JPH0525183A - Polyfluorosilicon compound and its production - Google Patents

Abstract

PURPOSE:To obtain the subject new compound excellent in low surface tension, low refractivity, heat resistance, electrical insulating properties, etc., by reacting a difluoroalkanoyl peroxide with an acryl-containing organosilicon compound. CONSTITUTION:A compound expressed by formula I [RF is formula II (X is H, F or Cl; n1 is 1-10) or formula III (n2 is 0-8)] is industrially made to react with a compound expressed by formula IV (R1 and R2 are 1-10C alkyl, alkoxy, etc.; m2 is 1-5), preferably at 1:(0.5-300) molar ratio, preferably in a solvent such as methylene chloride, preferably at 0-100 deg.C for 1-10hr to afford the objective compound expressed by formula V (m1 is 1-500), e.g. a compound expressed by formula VI.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyfluorosilicon compound and a method for producing the same.

[0002]

2. Description of the Related Art A compound containing a fluoroalkyl group in an organic compound has been attracting attention as a compound having useful properties such as light resistance, water and oil repellency, and physiological activity. In particular, fluoroalkyl group-containing silicon oligomers in which fluoroalkyl groups have been introduced into siloxanes have low surface tension, low refractivity, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, releasability, and defoaming. Since it has excellent properties such as chemical resistance and chemical resistance, in various fields, for example, synthetic intermediates for medicines, agricultural chemicals, etc., adhesion improvers such as resists in the production process of semiconductor devices, optical lenses, eyeglasses It is widely used in the field of surface treatment agents for imparting water and oil repellency and stain resistance on the surfaces of lenses for lenses, glass appliances, etc., and materials for imparting releasability. JP-A-219829 and JP-A-2-21
In Japanese Patent Publication No. 9830, compounds each having a fluoroalkyl group introduced into polysiloxane are disclosed. However, at present, little is known about the polyfluorosilicon compound in which the fluoroalkyl group is introduced into the acrylic group-containing organosilicon compound shown in the present invention.

[0003]

The objects of the present invention are low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electric insulation, water repellency, oil repellency, releasability, defoaming property, A novel polyfluorosilicon compound having a fluoroalkyl group introduced into an acrylic group-containing organosilicon compound, which has excellent properties such as stain resistance and chemical resistance, and a method for producing the same.

Another object of the present invention is to provide a method for easily producing a polyfluorosilicon compound in a high yield without using a reaction catalyst and special equipment.

[0005]

According to the present invention, there is provided a polyfluorosilicon compound represented by the following general formula 4 (hereinafter referred to as silicon compound 1).

[0006]

[Chemical 4]

According to the present invention, difluoroalkanoyl peroxide represented by the following general formula 5 (hereinafter referred to as fluoroalkanoyl 2) and an acryl group-containing organosilicon compound represented by the following general formula 6 (hereinafter organic A method for producing a polyfluorosilicon compound, which comprises reacting with a silicon compound 3).

[0008]

[Chemical 5]

[0009]

[Chemical 6]

The present invention will be described in more detail below.

The polyfluorosilicon compound of the present invention is
It is the silicon compound 1 represented by the general formula 4. In Formula 4, R ₁ and R ₂ are the same or different and represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylcarbonyloxy group. Carbon number 1-10
Preferred examples of the alkyl group include a methyl group, ethyl group, propyl group and butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and an alkylcarbonyl group As the oxy group, an acetyloxy group,
Preferable examples include a propionyloxy group, a butyryloxy group, and a pentylyloxy group. In the general formula 4, m ₁ represents an integer of ₁ to 500, and m ₂ represents an integer of 1 to 5. When R ₁ and R ₂ are an alkyl group, an alkoxy group, or an alkylcarbonyloxy group having 11 or more carbon atoms, and when m ₁ exceeds 500 and when m ₂ is 6 or more, the production is difficult. Because it cannot be used.

In the silicon compound 1, RF
- is - shows a (CF ₂₎ n ₁ X or the following general formalized 7. Here, X represents a hydrogen atom, a fluorine atom or a chlorine atom. n
₁ represents an integer of ₁ to 10 and n ₂ represents an integer of 0 to 8. Fluoroalkyl group RF- is - (CF ₂₎ a specifically given below and as follows in the case of n ₁ X. _{CF 3 -, F (CF 2} ) 2 -, F (CF 2) 3 -, F (C
F ₂ ) ₄ −, F (CF ₂ ) ₅ −, F (CF ₂ ) ₆ −, F (CF
_{2) 7 -, F (CF} 2) 8 -, F (CF 2) 9 -, F (C
_{F 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 (C
F ₂ ) ₅ −, Cl (CF ₂ ) ₆ −, Cl (CF ₂ ) ₇ −, Cl
_{(CF 2) 8 -, Cl} (CF 2) 9 -, Cl (CF 2) 10 -
Further, when the fluoroalkyl group RF-is represented by the following general formula 7, the following chemical formulas 8, 9, and 1
0, chemical formula 11, chemical formula 12, chemical formula 13, chemical formula 14, chemical formula 15, chemical formula 16
Is the street.

[0013]

[Chemical 7]

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10]

[0017]

[Chemical 11]

[0018]

[Chemical 12]

[0019]

[Chemical 13]

[0020]

[Chemical 14]

[0021]

[Chemical 15]

[0022]

[Chemical 16]

The carbon number of RF-, that is, n ₁ is 10,
_{When 2} exceeds 8, it cannot be used because the solubility in the solvent decreases.

As the silicon compound 1, specifically, for example, the following chemical formulas 17, 18, 19 and 2 can be used.
0, chemical 21, chemical 22, chemical 23, chemical 24, chemical 25, chemical 2
6, chemical formula 27, chemical formula 28, chemical formula 29, chemical formula 30, chemical formula 31, chemical formula 32
And the like (however, the above chemical formula 1
7, chemical formula 18, chemical formula 19, chemical formula 20, chemical formula 21, chemical formula 22, chemical formula 2
3, 24, 25, 26, 27, 28, 2
9, Chemical formula 30, Chemical formula 31, and Chemical formula 32, m ₁ represents an integer of ₁ to 500, and m ₂ represents an integer of 1 to 5). The average molecular weight of the silicon compound 1 is preferably in the range of 500 to 1,000,000. When the molecular weight is less than 500 and the molecular weight exceeds 1,000,000, it becomes difficult to produce. Furthermore, it is preferable that the silicon compound 1 be soluble in an ordinary halogen-based solvent.

[0025]

[Chemical 17]

[0026]

[Chemical 18]

[0027]

[Chemical 19]

[0028]

[Chemical 20]

[0029]

[Chemical 21]

[0030]

[Chemical formula 22]

[0031]

[Chemical formula 23]

[0032]

[Chemical formula 24]

[0033]

[Chemical 25]

[0034]

[Chemical formula 26]

[0035]

[Chemical 27]

[0036]

[Chemical 28]

[0037]

[Chemical 29]

[0038]

[Chemical 30]

[0039]

[Chemical 31]

[0040]

[Chemical 32]

The method for producing a polyfluorosilicon compound of the present invention is characterized by reacting a specific difluoroalkanoyl peroxide with a specific acryl group-containing organosilicon compound.

The difluoroalkanoyl peroxide used in the present invention is fluoroalkanoyl 2 represented by the above general formula 5. In the general formula 5, X represents a hydrogen atom, a fluorine atom or a chlorine atom, and n ₁ is 1 to 10
And n ₂ represents an integer of 0-8. In the above fluoroalkanoyl 2, when n ₁ is 11 or more, or n ₂
When 9 is 9 or more, the solubility of the fluoroalkanoyl 2 is lowered when the reaction is carried out in the presence of a solvent, and therefore it cannot be used. Further, RF-in the fluoroalkanoyl 2 is the same as RF-specifically listed in the silicon compound 1. Specific examples of the fluoroalkanoyl 2 include diperfluoro-2-methyl-3 peroxide.
-Oxahexanoyl, diperfluoro-2,5 peroxide
Preferred examples thereof include dimethyl-3,6-dioxanonanoyl, diperfluorobutyryl peroxide, and diperfluoroheptanoyl peroxide.

The specific acrylic group-containing organosilicon compound used in the present invention is the organosilicon compound 3 represented by the general formula 6. In the general formula 6, R ₁ and R ₂
Are the same as R ₁ and R ₂ of the silicon compound 1. R ₁ and R ₂ are alkyl groups having 11 or more carbon atoms, alkoxy groups,
Or an alkylcarbonyloxy group and m ₂ is 6
In the above cases, it is difficult to manufacture and cannot be used.

Specific examples of the organosilicon compound 3 include 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and the like.
3-acryloxypropyldiacetyloxymethylsilane, 3-acryloxypropyldiethoxymethylsilane, 3-acryloxypropyltriacetyloxysilane, 3-acryloxypropyltriisopropoxysilane, 3-acryloxypropyltrimethylsilane, 3-
Preferable examples include acryloxypropyl tri-tert-butoxysilane, 3-acryloxypropylethoxydimethylsilane, 3-acryloxypropylethoxydiethylsilane, and 3-acryloxypropyldiethylmethylsilane.

In the present invention, when the fluoroalkanoyl 2 and the organosilicon compound 3 are reacted, the molar ratio of the fluoroalkanoyl 2 and the organosilicon compound 3 charged is preferably 1: 0.1 to 50.
It is preferably in the range of 0, and particularly preferably in the range of 1: 0.5 to 300. When the charged molar ratio of the organosilicon compound 3 is less than 0.1, a large amount of a product due to the self-decomposition of peroxide is generated, and when the molar ratio exceeds 500, the purpose is Silicon compound 1
It is not preferable because the yield of the product decreases. The reaction can be carried out at normal pressure, and the reaction temperature is -20 to +
It is preferably in the range of 150 ° C., particularly preferably 0.
It is preferably in the range of -100 ° C. If the reaction temperature is lower than -20 ° C, the reaction takes a long time,
If the temperature exceeds ℃, the pressure during the reaction becomes high and the reaction operation becomes difficult, which is not preferable. Furthermore, the reaction time is 30 minutes to 2
It can be performed within a range of 0 hours, and is industrially 1 to 10
It is desirable to set the time range.

In the production method of the present invention, the desired silicon compound 1 can be obtained by a one-step reaction by reacting the fluoroalkanoyl 2 with the organosilicon compound 3 under the various reaction conditions described above. It is preferable to use a solvent so that the fluoroalkanoyl 2 can be handled and reacted more smoothly. A halogenated aliphatic solvent is particularly preferable as the solvent, and specific examples thereof include methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, and 1,2-dibromohexa. Fluoropropane, 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. Particularly, industrially, 1,1,2-trichlorotrifluoroethane can be preferably mentioned. When using the solvent,
The concentration of the fluoroalkanoyl 2 in the reaction solvent is
It is desirable to set it 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 a known method such as distillation or column chromatography.

[0048]

The polyfluorosilicon compound of the present invention is a novel compound and has low surface tension, low refractivity, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, oil repellency, and releasability. , Compounds having properties such as antifoaming property, stain resistance and chemical resistance, especially synthetic intermediates for pharmaceuticals, agricultural chemicals, etc., adhesion improvers for semiconductor device resists, optical lenses, spectacle lenses, glassware A surface treatment agent for imparting water and oil repellency and stain resistance to the surface of biomaterials,
It can be used as a material that imparts releasability, a biomaterial, and the like. In addition, the production method of the present invention allows a polyfluorosilicon compound to be produced in a short time in a high yield and easily by a one-step reaction without using a reaction catalyst and a special apparatus. Furthermore, in the production method of the present invention, the molecular weight of the target polyfluorosilicon compound can be adjusted by arbitrarily changing the charged molar ratio of the difluoroalkanoyl peroxide and the acrylic group-containing silicon compound.

[0049]

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

[0050]

Example 1 3-acryloxypropyltrimethoxysilane (1.2 g, 5.0 mmol) was added to diperfluoro-2-methyl-3-oxahexanoyl peroxide (3.3 g,
60 g of a 1,1,2-trichlorotrifluoroethane solution containing 5.0 mmol) was added, and the reaction was carried out at 30 ° C. for 5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solvent was removed and vacuum drying was carried out at 50 ° C. to obtain a product in a yield of 2.50 g. The obtained product was analyzed by gel permeation chromatography (GPC), IR, ¹ H-NMR, ¹⁹ F
-As a result of analysis by NMR, the following structural formula 33
Was a polyfluorosilicon compound. The analysis results are shown in Table 1. From the GPC analysis result, it was found that the mixture was a binary mixture of an oligomer product and a high molecular weight product, and from the gas chromatography (GC) analysis result, the ratio of the oligomer product was 20%.

[0051]

[Chemical 33]

[0052]

[Table 1]

[0053]

Example 2 Diperfluoro-2-methyl-3-peroxide
The reaction was performed in the same manner as in Example 1 except that the charged molar ratio of oxahexanoyl was changed from 5.0 mmol to 3.3 mmol, and a polyfluorosilicon compound represented by the following structural formula 34 was obtained in a yield of 2.10 g. . The analysis results are shown in Table 2.

[0054]

[Chemical 34]

[0055]

[Table 2]

[0056]

Example 3 Diperfluoro-2-methyl-3-peroxide
The reaction was performed in the same manner as in Example 1 except that the charged molar ratio of oxahexanoyl was changed from 5.0 mmol to 0.5 mmol to obtain a polyfluorosilicon compound represented by the following structural formula 35 in a yield of 1.35 g. . The analysis results are shown in Table 3.

[0057]

[Chemical 35]

[0058]

[Table 3]

[0059]

Example 4 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl, diperfluoro-2,5 peroxide
-A reaction was performed in the same manner as in Example 1 except that dimethyl-3,6-dioxanonanoyl was used, and the yield of the polyfluorosilicon compound represented by the following structural formula 36 was 3.21 g.
Got with. The analysis results are shown in Table 4. According to the GPC analysis result, it is a binary mixture of an oligomer product and a high molecular weight product, and according to the GC analysis result, the ratio of the oligomer product is 3
It was found to be 1%.

[0060]

[Chemical 36]

[0061]

[Table 4]

[0062]

Example 5 Diperfluoro-2-methyl-3-peroxide
Diperfluoro-peroxide instead of oxahexanoyl
Using 2,5-dimethyl-3,6-dioxanonanoyl, the reaction was carried out in the same manner as in Example 1 except that the charged molar ratio was changed from 5.0 mmol to 3.3 mmol.
The yield of the polyfluorosilicon compound represented by 7 was 3.1.
Obtained in 2 g. The analysis results are shown in Table 5.

[0063]

[Chemical 37]

[0064]

[Table 5]

[0065]

EXAMPLE 6 Diperfluoro-2-methyl-3-peroxide
Oxahexanoyl, diperfluoro-2,5 peroxide
The reaction was performed in the same manner as in Example 1 except that the charged molar ratio was changed from 5.0 mmol to 0.5 mmol instead of -dimethyl-3,6-dioxanonanoyl, and the polyfluoro represented by the following structural formula 38 was used. The silicon compound was obtained in a yield of 2.98 g. The analysis results are shown in Table 6.

[0066]

[Chemical 38]

[0067]

[Table 6]

[0068]

Example 7 Diperfluoro-2-methyl-3-peroxide
The reaction was performed in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluorobutyryl peroxide to obtain a polyfluorosilicon compound represented by the following structural formula 39 in a yield of 2.20 g. The analysis results are shown in Table 7. From the GPC analysis result, it was found that it was a binary mixture of an oligomer product and a high molecular weight product, and from the GC analysis result, the ratio of the oligomer product was 29%.

[0069]

[Chemical Formula 39]

[0070]

[Table 7]

[0071]

Example 8 Diperfluoro-2-methyl-3-peroxide
The reaction was performed in the same manner as in Example 1 except that oxahexanoyl was replaced with diperfluoroheptanoyl peroxide to obtain a polyfluorosilicon compound represented by the following structural formula 40 in a yield of 2.34 g. The analysis results are shown in Table 8. GP
From the results of C analysis, 2
As a result of GC analysis, it was found that the ratio of the oligomer product was 36% as the component mixture.

[0072]

[Chemical 40]

[0073]

[Table 8]

Claims (2)

[Claims] 1. A polyfluorosilicon compound represented by the following general formula 1. [Chemical 1] 2. A method for producing a polyfluorosilicon compound, which comprises reacting a difluoroalkanoyl peroxide represented by the following general formula 2 with an acrylic group-containing organosilicon compound represented by the following general formula 3. [Chemical 2] [Chemical 3]