JPH04253985A - Organosilicon compound containing fluoroalkyl group and its production - Google Patents

Abstract

PURPOSE:To obtain the subject compound having useful properties such as light-resistance and water and oil repellency, exhibiting low surface tension, low refractive index, excellent chemical resistance, etc., and useful as a synthetic intermediate for pharmaceuticals, agricultural chemicals, etc., and an agent for improving the adhesiveness of a resist in the production of a semiconductor device. CONSTITUTION:The compound of formula I [R is 1-10C alkyl, alkoxy, etc.; RF is (CF2)n1X (X is H, F, etc.; n1 is 1-10) or group of formula II (n2 is 0-8); m is 1-10]. For example, the compound of formula III or formula I can be produced on an industrial scale in one step at a low cost by compounding a compound of formula IV and a compound of formula V at a ratio of preferably 1:(1.2-5.0) and reacting at 0-100 deg.C for 3-10hr. In the case of industrial production of the compound of formula I, preferably 1,1,2-trichlorotrifluoroethane is used as the reaction solvent and the amount of the compound of formula IV is adjusted to 0.5-30wt.% based on the total solution.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel fluoroalkyl group-containing organosilicon compound and a method for producing the same.

0002

BACKGROUND OF THE INVENTION Organic compounds containing fluoroalkyl groups have attracted attention as compounds that exhibit useful properties such as light resistance, water and oil repellency, and physiological activity. In particular, fluoroalkyl group-containing silicone compounds, in which fluoroalkyl groups are introduced into siloxanes, have low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation,
Because it has excellent properties such as water repellency, mold release, antifoaming properties, and chemical resistance, it is used in various fields, such as synthetic intermediates for pharmaceuticals and agricultural chemicals, and resists in the production process of semiconductor devices. Adhesion improvers, optical lenses, eyeglass lenses,
It is widely used in the fields of surface treatment agents for imparting water and oil repellency, stain resistance, etc. to the surfaces of glassware, etc., and also as materials for imparting mold releasability. As the fluoroalkyl group-containing silicone compound, compounds in which a fluoroalkyl group is introduced into polysiloxane are disclosed in JP-A-2-219829 and JP-A-2-219830, respectively. However, at present, no fluoroalkyl group-containing organosilicon compound in which a fluoroalkyl group is introduced into the organosilicon compound shown in the present invention is known.

0003

[Problems to be Solved by the Invention] The objects of the present invention are low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, fiber processing properties, mold release properties, and antifoaming properties. An object of the present invention is to provide a novel fluoroalkyl group-containing organosilicon compound in which a fluoroalkyl group is introduced into an unsaturated group-containing organosilicon compound, which has excellent properties such as chemical resistance, and a method for producing the same.

Another object of the present invention is to provide a method for easily producing a fluoroalkyl group-containing organosilicon compound in high yield without using a reaction catalyst or special equipment.

[0005]

According to the present invention, a fluoroalkyl group-containing organosilicon compound represented by the following general formula 4 (hereinafter referred to as organosilicon compound 1) is provided.

[0006]

[Image Omitted] Furthermore, according to the present invention, a difluoroalkanoyl peroxide (hereinafter referred to as difluoroalkanoyl 2) represented by the following general formula 5 and an unsaturated group-containing organosilicon compound represented by the following general formula 6 ( (hereinafter referred to as organosilicon compound 3)
Provided is a method for producing a fluoroalkyl group-containing organosilicon compound, the method comprising reacting with the fluoroalkyl group-containing organosilicon compound.

[0007]

[C5]

[0008]

[C6] The present invention will be explained in more detail below.

The fluoroalkyl group-containing organosilicon compound of the present invention is organosilicon compound 1 represented by the general formula 4 above. In the organosilicon compound 1, when R is an alkyl group, alkoxy group, or alkylcarbonyloxy group having 11 or more carbon atoms, when m exceeds 10, production is difficult, and when n1 exceeds 10, or When n2 exceeds 8, the solubility in a solvent decreases, so that it cannot be used.

In addition, in the organosilicon compound 1, the applicable RF, ie, -(CF2)n1X or the following general formula 7 is specifically enumerated: F3C-,F(CF
2) 2-, F(CF2)3-, F(CF2)4-, F(
CF2)5-, F(CF2)6-, F(CF2)7-,
F(CF2)8-, F(CF2)9-, F(CF2)1
0-, HCF2-, H(CF2)2-, H(CF2)3
-, H(CF2)4-, H(CF2)5-, H(CF2
)6-, H(CF2)7-, H(CF2)8-, H(C
F2)9-, H(CF2)10-, ClCF2-, Cl
(CF2)2-, Cl(CF2)3-, Cl(CF2)
4-, Cl(CF2)5-, Cl(CF2)6-, Cl
(CF2)7-, Cl(CF2)8-, Cl(CF2)
9-, Cl(CF2)10-, the following chemical formula 8, chemical formula 9,
Chemical formula 10, chemical formula 11, chemical compound 12, chemical compound 13, chemical compound 14, chemical compound 15, chemical compound 16.

[0011]

[C7]

0012

[Chemical formula 8]

[0013]

[Chemical formula 9]

[0014]

[Chemical formula 10]

[0015]

[Chemical formula 11]

[0016]

[Chemical formula 12]

[0017]

[Chemical formula 13]

[0018]

[Chemical formula 14]

[0019]

[Chemical formula 15]

[0020]

embedded image Specifically, the organosilicon compound 1 is, for example,
The following chemical formulas 17, 18, 19, 20, 21,
Chemical 22, Chemical 23, Chemical 24, Chemical 25, Chemical 26, Chemical 27, Chemical 28, Chemical 29, Chemical 30, Chemical 31, Chemical 32, Chemical 33, Chemical 3
4, Chemical 35, Chemical 36, Chemical 37, Chemical 38, Chemical 39, Chemical 40
, Chemical 41, Chemical 42, Chemical 43, Chemical 44, Chemical 45, Chemical 46,
Compounds 47, 48, 49, etc. can be preferably mentioned (however, m in the above structural formula represents an integer of 1 to 10).

[0021]

[Chemical formula 17]

[0022]

[Chemical formula 18]

[0023]

[Chemical formula 19]

[0024]

[C20]

[0025]

[C21]

[0026]

[C22]

[0027]

[C23]

[0028]

[C24]

[0029]

[C25]

[0030]

[C26]

[0031]

[C27]

[0032]

[C28]

[0033]

[C29]

[0034]

[C30]

[0035]

[Chemical formula 31]

[0036]

[C32]

[0037]

[Chemical formula 33]

[0038]

[C34]

[0039]

[C35]

[0040]

[C36]

[0041]

[C37]

[0042]

[C38]

[0043]

[C39]

[0044]

[C40]

[0045]

[C41]

[0046]

[C42]

[0047]

[C43]

[0048]

[C44]

[0049]

[C45]

[0050]

[C46]

[0051]

[C47]

[0052]

[C48]

[0053]

embedded image The method for producing a fluoroalkyl group-containing organosilicon compound of the present invention is characterized by reacting a specific difluoroalkanoyl peroxide with a specific unsaturated group-containing organosilicon compound.

The difluoroalkanoyl peroxide used in the present invention is difluoroalkanoyl 2 represented by the general formula 5 above. In the difluoroalkanoyl 2, when n1 is 11 or more or when n2 is 9 or more, the solubility of the difluoroalkanoyl 2 decreases when reacting in the presence of a solvent, so it cannot be used.

In addition, R in the difluoroalkanoyl 2
F is the same as RF specifically listed in the organosilicon compound 1 above.

The specific unsaturated group-containing organosilicon compound used in the present invention is organosilicon compound 3 represented by the general formula 6. In the organosilicon compound 3, when R is an alkyl group, alkoxy group, or alkylcarbonyloxy group having 11 or more carbon atoms, or when m is 11 or more, production is difficult.

Specific examples of the unsaturated group-containing organosilicon compound 3 include allyltrimethylsilane, allyltrimethoxysilane, allyltriethoxysilane,
Allyltriacetyloxysilane, 3-butenyltrimethylsilane, 3-butenyltrimethoxysilane, 3-butenyltriethoxysilane, 3-butenyltriacetyloxysilane, 4-pentenyltrimethylsilane, 4-
Preferably pentenyltrimethoxysilane, 4-pentenyltriethoxysilane, 4-pentenyltriacetyloxysilane, 5-hexenyltrimethylsilane, 5-hexenyltrimethoxysilane, 5-hexenyltriethoxysilane, 5-hexenyltriacetyloxysilane, etc. can be mentioned.

In the present invention, when the difluoroalkanoyl 2 and the organosilicon compound 3 are reacted, the molar ratio of the difluoroalkanoyl 2 and the organosilicon compound 3 is preferably 1:1.0 to 1.0.
10.0, particularly preferably 1:1.2 to 5
．． It is desirable to set it in the range of 0. If the charged molar ratio of the organosilicon compound 3 is less than 1.0 or more than 10, it is not preferable because it is difficult to obtain the desired fluoroalkyl group-containing organosilicon compound. In addition, the reaction can be carried out at normal pressure, and the reaction temperature is -20 to +
The temperature is preferably in the range of 150°C, particularly preferably 0.
-100°C. When the reaction temperature is less than -20°C, the reaction takes a long time, and when it exceeds +150°C, the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable. Furthermore, the reaction time can be carried out in the range of 30 minutes to 20 hours, and industrially it is preferably in the range of 3 to 10 hours.

In the production method of the present invention, the desired organosilicon compound 1 can be obtained through a one-step reaction by reacting the difluoroalkanoyl 2 with the organosilicon compound 3 under the various reaction conditions described above. , the handling and reaction of the difluoroalkanoyl 2,
It is preferable to use a solvent in order to perform the process more smoothly. The solvent is particularly preferably a halogenated aliphatic solvent, specifically, for example, methylene chloride, chloroform, 2
-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-dibromohexafluoropropane,
1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro-2,3,3-trichlorobutane, 1,1,1,3
-Tetrachlorotetrafluoropropane, 1,1,1-
Trichloropentafluoropropane, 1,1,2-trichlorotrifluoroethane, etc. can be used, and 1,1,2-trichlorotrifluoroethane is particularly preferred from an industrial standpoint. When the solvent is used, the concentration of the difluoroalkanoyl 2 in the entire solution is preferably in the range of 0.5 to 30% by weight.

The reaction product obtained by the production method of the present invention can be purified by known methods such as distillation and column chromatography.

[0061]

Effects of the Invention The fluoroalkyl group-containing organosilicon compound of the present invention is a new compound, and has low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency,
Compounds with properties such as mold releasability, antifoaming properties, and chemical resistance, especially synthetic intermediates for pharmaceuticals and agricultural chemicals, adhesion improvers for semiconductor device resists, optical lenses, eyeglass lenses, glassware, etc. It can be used as a surface treatment agent for imparting water- and oil-repellency, anti-staining properties, etc. to the surface of a product, as well as a fiber treatment agent and a material that imparts mold releasability. Further, according to the production method of the present invention, a fluoroalkyl group-containing organosilicon compound can be easily produced in a short time, with good yield, and in a one-step reaction without using a reaction catalyst or special equipment.

[0062]

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0063]

[Example 1] Allyltrimethylsilane (0.69g, 6
mmol), diperfluoro-2-methyl-3 peroxide
-1,1,2-trichlorotrifluoroethane solution containing oxahexanoyl (2.0 g, 3 mmol) 17.
5 g was added, and the reaction was carried out at 30° C. for 5 hours under a nitrogen atmosphere. After the reaction is completed, the reaction solvent is removed, followed by distillation,
The product was obtained with a yield of 83%. The obtained product is IR,1
As a result of analysis by H-NMR, 19F-NMR, and Mass spectrum, it was found to be a mixture of fluoroalkyl group-containing organosilicon compounds represented by the following structural formula 50. The analysis results are shown below.

[0064]

[C50]

[0065]

[Example 2] Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl, diperfluoro-2,5 peroxide
The reaction was carried out in the same manner as in Example 1 except that -dimethyl-3,6-dioxanonanoyl was used, and a compound represented by the following structural formula 51 was obtained in a yield of 66%. The analysis results are shown below.

[0066]

[C51]

[0067]

[Example 3] Diperfluoro-2-methyl-3-peroxide
The reaction was carried out in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluorobutyryl peroxide, and a compound represented by the following structural formula 52 was obtained in a yield of 77%. The analysis results are shown below.

[0068]

[C52]

[0069]

[Example 4] Diperfluoro-2-methyl-3-peroxide
The reaction was carried out in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluoroheptanoyl peroxide, and a compound represented by the following structural formula 53 was obtained in a yield of 69%. The analysis results are shown below.

[0070]

[C53]

[0071]

[Example 5] The reaction was carried out in the same manner as in Example 1 except that allyltrimethoxysilane was replaced with allyltrimethoxysilane, and a compound represented by the following structural formula 54 was produced in a yield of 71%.
I got it from The analysis results are shown below.

[0072]

[C54]

[0073]

Example 6 The reaction was carried out in the same manner as in Example 1 except that allyltrimethylsilane was replaced with allyltriacetyloxysilane, and a compound represented by the following structural formula 55 was obtained in a yield of 79%. The analysis results are shown below.

[0074]

[C55]

Claims (2)

[Claims] 1. A fluoroalkyl group-containing organosilicon compound represented by the following general formula 1. [Chemical formula 1] 2. A fluoroalkyl group-containing organosilicon compound, characterized in that a difluoroalkanoyl peroxide represented by the following general formula 2 is reacted with an unsaturated group-containing organosilicon compound represented by the following general formula 3. manufacturing method. [Chemical formula 2] [Chemical formula 3]