JP3328986B2 - Fluoroalkyl group-containing silicone oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluoroalkyl group-containing silicone oil which can be used as a lubricant or the like.

[0002]

2. Description of the Related Art Compounds containing a fluoroalkyl group in an organic compound have been receiving attention as having useful properties such as light resistance, water / oil repellency, and physiological activity. In particular, a fluoroalkyl group-containing organosilicon compound in which a fluoroalkyl group has been introduced into the organosilicon compound has a low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electric insulation, water repellency, and mold releasability. Because of its excellent properties such as antifoaming property and chemical resistance, it is used in various fields.

Conventionally, it has been known to use dimethyl silicone oil as a synthetic oil having excellent heat resistance and cold resistance. As an oil having improved oil resistance and solvent resistance,
Fluorosilicones into which a fluoroalkyl group such as a trifluoromethyl group has been introduced are known (Japanese Patent Application Laid-Open No.
-189933).

However, with the recent expansion of the field of use of silicone oil, various physical properties such as refractive index, surface tension, solubility in organic solvents, etc. can be controlled over a wide range, and high performance fluorocarbons usable for a wide range of applications can be used. Development of silicone oil is desired.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a fluoroalkyl group-containing silicone oil having excellent lubricity and the like.

[0006]

According to the present invention, there is provided a fluoroalkyl group-containing silicone oil containing a fluoroalkyl group-containing silicone represented by the following general formula (hereinafter referred to as silicone 1).

[0007]

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Hereinafter, the present invention will be described in more detail.

The fluoroalkyl group-containing silicone oil of the present invention is a silicone oil represented by the general formula (2).
including. In the silicone 1, when R is an alkyl group, an alkoxy group or an alkylcarbonyloxy group having 11 or more, production is difficult. When n ₁ exceeds 10, or when n ₂ exceeds 8, a solvent is used. Can not be used because its solubility in water decreases.

In the silicone 1, the applicable RF, ie,-(CF ₂ ) n ₁ X or the following general formula 3 can be specifically listed as F ₃ C-, F (CF ₂ ) _2- , F (C
F ₂ ) ₃ −, F (CF ₂ ) ₄ −, F (CF ₂ ) ₅ −, F (CF
_{2) 6 -, F (CF} 2) 7 -, F (CF 2) 8 -, F (C
_{F 2) 9 -, F (} CF 2) 10 -, HCF 2 -, H (CF 2) 2
−, H (CF ₂ ) ₃ −, H (CF ₂ ) ₄ −, H (CF ₂ )
_{5 -, H (CF 2)} 6 -, H (CF 2) 7 -, H (CF 2) 8
−, H (CF ₂ ) ₉ −, H (CF ₂ ) ₁₀ −, ClCF ₂ −,
_{Cl (CF 2) 2 -,} Cl (CF 2) 3 -, Cl (CF 2) 4
−, Cl (CF ₂ ) ₅ −, Cl (CF ₂ ) ₆ −, Cl (CF
_{2) 7 -, Cl (CF} 2) 8 -, Cl (CF 2) 9 -, Cl
(CF _{2) 10} -, it is the following chemical formula of 4-12.

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[0021] As the silicone 1, specifically, for example, can be preferably exemplified a following general formalized 13-30, etc. (where, n in the formula is an integer of 1 to 10, m ₁
Represents an integer of 0 to 50).

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[0039]

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In the present invention, the molecular weight of the silicone 1 is preferably in the range of 500 to 50,000, and the viscosity is preferably 10,000 centipoise (hereinafter referred to as cp) or less. When the viscosity exceeds 10,000 cp, fluidity,
Particularly, the fluidity at a low temperature is unfavorably reduced.

In the present invention, the silicone 1 is prepared by, for example, reacting a difluoroalkanoyl peroxide represented by the following general formula 31 with a vinyl group-containing silicone compound represented by the following general formula 32. Obtainable.

[0042]

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[0043]

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R in the vinyl group-containing silicone compound
Is an alkyl group, an alkoxy group, or an alkylcarbonyloxy group having 11 or more carbon atoms, which is not preferred because production is difficult. The RF of the difluoroalkanoyl peroxide is the same as the RF of the silicone oil 1.

Examples of the difluoroalkanoyl peroxide represented by the above general formula 31 include diperfluoro-2-methyl-3-oxahexanoyl peroxide and diperfluoro-2,5-dimethyl-3,6-diperoxide. Oxano nanoyl, diperfluoro-2,5,8-trimethyl-3,6,9-trioxadodecanoyl peroxide, diperfluorobutyryl peroxide, diperfluoroheptanoyl peroxide and the like can be preferably exemplified. as the vinyl group-containing silicone compound represented by the general formalized 32, for example, the following general formalized 33-41 and the like preferably (but, m ₁ is an integer of 0 to 50).

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In reacting the difluoroalkanoyl peroxide with the vinyl-containing silicone compound, the molar ratio of the charged difluoroalkanoyl peroxide to the vinyl-containing silicone compound is 1: 0.1 to
10.0 is preferred, and particularly preferably 1: 0.5-5.0. The reaction can be carried out at normal pressure, and the reaction temperature is usually in the range of -20 ° C to + 150 ° C, preferably in the range of 0 to 100 ° C. Further, the reaction time can be generally in the range of 30 minutes to 20 hours, but it is desirable to set conditions so that it is practically 3 to 10 hours.

The fluoroalkyl group-containing silicone oil of the present invention may contain the silicone 1, and the content of the silicone 1 in the fluoroalkyl-containing silicone oil is preferably 0.01 to 100%. , Especially 0.1 to 50%.

The fluoroalkyl group-containing silicone oil of the present invention has heat resistance, cold resistance, chemical resistance, oxidation resistance, lubricity, inertness to rubber and plastics, viscosity temperature characteristics, water / oil repellency, low surface Tension, low reflection, low moisture absorption,
Lubricant, especially for thermal transfer recording receivers, magnetic recording media, magnetic heads, impregnated bearings, etc., because they have properties such as flexibility, oxygen supply capacity, high breakdown voltage, low vapor pressure and other unique surface properties; Vacuum pump oil; working oil such as traction oil, brake oil, coupling oil, etc .; anti-vibration oil for automobiles, aircraft instruments, player pickups, etc .; damper oil such as dash bot dampers, shock absorbers; release agents; Roller compositions for copiers and electrophotographic machines; Surface coating agents; Film blocking inhibitors for thermal transfer recording ink sheets; Incorporation into makeup cosmetics, lipsticks, hair cosmetics, antiperspirants, deodorants, etc. Oil; hair dye; hair treatment agent such as shampoo and rinse; gel ointment composition; Engineering agents, fiber treatment agents such as lubricants imparting agent sewing thread; transformer oil, insulation oil condenser oil, and the like; heating medium; leveling agents, antiblocking agents,
Additives to plastics, paints, etc., such as color unevenness inhibitor and yuzu skin inhibitor; plasticizers for rubber and resin; modifiers; base oils, such as grease and compounds; differential pressure gauge liquids for various measuring instruments; Agent; oil blended in wax; toner treatment agent; oil sealant; rust inhibitor; antistatic agent; anti-clouding agent;
Additives to pharmaceuticals; Polishing agents; surface treatment agents for glass, ceramics, powders, etc.

In particular, when the fluoroalkyl group-containing silicone oil is used as a lubricant, it can be used as it is or by adding it to a known lubricant and mixing it.

[0059]

The fluoroalkyl group-containing silicone oil of the present invention has heat resistance, cold resistance, chemical resistance, oxidation resistance,
Lubricity, inertness to rubber and plastics, viscosity-temperature characteristics, water / oil repellency, low surface tension, low reflectivity, low moisture absorption, flexibility, oxygen supply ability, high breakdown voltage, low vapor pressure, etc. And excellent surface fluidity, and can be used in a wide range of fields such as lubricants and additives to various oils.

[0060]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, the viscosity in an example is a viscosity in 25 degreeC.

[0061]

Synthesis Example 1 In 17.9 g (10 mmol) of a vinyl group-containing silicone compound represented by the following general formula 42,
1,1,1,2 containing 3.3 g (5.0 mmol) of diperfluoro-2-methyl-3-oxahexanoyl peroxide.
-50 g of a trichlorotrifluoroethane solution was added, and the mixture was reacted at 30 ° C for 5 hours under a nitrogen atmosphere. After the completion of the reaction, the reaction solvent was removed and then dried under vacuum to obtain the desired colorless liquid product represented by the following general formula 43. The yield of the product obtained is 20.4
g and viscosity were 135 cp.

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Synthesis Example 2 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl is converted to diperfluoro-2,5 peroxide
When the reaction was carried out in accordance with Synthesis Example 1 except that -dimethyl-3,6-dioxanonanol was used, a product represented by the following general formula 44 was obtained. The yield of the obtained product was 22.4 g, and the viscosity was 155 cp.

[0065]

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Synthesis Example 3 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl is converted to diperfluoro-2,2 peroxide
The reaction was carried out in accordance with Synthesis Example 1 except that 5,8-trimethyl-3,6,9-trioxadodecanoyl was used, to obtain a product represented by the following general formula 45. The yield of the obtained product was 24.0 g, and the viscosity was 200 cp.

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Synthesis Example 4 Diperfluoro-2-methyl-3-peroxide
The reaction was carried out according to Synthesis Example 1 except that oxahexanoyl was replaced with diperfluorobutyryl peroxide.
A product represented by the following general formula 46 was obtained. The yield of the obtained product was 18.9 g, and the viscosity was 105 cp.

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Synthesis Example 5 Diperfluoro-2-methyl-3-peroxide
The reaction was carried out according to Synthesis Example 1 except that oxahexanoyl was replaced with diperfluoroheptanoyl peroxide, to give a product represented by the following general formula 47. The yield of the obtained product was 20.1 g, and the viscosity was 120 cp.

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Synthesis Example 6 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl is converted to diperfluoro-2,5 peroxide
Mn = 1790 of the vinyl group-containing silicone compound represented by the general formula (42), Mw = 4900, and Mw / Mn =
The reaction was carried out according to Synthesis Example 1 except that 1.27 was changed to Mw / Mn = 1.20, and a product having a structure represented by the general formula 44 was obtained. The yield of the obtained product was 28.0 g, and the viscosity was 170 cp.

[0073]

Synthesis Example 7 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl is converted to diperfluoro-2,5 peroxide
Mn = 1790 of the vinyl group-containing silicone compound represented by the general formula (42) was added to Mw = 11,000 and Mw / Mn =
The reaction was carried out according to Synthesis Example 1 except that 1.27 was changed to Mw / Mn = 1.19, and a product having a structure represented by the general formula 44 was obtained. The yield of the obtained product was 31.0 g, and the viscosity was 290 cp.

[0074]

Comparative Example 1 The value of the kinetic friction coefficient of liquid paraffin at point contact between a stainless steel (SUS304) ball and a glass plate was determined by a load-bearing capacity test (JIS K2519). Table 1 shows the results.

[0075]

Examples 1 to 7 Comparative examples were conducted in the same manner as in Comparative example 1 except that the liquid paraffin was replaced by an oil to which the fluorosilicone compound synthesized in each of the synthesis examples shown in Table 1 was added to the liquid paraffin. The value of the coefficient of kinetic friction was measured according to 1. Table 1 shows the results.

[0076]

Comparative Example 2 The liquid paraffin of Comparative Example 1 was added with 0.6% by weight of a non-fluorinated silicone compound (dimethyl silicone oil, product name "KF96" manufactured by Shin-Etsu Chemical Co., Ltd.) to the liquid paraffin. Except for using oil, the value of the dynamic friction coefficient was measured according to Comparative Example 1. The results are shown in Table 1.

[0077]

[Table 1]

──────────────────────────────────────────────────続 き Continued on front page (56) References Oil Chemistry, Vol. 40, no. 9 (1991) p. 730-p. 737 J.C. Chem. Soc. , Chem. Commun. , No. 10 (1991) p. 677-p. 678 (58) Field surveyed (Int. Cl. ⁷ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A fluoroalkyl group-containing silicone oil containing a fluoroalkyl group-containing silicone represented by the following general formula 1. Embedded image