JPH09143270A - New siloxane derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a new siloxane derivative useful as a cosmetic, excellent in lubricity, water/oil repellencies and having a good touch and functions to prevent messy makeup by carrying out the hydrosilylating reaction of an Si-H group-containing siloxane with an unsaturated fluorine-containing macromer in the presence of a catalyst. SOLUTION: This new siloxane derivative is represented by formula I at least one of R<1> to R<3> is a substituent group represented by formula II [R<5> is H, a 1-18C alkyl, phenyl, an alkenyl, etc.; R<6> is a 2-18C hydrocarbon; (n) is 2-500]; R<1> to R<3> other than those described above and R<4> are each a 1-18C alkyl; (a) and (b) are each a number so as to provide 1-3000 average value of [(a)+(b)]}. The siloxane derivative has a siloxane skeleton in the same molecule and a fluorine-containing polyether skeleton and is useful for a cosmetic, etc., having good lubricity and water/oil repellencies together and further a good touch and functions to prevent messy makeup. The compound is obtained by carrying out the hydrosilylating reaction of an Si-H group-containing siloxane represented by formula III (at least one of R<7> to R<9> is H and the others are each a 1-18C alkyl) with a fluorine-containing macromer represented by formula IV (R<10> is a 0-16C hydrocarbon) in the presence of a catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel fluorine-containing organopolysiloxane and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Organopolysiloxane has low surface tension and low refractive index, and has heat resistance, cold resistance, electric insulation, water repellency, releasability, defoaming property,
Due to its excellent properties such as chemical resistance, it is used in a wide range of industrial fields today (Reference: Silicone Handbook, edited by Kunio Ito, Nikkan Kogyo Shimbun, 1990.
Year).

On the other hand, a fluorine-containing compound generally has a very low surface free energy, so that it has water repellency, oil repellency, antifouling property, non-adhesiveness, and low friction, and a liquid substance has a high surface tension. It is known to exhibit unique properties such as wettability and permeability (reference: Fluororesin Handbook, edited by Takaomi Satokawa, Nikkan Kogyo Shimbun, 1990).

Recently, a polysiloxane containing a perfluoroalkyl group or a perfluoropolyether group as a substituent has been developed as a substance having both of these physical properties (JP-A-63-27530, JP-A-63-30530). 63-41535, Japanese Patent Publication No. 6-18880, etc.). However, all of them have poor compatibility with other materials, so that there is a problem that it is difficult to make them into a blend.

An object of the present invention is to provide a novel siloxane derivative having a perfluoroalkyl group with improved compatibility with various materials such as cosmetic raw materials.

[0006]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and as a result, the following general formula (1):

[0007]

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[Wherein at least one of R ¹ , R ² and R ³ is represented by the following formula (2) or (3)

[0009]

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(R ⁵ is hydrogen or a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or an alkenyl group; R ⁶ is a hydrocarbon group having an average carbon number of 2 to 18; Is a number of 2 to 500 on average) (including the case where a part of R ³ is substituted), and R ¹ , R ² and R ³ and R ⁴ other than the above are carbon numbers. 1 to 18 alkyl groups, and a and b are numbers in which the average value of a + b is 1 to 3000.
However, R ¹ , R ² and a plurality of R ³ may be the same or different. ] The siloxane derivative represented by
A substance having excellent compatibility with other base materials (for example, cosmetic raw materials) and having the above-mentioned excellent properties of organopolysiloxane and excellent properties of a fluorine compound, and a method for producing the substance, Completed the invention.

That is, the present invention provides a novel fluorine-containing siloxane derivative represented by the above general formula (1) and a method for producing the same. The present invention will be described in more detail below. The siloxane derivative (1) of the present invention can be produced by the method shown in the following (A) or (B).

According to the method (A), the siloxane derivative (1) of the present invention has at least one hydrogen atom bonded to a silicon atom in one molecule in the presence of a hydrosilylation catalyst according to the following reaction formula. A siloxane (4) represented by the following general formula (4) and a fluorine-containing macromonomer (5) or (6) having a carbon-carbon double bond represented by the following formula (5) or (6): It is produced by a hydrosilylation reaction.

[0013]

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[0014] (In the formula (4), at least one hydrogen of R ^7, R ⁸ and R ^9, R ⁷ other than the above, R ⁸ and R ⁹ as well as
R ⁴ is an alkyl group having 1 to 18 carbon atoms, and a and b are numbers having an average value of a + b of 1 to 3000. Also, equations (5) and (6)
Wherein R ⁵ is hydrogen or an alkyl group having 6 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, and n
Is 2 to 500 on average. ) Examples of the siloxane (4) used in the above reaction include pentamethyldisiloxane, heptamethyltrisiloxane, nonamethyltetrasiloxane, undecamethylpentasiloxane, tridecamethylhexasiloxane, tetramethyldisiloxane, hexamethyltrisiloxane. From the relatively short chain length siloxanes represented by siloxane, octamethyltetrasiloxane, decamethylpentasiloxane, dodecamethylhexasiloxane, etc.
Up to about 10,000 long-chain polysiloxanes, that is, a +
The average value of b is 1 to 3000, and at least 1 is present in the molecule.
Any one containing one Si-H group can be used.

As the hydrosilylation catalyst, one containing platinum, rhodium, palladium, osmium, iridium or the like can be used. Specifically, it is chloroplatinic acid or the like. The amount of catalyst used is 20 × 10 ⁻⁶ to 500 for Si-H bond.
It is about 10 ⁻⁶ mol.

The fluorine-containing macromonomer (5) having a carbon-carbon double bond is an alkali metal alkoxide or an alkali metal water in the presence of a hydrocarbon alcohol having a carbon-carbon double bond and having an average carbon number of 2-18. By polymerizing trifluoropropylene oxide using an oxide as a catalyst, and the fluorine-containing macromonomer (6) is polymerized with trifluoropropylene oxide using an alkali metal alkoxide or an alkali metal hydroxide as a catalyst, and then using an allyl halide. It can be easily produced by stopping the reaction. The molecular weights of the fluorine-containing macromonomers (5) and (6) are respectively the number of moles of allyl alcohol to the number of moles of trifluoropropylene oxide as a monomer, and the amount of alkali metal alkoxide or alkali metal hydroxide as a catalyst. It can be arbitrarily controlled by the number of moles.

In the hydrosilylation reaction of the above siloxane (4) with the fluorine-containing macromonomer (5) or (6), the fluorine-containing macromonomer (5) or (6) having a carbon-carbon double bond. Siloxane (4)
It is about 0.1 to 3.0 mol relative to the Si-H bond. However, when only a part of the Si-H bond is hydrosilylated, a hydrocarbon having a carbon-carbon double bond and having 2 to 18 carbon atoms,
For example, unreacted Si-H bond is reacted with 1-hexene or the like to be substituted with a hydrocarbon group.

The hydrosilylation reaction is generally from 0 to 150
It is carried out in a temperature range of ° C, and a solvent such as n-pentane, n-heptane, n-octane, benzene, toluene, or xylene can be used as necessary for controlling the reaction temperature and the viscosity of the reaction system. .

Further, according to the method (b), the siloxane derivative of the present invention is obtained by one or more cyclic polysiloxanes (7) represented by the formula (7) in the presence of an acid catalyst or a base catalyst according to the following reaction formula. And a mixture of one or more kinds of chain siloxanes (8) represented by the formula (8) are equilibrated.

[0020]

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(Here, R ¹ , R ² , R ³ , R ⁴ , a, and b are the same as above) The siloxane derivative (1) to be produced is not particularly limited in molecular weight, but cyclic polysiloxane (7) It can be arbitrarily controlled by adjusting the number of moles of the chain siloxane (8) charged.

Acids or bases are used as the catalyst. Specifically, as the acid catalyst, inorganic acids such as sulfuric acid, sulfonic acids such as methanesulfonic acid, carboxylic acids such as trifluoroacetic acid, solid acids such as ion exchange resins, etc. However, as the base catalyst, hydroxides of alkali metals such as potassium hydroxide and cesium hydroxide, tetraalkylammonium hydroxide, and silanolates prepared from tetraalkylammonium hydroxide and cyclic polysiloxane are preferably used. The amount of the catalyst used is not particularly limited, but about 0.001 to 1 mol% is sufficient with respect to the number of moles of the siloxane unit.

The equilibrium polymerization can be carried out generally in the temperature range of 20 to 300 ° C, preferably 60 to 200 ° C. If the temperature is lower than 20 ° C, the reaction system becomes non-uniform, and if it exceeds 300 ° C, by-products such as cyclic siloxane are likely to occur, which is not preferable. In addition, the solvent may include n-pentane, n-heptane, n-octane, and n-octane, if necessary, for controlling the reaction temperature, controlling the viscosity of the reaction system, and increasing the compatibility of the catalyst and raw materials.
It is also possible to use solvents such as benzene, toluene and xylene.

The reaction time varies considerably depending on the reaction conditions such as the amount of charged raw materials, the temperature and the catalyst, but it is usually about 1 hour to 1 week.

[0025]

FUNCTION AND EFFECT OF THE INVENTION The novel siloxane derivative (1) of the present invention is a substance having a siloxane skeleton and a fluorine-containing polyether skeleton in the same molecule, and has physical properties of both organopolysiloxane and fluorine-containing compound. It has low surface tension and low refractive index, and has very low organopolysiloxane properties such as heat resistance, cold resistance, electrical insulation, water repellency, releasability, defoaming and chemical resistance, and surface free energy. Therefore, it has water repellency, oil repellency, antifouling property, non-adhesiveness and low friction, and the liquid substance has high wettability due to its low surface tension,
It is a substance that has the characteristics of a fluorine-containing compound exhibiting penetrability as well as compatibility with other materials, which was a problem of polysiloxane containing a perfluoroalkyl group or a perfluoropolyether group as a substituent. This is a dramatic improvement.

Therefore, the novel siloxane derivative of the present invention
(1) are cosmetic raw materials, lubricants for magnetic recording materials and precision machines, fiber treatment agents, antistatic agents, paint finishes for automobiles, paint additives, emulsifiers, resin modifiers, polishes,
It can be applied to a very wide range of fields such as inorganic treatment agents.

[0027]

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

In the following Examples, the reagents were sufficiently dried, the interior was replaced with an inert gas such as dry nitrogen or dry argon, and the reaction was carried out in a glass container equipped with a dropping funnel, a thermometer, and a three-way stopcock, to give a reagent. Was injected through the three-way stopcock using a syringe under a stream of an inert gas such as dry nitrogen or dry argon.

Example 1 [(A) Synthesis of fluorinated macromonomer (5a) having carbon-carbon double bond]

[0030]

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After sufficiently drying, the inside was replaced with dry argon, 3.07 g (27.4 mmol) of potassium t-butoxide was charged into a glass container equipped with a dropping funnel, a thermometer, and a three-way stopcock, and then the inside of the reaction container was again charged. The atmosphere was replaced with argon, and heat drying was performed with a plaster under vacuum. 50 ml of dimethoxyethane and 1.96 ml (1.67 g, 28.8 mmol) of allyl alcohol dried with Molecular Sieves 4A were charged under a stream of dry argon using a syringe through a three-way stopcock, and stirred for 15 minutes. Then, 64.55 g (576 mmol) of trifluoropropylene oxide dried with molecular sieves 4A was placed in a reaction vessel immersed in a constant temperature bath of 10 ° C. under a stream of dry argon so that the temperature of the reaction system did not exceed 40 ° C. from the dropping funnel. While paying attention to. After stirring for 3 hours, the reaction was stopped by adding 1N hydrochloric acid with stirring until the reaction solution became neutral. The reaction product was extracted with ether, washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 65.3 g (yield 99%) of a semitransparent pale yellow waxy fluorine-containing macromonomer. ^{According to 1} H-NMR analysis, it had an allyl group at the terminal and the average degree of polymerization was 21. Moreover, the peak molecular weight in GPC (Tosoh, G4000HXL + G2000HX
L, 50 mM AcOH / THF) is 3.3 × 10 ^{3 in} terms of polystyrene,
It was Mw / Mn = 1.23.

IR (liquid film, cm ^-1 ): 3500, 2950, 2900,
1460, 1370, 1320, 1270, 1180, 1130, 1050, 860, 720 ¹ H-NMR (δppm, tetramethylsilane standard: 0 pp
m): 4.4 to 3.9 and 3.75 to 3.55 (m, 62H) -C H (CF ₃ ) -C H ₂ O- 5.4 to 5.1 (m, 2H) C H ₂ = CH- 6.05 to 5.80 (m, 1H) CH ₂ = C H -5.5 (d, 1H) OH [Synthesis of (B) compound (1a)]

[0033]

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In a glass reaction vessel, 11.0 g (0.573 mmol) of hydrogen polysiloxane represented by the following formula (4a),

[0035]

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20 ml of toluene, 0.1 wt% of H ₂ PtCl ₆ .H ₂ O
Isopropyl alcohol solution 0.376 mg (9.17 × 10 ^-4 mmol,
200ppm vs. Si-H). The reaction mixture was heated to 40 ° C., 30 ml of a toluene solution of 2.76 g (1.145 mmol) of the fluorine-containing macromonomer (5a) having a carbon-carbon double bond synthesized in (A) was added dropwise over 30 minutes, and then 5 hours. Stirring was performed.
Then, 2.9 ml (23 mmol) of 1-hexene was added, and the mixture was stirred for further 5 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel short column chromatography to give the desired siloxane derivative (1a). Got (10.3
g, 77% yield).

IR (liquid film, cm ^-1 ): FIG. 1 3500, 2950, 2900, 1410, 1320, 1260, 1180, 1090, 10
20, 860, 800, 700 ¹ H-NMR (δppm, acetone-d ₆ standard: 2.05ppm): Fig. 2 -0.1 to 0.2 (m, about 1540H) Si-C H ₃ 0.4 to 0.5 (m, 16H) Si _{-C H 2 - 0.7~0.9 (m,} 19.5H) Si-CH 2 -C 4 H 8 -C H 3 1.1~1.35 (m, 52H) Si-CH 2 -C 2 H 8 -CH 3 1.45 ~1.7 (m, 3H) Si-CH ₂ -C H ₂ -CH ₂ -O- 3.4 (t, 3H) Si-CH ₂ -CH ₂ -C H ₂ -O- 4.4 to 3.9 and 3.75 to 3.55 (m, 94.5 _{H) -C H (CF 3)} -C H 2 O- 4.95 (d, [ synthesis of compound (1b)] from about 1.5 H) O H example 2

[0038]

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In a glass reaction vessel, 7.37 g (1.518 mmol) of hydrogen polysiloxane represented by the following formula (4b),

[0040]

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20 ml of toluene, 0.1 wt% of H ₂ PtCl ₆ .H ₂ O
Isopropyl alcohol solution 0.496 mg (1.21 × 10 ^-3 mmol,
400ppm vs. Si-H). The reaction mixture was heated to 40 ° C., and 9.15 g (3.7 g) of the fluorine-containing macromonomer (5a) having a carbon-carbon double bond synthesized in Example 1 (A) above was used.
30 mmol of toluene solution (95 mmol) was added dropwise over 30 minutes, and the mixture was stirred for 5 hours. Then, 1.89 ml (15.18 mmol) of 1-hexene was added, the mixture was stirred for 5 hours, and then the solvent was distilled off under reduced pressure.
By purifying the residue by silica gel short column chromatography, the desired siloxane derivative (1
b) was obtained (11.8 g, yield 79%).

IR (liquid film, cm ^-1 ): 3550, 2960, 2920,
1380, 1320, 1260, 1195, 1140, 1100, 1030, 860, 80
0,710 ¹ H-NMR (δppm, acetone -d ₆ standards: 2.05ppm): -0.1~0.2 (m, about _{390H) Si-C H 3 0.4~0.5} (m, 8H) Si-C H 2 - 0.7~0.9 (m, 6H) Si-CH ₂ -C ₄ H ₈ -C H ₃ 1.1 to 1.35 (m, 16H) Si-CH ₂ -C ₂ H ₈ -CH ₃ 1.45 to 1.7 (m, 4H) Si-CH ₂ -C H ₂ -CH ₂ -O- 3.4 (t, 4H) Si-CH ₂ -CH ₂ -C H ₂ -O- 4.4 to 3.9 and 3.75 to 3.55 (m, 126H) -C H (CF ₃ )- C H ₂ O- 4.95 (d, about 2H) OH Example 3 [Synthesis of compound (1c)]

[0043]

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In a glass reaction vessel, 2.0 g (4.64 mmol) of hydrogen polysiloxane represented by the following formula (4c),

[0045]

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20 ml of toluene, 0.1 wt% of H ₂ PtCl ₆ .H ₂ O
Isopropyl alcohol solution 0.761 mg (1.857 × 10 ^-3 mmo
1, 200 ppm vs. Si-H). The reaction mixture was heated to 40 ° C., and 13.4 g of the fluorine-containing macromonomer (5a) having a carbon-carbon double bond synthesized in Example 1 (A) above.
30 ml of a toluene solution of (5.57 mmol) was added dropwise over 30 minutes, and the mixture was stirred for 5 hours. Then, 5.8 ml (46.4 mmol) of 1-hexene was added, and the mixture was further stirred for 5 hours, and then the solvent was distilled off under reduced pressure.
By purifying the residue by silica gel short column chromatography, the desired siloxane derivative (1
c) was obtained (11.0 g, yield 81%).

IR (liquid film, cm ^-1 ): 3450, 2960, 2920,
1470, 1440, 1380, 1320, 1260, 1195, 1140, 1100, 103
0, 940, 900, 860, 800, 710, 550 ¹ H-NMR (δppm, acetone-d ₆ standard: 2.05ppm): -0.1 to 0.2 (m, about 72H) Si-C H ₃ 0.4 to 0.5 (m _{, 4H) Si-C H 2} - 0.7~0.9 (m, 8H) Si-CH 2 -C 4 H 8 -CH 3 1.45 ~1.7 (m, 2H) Si-CH 2 -C H 2 -CH 2 -O -3.4 (t, 2H) Si-CH ₂ -CH ₂ -C H ₂ -O- 4.4 to 3.9 and 3.75 to 3.55 (m, about 63H) -C H (CF ₃ ) -C H ₂ O- 4.95 (d , About 1H) OH Example 4 [(A) Synthesis of fluorinated macromonomer (6a) having carbon-carbon double bond]

[0048]

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After thoroughly drying and replacing the inside with dry argon, 12.9 g (115.2 mmol) of potassium t-butoxide was charged in a glass container equipped with a dropping funnel, a thermometer, and a three-way stopcock, and then charged again in the reaction container. The atmosphere was replaced with argon, and heat drying was performed with a plaster under vacuum. Then, 50 ml of dimethoxyethane dried with Molecular Sieves 4A was charged under a stream of dry argon using a syringe through a three-way stopcock, and the mixture was stirred for 15 minutes. Then, 64.55 g (576 mmol) of trifluoropropylene oxide dried with molecular sieves 4A was placed in a reaction vessel immersed in a constant temperature bath of 10 ° C. under a stream of dry argon so that the temperature of the reaction system did not exceed 40 ° C. from the dropping funnel. While paying attention to. After stirring for 3 hours,
The reaction was stopped by adding 38.7 g (230.4 mmol) of allyl iodide with stirring until it became neutral. The reaction product was extracted with ether, washed with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 76.9 g (yield 99%) of a semitransparent pale yellow oily fluorine-containing macromonomer. ¹ H-NMR
It has an allyl group at the end from the analysis, and the average degree of polymerization is 5.
It was 0. The peak molecular weight measured by GPC (Tosoh, G
4000HXL + G2000HXL, 50 mM AcOH / THF) was 1100 in terms of polystyrene and Mw / Mn = 1.05.

IR (liquid film, cm ^-1 ): 3080, 3010, 2980,
2920, 2860, 1640, 1460, 1420, 1370, 1320, 1270, 118
0, 1130, 1050, 860, 720 ¹ H-NMR (δppm, tetramethylsilane standard: 0 pp
m): 1.2 (s, 9H) -C (C H ₃ ) ₃ 4.4 to 3.9 and 3.75 to 3.55 (m, 62H) -C H (CF ₃ ) -C H ₂ O- 5.4 to 5.1 (m, 2H) _{C H 2 = CH- 6.05~5.80 (m} , 1H) CH 2 = C H - [ synthesis of compound (1d)]

[0051]

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5.0 g (3.09 mmol) of hydrogen polysiloxane represented by the following formula (5d) was placed in a glass reaction vessel.

[0053]

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20 ml of toluene, 0.1 wt% of H ₂ PtCl ₆ .H ₂ O
Isopropyl alcohol solution 0.253 mg (6.18 × 10 ^-4 mmol,
200ppm vs. Si-H). The reaction mixture was heated to 40 ° C., and 5.0 g (7.4 g) of the fluorine-containing macromonomer (5d) having a carbon-carbon double bond synthesized in Example 1 (A) above.
(2 mmol) of a toluene solution (30 ml) was added dropwise over 30 minutes, the mixture was stirred for 5 hours, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel short column chromatography.
The desired siloxane derivative (1d) was obtained (6.9 g,
Yield 75%).

IR (liquid film, cm ^-1 ): 3500, 2950, 2920,
1380, 1320, 1260, 1195, 1140, 1100, 1030, 860, 80
0,710 ¹ H-NMR (δppm, acetone -d ₆ standards: 2.05ppm): -0.1~0.2 (m, about _{132H) Si-C H 3 0.4~0.5} (m, 4H) Si-C H 2 - 1.45 ~1.7 (m, 4H) Si-CH ₂ -C H ₂ -CH ₂ -O- 3.4 (t, 4H) Si-CH ₂ -CH ₂ -C H ₂ -O- 4.4 to 3.9 and 3.75 to 3.55 (m, 30H ) -C H (CF ₃ ) -C H ₂ O- Test Example 1 (Measurement of contact angle) A chloroform solution of a polymer was applied to the PET film surface and left standing in a desiccator at atmospheric pressure for one day or more. Kyowa Interface Science Co., Ltd. CA
The contact angle for water and squalene was measured using a -D contact angle meter. Table 1 shows the results.

Test Example 2 (Measurement of Solubility) 10 wt% of a polymer was added to a solvent, and its solubility was visually evaluated. Table 1 shows the results. ○: Transparent dissolution △: Emulsification ×: Insoluble (separation layer)

[0057]

[Table 1]

[Brief description of the drawings]

1 is an IR spectrum of the siloxane derivative obtained in Example 1. FIG.

FIG. 2 H-NMR of the siloxane derivative obtained in Example 1.
It is a spectrum.

Claims (9)

[Claims] 1. General formula (1): [Wherein at least one of R ¹ , R ² and R ³ has the following formula: (R ⁵ is hydrogen or a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, R ⁶ is a hydrocarbon group having an average carbon number of 2 to 18, and n is an average. 2 to 500), wherein R ¹ , R ² and R ³ and R ⁴ other than the above are alkyl groups having 1 to 18 carbon atoms, and a and b have an average value of a + b of 1 to 3000. Indicates the number of.
However, R ¹ , R ² and a plurality of R ³ may be the same or different. ] The siloxane derivative represented by these. 2. In the general formula (1), at least one of R ¹ , R ² and R ³ has the following formula: (R ⁵ is hydrogen or a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, R ⁶ is a hydrocarbon group having an average carbon number of 2 to 18, and n is an average. 2 to 500), wherein R ¹ , R ² and R ³ and R ⁴ other than the above are alkyl groups having 1 to 6 carbon atoms. 3. The siloxane derivative according to claim 1, wherein in the general formula (1), a and b have a mean value of a + b of 1 to 1000. 4. In the general formula (1), at least one of R ¹ , R ² and R ³ is represented by the following formula: (R ⁵ is hydrogen or a hydrocarbon group such as an alkyl group having 6 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, R ⁶ is a hydrocarbon group having an average carbon number of 2 to 18, and n is an average value. 2 to 500), wherein R ¹ , R ² and R ³ and R ⁴ other than the above are alkyl groups having 1 to 6 carbon atoms, and a and b have an average value of a + b of 1 to 1000. The siloxane derivative according to claim 1, wherein 5. General formula (4): (In the formula, at least one of R ⁷ , R ⁸ and R ⁹ is hydrogen, R ⁷ other than the above, R ⁸ and R ⁹ and R ⁴ are alkyl groups having 1 to 18 carbon atoms, and a and b are a + b. The hydrogen atom bonded to the silicon atom represented by
A siloxane having at least one siloxane in the molecule, and a compound represented by the general formula (5) or (6): (R ⁵ is hydrogen or a hydrocarbon group such as an alkyl group having 6 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, R ¹⁰ is a hydrocarbon group having an average carbon number of 0 to 16, and n is an average. 2-500) and a fluorine-containing macromonomer having a carbon-carbon double bond represented by the formula (2 to 500) is bonded by a hydrosilylation reaction in the presence of a hydrosilylation catalyst. Method for producing derivative. Wherein R ^7, at least one of R ⁸ and R ⁹ are hydrogen, R ^7, R ⁸ and R ⁹ and R ⁴ other than the above carbon number of 1
6. The method for producing a siloxane derivative according to claim 5, wherein the siloxane derivative is an alkyl group of 6 to 6. 7. The method for producing a siloxane derivative according to claim 5, wherein in the general formula (4), a and b are numbers in which a + b has an average value of 1 to 1000. 8. The method for producing a siloxane derivative according to claim 5, wherein the hydrosilylation catalyst is chloroplatinic acid. 9. General formula (7): [Wherein R ³ is the following formula: (R ⁵ is hydrogen or a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, R ⁶ is a hydrocarbon group having an average carbon number of 2 to 18, and n is an average. 2 to 500)), R ³ and R ⁴ other than this are alkyl groups having 1 to 18 carbon atoms, and a and b are numbers having an average value of 0 to 3000. Indicates.
However, either a or b is 1 or more. ] One or more types of cyclic polysiloxanes represented by the following formulas and the following formula (8): [Wherein at least one of R ¹ and R ² is the following formula: (R ⁵ is hydrogen or a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, R ⁶ is a hydrocarbon group having an average carbon number of 2 to 18, and n is an average. 2 to 500), other than this case, R ¹ , R ² and R ⁴ are alkyl groups having 1 to 18 carbon atoms, and a and b have an average value of a + b of 1 to 1 Indicates the number of 3000. However, R ¹ and R ² may be the same or different. ] A mixture with one or more kinds of linear siloxanes represented by the formula (wherein at least one of R ¹ , R ² and R ³ is a substituent represented by the above formula (2) or (3)).
Is subjected to equilibrium polymerization in the presence of an acid catalyst or a base catalyst.
The method for producing the siloxane derivative according to item 1.