4. In Table 4, the reduction rate of the mass after heating with respect to the mass before heating (heating loss: mass%) is also shown.

According to cold resistance JIS K 6301, the test piece was cooled to −70 ° C. in dry ice / ethanol and then heated at a rate of 1 ° C./min. The rigidity at each temperature at this time was measured with a Gehman torsion tester manufactured by Ueshima Seisakusho, and the temperatures when the rigidity at room temperature was 2, 5, 10 and 100 times the T ₂ respectively. It was measured as _{T 5, T 10, T 100} . The results are shown in Table 5. The fluoro rubber in Table 5 is Viton E-60C manufactured by DuPont, which was used for comparison.

The moisture-permeable elastic body was charged into a L80-5000 water vapor transmission meter manufactured by Lyssy, and the water vapor transmission rate was measured. The results are shown in Table 6.

Amine resistance The elastic body was immersed in an amine at 40 ° C. for 1 week, and the amine resistance was evaluated by the amount of change in hardness. The results are shown in Table 7. The hardness in a table | surface is the value measured using the spring type hardness tester (A type). The elastic body I obtained from the composition I of Example 5 tended to have a lower hardness change rate when immersed in ethylenediamine and diethylamine than the elastic body II obtained from the composition II of Comparative Example 3. .

[Example 6]
A mixture of 100 parts by mass of the fluorine-containing organosilicon compound of formula (12) obtained in Example 1 and 2 parts by mass of methyltrimethoxysilane was dissolved in metaxylene hexafluoride to prepare a 20% by mass solution of the mixture. did. After dipping the slide glass in this solution for 30 seconds, it was allowed to stand for 18 hours at 20 ° C. and 55% RH to form a cured film on the surface of the slide glass. When one drop of n-hexadecane was placed on the slide glass on which this cured film was formed, and when one drop of pure water was placed, the contact angle of each droplet with respect to the slide glass was measured. The results are shown in Table 8.

[Example 7]
A mixture of 100 parts by mass of the fluorine-containing organosilicon compound of the formula (12) obtained in Example 1, 2 parts by mass of methyltrimethoxysilane, and 0.2 parts by mass of dibutyltin dilaurate was dissolved in metaxylene hexafluoride, A 50% by weight solution of the mixture was prepared. This solution was applied to the surface of the slide glass and allowed to stand at 20 ° C. and 55% RH for 6 hours to form a cured film on the surface of the slide glass. The contact angle of the slide glass on which this cured film was formed was measured in the same manner as in Example 6. The results are shown in Table 8.

[Comparative Example 4]
A mixture of 100 parts by mass of the fluorine-containing organosilicon compound of formula (22) obtained in Comparative Example 2 and 2 parts by mass of methyltrimethoxysilane was dissolved in metaxylene hexafluoride to prepare a 20% by mass solution of the mixture. did. After dipping the slide glass in this solution for 30 seconds, it was allowed to stand for 18 hours at 20 ° C. and 55% RH to form a cured film on the surface of the slide glass. The contact angle of the slide glass on which this cured film was formed was measured in the same manner as in Example 6. The results are shown in Table 8.

Claims (7)

The following general formula (1):

[Wherein, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ¹ and R ² are independently an unsubstituted or substituted monovalent hydrocarbon group, and R ³ is independently not A substituted or substituted saturated aliphatic divalent hydrocarbon group, Rf is independently a perfluoroalkylene group or a divalent perfluoropolyether group, X is independently a hydrolyzable group, and Ph is a phenyl group Q is the following general formula (2) or the following general formula (3):

(In the formula, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding, and Ph is a phenyl group. .)

(In the formula, R ⁵ and R ⁶ are each independently an unsubstituted or substituted divalent hydrocarbon group.)
A is an integer of 0 or more, and b is 1, 2 or 3. ]
The fluorine-containing organosilicon compound represented by these. The following general formula (4):

[Wherein, A is independently an unsubstituted or substituted aliphatic divalent hydrocarbon group, R ² is independently an unsubstituted or substituted monovalent hydrocarbon group, and Rf is independently a perfluoroalkylene group or A divalent perfluoropolyether group, R ¹² independently represents an unsubstituted or substituted monovalent hydrocarbon group having an aliphatic unsaturated bond, Ph represents a phenyl group, and Q represents the following general formula (2 ) Or the following general formula (3):

(In the formula, R ⁴ is an unsubstituted or substituted divalent hydrocarbon group which may have at least one selected from the group consisting of an oxygen atom, a nitrogen atom and a silicon atom in the middle of bonding, and Ph is a phenyl group. .)

(In the formula, R ⁵ and R ⁶ are each independently an unsubstituted or substituted divalent hydrocarbon group.)
A is an integer of 0 or more. ]
A fluorine-containing organosilicon compound having an aliphatic unsaturated bond represented by the following general formula (5):

(In the formula, R ¹ is an unsubstituted or substituted monovalent hydrocarbon group, X is a hydrolyzable group, and b is 1, 2 or 3.)
The method for producing a fluorinated organosilicon compound according to claim 1, comprising a step of hydrosilylation addition reaction with the (organo) hydrogensilane compound represented by the formula:   A room temperature-curable fluorine-containing rubber composition containing the fluorine-containing organosilicon compound according to claim 1 and a curing catalyst.   The room temperature curable fluorinated rubber composition according to claim 3, further comprising at least one selected from a crosslinking agent, a filler, an adhesion aid, a heat resistance imparting agent, and a colorant.   A fluorine-containing rubber comprising a cured product of the room temperature-curable fluorine-containing rubber composition according to claim 3 or 4.   The heat-resistant, chemical resistance, solvent resistance, and repellent properties of the fluorinated rubber cured product comprising a step of curing the room temperature-curable fluorinated rubber composition according to claim 3 or 4 at room temperature to obtain a fluorinated rubber cured product. A method for improving aqueous and / or low moisture permeability.   An article having a cured product layer of the room temperature curable fluorinated rubber composition according to claim 3 or 4.