JPH04193887A - Fluoroalkyl group-containing organosilicon oligomer and its production - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [R, X and Y are 1-10C alkyl, alkoxy or alkylcarbonyloxy; RF is (CF2)n X (X is H, F or Cl; (n1) is 1-10) or formula II ((n2) is 0-8); (n) is 1-3; (m1) is 1-10; (m2) is 0-10]. EXAMPLE:A compound expressed by formula III. USE:A synthetic intermediate for medicines, agricultural chemicals, etc., an adhesion improver such as a resist, etc., for semiconductor devices, a surface treating agent and a mold release agent for imparting water and oil repellency, antifouling properties, etc., to the surfaces of optical lenses, lenses for eyeglasses, glasswares, etc., excellent in low surface tension, low refractivity, heat, cold, oil and chemical resistances, electrical insulating properties, water repellency, mold release characteristics, antifoaming properties, etc. PREPARATION:A difluoroalkanoyl peroxide expressed by formula IV [RF is (CF2)n X or formula II] is made to react with a vinyl group-containing organosilicon compound expressed by formula V.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel fluoroalkyl group-containing organosilicon oligomer and a method for producing the same.

<Prior Art> Compounds containing fluoroalkyl groups in organic compounds are attracting attention as compounds that exhibit useful properties such as light resistance, water and oil repellency, and even physiological activity. In particular, fluoroalkyl group-containing silicone oligomers, in which fluoroalkyl groups are introduced into siloxanes, have low surface tension, low refraction, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, mold release properties, and antifoaming properties. Due to its excellent properties such as hardness and chemical resistance, it is used in various fields, such as synthetic intermediates for pharmaceuticals and agricultural chemicals, adhesion improvers for resists in the production process of semiconductor devices, optical lenses, and eyeglasses. It is widely used in the fields of surface treatment agents for imparting water- and oil-repellency and stain-proofing properties to the surfaces of lenses, glassware, etc., and materials that impart mold release properties. The fluoroalkyl group-containing silicone oligomer is disclosed in JP-A-2-21
No. 9829 and JP-A-2-219830 each disclose compounds in which a fluoroalkyl group is introduced into a polysiloxane. However, at present, little is known about fluoroalkyl group-containing organosilicon oligomers in which fluoroalkyl groups are introduced into vinyl group-containing organosilicon compounds.

<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, mold releasability, antifoaming properties, and chemical resistance. An object of the present invention is to provide a novel fluoroalkyl group-containing organosilicon oligomer having excellent properties such as the above, and a method for producing the same.

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

<Means for Solving the Problems> According to the present invention, the following general formula (1) [wherein R, X and Y are respectively the same or different groups, and an alkyl group having 1 to 10 carbon atoms, Indicates an alkoxy group or an alkylcarbonyloxy group. Furthermore, R1 represents (CF2)n1X or (where X represents a hydrogen atom, a fluorine atom, or a chlorine atom, n represents an integer of 1 to 10, and R2 represents an integer of O to 8). Furthermore, there is provided a fluoroalkyl group-containing organosilicon oligomer represented by the following formula: n is an integer of 1 to 3, ml is an integer of 1 to 10, and m2 is an integer of O to 10.

Furthermore, according to the present invention, the following general formula (II) [wherein Rp is
(CF2) difluoroalkanoyl peroxide represented by The following general formula (m) CH2=CH(-8i R20+m2SjXnY3-n
... (m) (in the formula, R, X and Y are the same or different groups, and an alkyl group having 1 to 10 carbon atoms,
(representing an alkoxy group or an alkylcarbonyloxy group, n is an integer of 1 to 3, and 1m2 is an integer of O to 10). A method for producing a fluoroalkyl group-containing organosilicon oligomer represented by I) is provided.

The present invention will be explained in more detail below.

The fluoroalkyl group-containing organosilicon oligomer of the present invention can be represented by the following general formula (1), in which R,
and Y are the same or different groups, and each represents an alkyl group, an alkoxy group, or an alkylcarbonyloxy group having 1 to 1 o carbon atoms. Furthermore, Rp is (CF2)
n1X or (where X represents a hydrogen atom, fluorine atom or chlorine atom, nl represents an integer of 1 to 10, and n2 represents 0 to
(indicates an integer of 8). Furthermore, n is an integer of 1 to 3, ml
represents an integer from 1 to 10, and m2 represents an integer from O to 1o.

In this case, if at least one of R, When it exceeds 10 or when n2 exceeds 8, it cannot be used because the solubility in the solvent decreases.

RF in the fluoroalkyl group-containing organosilicon oligomer represented by the general formula (I), that is, (CF 2 )
Specifically enumerating n 1X and, CF3-, F (CF2+2. F (CF2-)-
3,F (CF, +4°F (CF2±st F (C
F, air, F <cF2)-7,F (CF2+8゜F
(CF2+g, F (CF2-)-, o, HCF
,-,H(CF2+2°H(CF2+3.H(CF2
±,, HCCF2+9. H(CF,-)-,.

H(CF2-)-7, H(CF2-)-Il, H(C
F2±,, H(CF2−)−0°.

ClCF2−, C1(CF2+2. C1(CF2±
3t el (cF2±4°C1(CF2-)-,,C
1 (CF2-)6. C1(CF2-)-7,C1,(
CF2-)-Il.

C1(CF2-)-,, C1(CF2-)-0°.

−7= It is.

Preferred examples of the fluoroalkyl group-containing organosilicon oligomer represented by the general formula (I) include (wherein m in the structural formula represents an integer of O to 10). The molecular weight of the fluoroalkyl group-containing organosilicon oligomer in the present invention is preferably in the range of 500 to 10,000.

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

The difluoroalkanoyl peroxide used in the present invention can be represented by the following format (II), where R, is (C
F2) represents nIX or (where X represents a hydrogen atom, a fluorine atom or a chlorine atom, n□ represents an integer of 1 to 10, and n2 represents an integer of O to 8). In this case, if n□ is 11 or more or n2 is 9
The following two cases are not preferred because the solubility of the difluoroalkanoyl peroxide represented by the above-mentioned formula (n) decreases when the reaction is carried out in the presence of a solvent. Rp in the difluoroalkanoyl peroxide represented by the above-mentioned format (n) is the same as R1 specifically listed in the fluoroalkyl group-containing organosilicon oligomer represented by the above-mentioned format (1).

The specific vinyl group-containing organosilicon compound used in the present invention can be represented by the following -format (III), CH2=CH(-8i R, ○+m2SiXnY3-n
...(m) In the formula, R, X and Y are the same or different groups, and represent an alkyl group, an alkoxy group, or an alkylcarbonyloxy group having 1 to 10 carbon atoms, and n is a 1 to 3 carbon number group. m2 represents an integer of 0 to 10.

If at least one of IIIR, X, or Y is an alkyl group, alkoxy group, or alkylcarbonyloxy group having 10 or more carbon atoms, or if m2 is 11 or more, production is difficult.

Specific examples of the vinyl group-containing organosilicon compound represented by the above formula (Ill) include trimethoxyvinylsilane, triethoxyvinylsilane, diacetyloxymethylvinylsilane, jetoxymethylvinylsilane, triacetyloxyvinylsilane, and triisopropoxy. Preferred examples include vinylsilane, trimethylvinylsilane, tri-t-butoxyvinylsilane, ethoxydiethylvinylsilane, and diethylmethylvinylsilane.

In the present invention, the charged molar ratio of the fluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound when the difluoroalkanoyl peroxide and the vinyl group-containing organosilicon compound represented by the -format (III) are reacted. is preferably in the range of 1:1.0 to 10.0,
The range of 1:1.2 to 5.0 is particularly preferred. If the molar ratio of the vinyl group-containing organosilicon compound is less than 1.0, a large amount of decomposition products of the difluoroalkanoyl peroxide will be produced, which is industrially undesirable; This is not preferred because the yield of the fluoroalkyl group-containing organosilicon oligomer is lowered.

Further, the reaction can be carried out at normal pressure, and the reaction temperature is preferably -20 to 150°C, particularly preferably 0.
-100°C. When the reaction temperature is less than 120°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 is preferably in the range of 30 minutes to 20 hours, and industrially it is particularly preferably carried out in the range of 3 to 10 hours.

In the production method of the present invention, under the various reaction conditions,
By reacting the difluoroalkanoyl peroxide with the vinyl group-containing organosilicon compound, the desired fluoroalkyl group-containing organosilicon oligomer can be obtained directly through a one-step reaction, but the handling and reaction of the difluoroalkanoyl peroxide It is preferable to use a solvent in order to carry out the process more smoothly. The solvent is particularly preferably a halogenated aliphatic solvent, specifically, for example, methylene chloride, chloroform, 2-dichloro-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, i,l,2-trichlorotrifluoroethane, etc. can be used, especially industrially. 1.
Preferably, 1,2-trichlorotrifluoroethane can be mentioned. When the solvent is used, it is preferable that the concentration of the difluoroalkanoyl peroxide in the solvent is 0.5 to 30% by weight based on the entire solution.

Furthermore, the reaction product obtained by the production method of the present invention can be produced by known methods such as distillation, column chromatography, recrystallization, and reprecipitation.

<Effects of the Invention> The fluoroalkyl group-containing organosilicon oligomer of the present invention is a novel compound, and has low surface tension, low refractive properties, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, and mold releasability. As a compound with properties such as antifoaming and chemical resistance, it is particularly useful as a synthetic intermediate for pharmaceuticals and agricultural chemicals, adhesion properties of resists for semiconductor devices, and surfaces of optical lenses, eyeglass lenses, glassware, etc. It can be used as a surface treatment agent for imparting water- and oil-repellent properties, anti-staining properties, etc., and as a material that imparts mold release properties. Further, according to the production method of the present invention, a fluoroalkyl group-containing organosilicon oligomer can be easily produced in a short time, with high yield, and without using a reaction catalyst or special equipment, by a one-step reaction.

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

11 pull Y trimethoxyvinylsilane 2.3g (15.4mmo
Q), 1 containing 5.1 g (7,7 mmon) of diberfluoro-2-methyl-3-oxahexanoyl peroxide,
1.2-1 Helichlorotrifluoroethane solution 150g
was added, and the reaction was carried out at 30°C for 5 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solvent was removed, followed by distillation to obtain a product in a yield of 4.5 g. The obtained product was subjected to gel permeation chromatography, IR, “H
-NMR, 19F NMR, Mass analysis results show that ml in the structural formula shown below is 1 to 1.
It was a mixture of 10 fluoroalkyl-containing organosilicon oligomers. The analysis results are shown below.

Average molecular weight = 850 MS m/z 69 (CFJ).

, 119 (CF, CF2) , 1.21 [5i(
OCH3)3] 169 (03F7).

6-1H-N (CDCl2) 61.4
8-1.73 (-CH2-).

3.61 (CH3-).

3.20-3.81 (-CH<) 19F-NMR (CDC1a, external standard CF3CO2+
1) δ -2,0 to -9,2 (8F).

-54,O(2F),55.5 (IF)IR(■-
”) 1240 (CF2), 1335 (CF
) Diberfluoro-2-methyl-3-oxahexanoyl peroxide to diberfluoro-2,5-dimethyl-3 peroxide
The reaction was carried out in the same manner as in Example 1 except that , 6-thioxanonanoyl was used, and m in the structural formula shown below was 1.
A mixture of fluoroalkyl-containing organosilicon oligomers ranging from ~10 was obtained in a yield of 5.7 g. The analysis results are shown below.

Average molecular weight: 1350 MS m/z 69 (CF3).

119 (CF, CF2), 169 (C3F7), :
L21 [S i (OCH3),].

'H-NMR (CDC1,) 61.50-1.8
0 (-CH2-), 3.59 (CH3-).

3.18-3.79 (-CH<) "F-NMR (CDCl2. External standard CF3Co□H)
δ -2,0 to -9,0 (13F).

-54,0 (2F), -55,2 (IF).

-69,8 (IF) IR (■-”) 1235 (CF2), 1330
('CF3) The reaction was carried out in the same manner as in Example 1, except that the main diberfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with diberfluorobutyryl peroxide, and the reaction was carried out in the same manner as in Example 1. A mixture of fluoroalkyl-containing organosilicon oligomers with a ml range of 1 to 10 was obtained in a yield of 4.2 g. The analysis results are shown below.

Average molecular weight near 10 MS rn/z 69 (CF3).

119 (CF, CF2).

121 C8i (OCH3) 3).

169 (C3p?).

634 [C3F7+CH2C1(+,C3F7)5i
(OCH3)a'H-NMR (CDCl2) δ 1.55-1.
88 (-CH2-), 3.62 (CH3-), 3.2
0-3.89 (-CH<)19F-NMR (CDC1
,,,external standard CF,,Co□H)δ -5,7(3
F), -32,4 (2F).

-51,8 (2F) IR(an-”) 1235 (CF2), 1
355 (CF3) The reaction was carried out in the same manner as in Example 1, except that diberfluoro-2-methyl-3-oxahexanoyl peroxide was replaced with diberfluoroheptanoyl peroxide, and the structure shown below was obtained. A mixture of fluoroalkyl-containing organosilicon oligomers in which m□ in the formula ranges from 1 to 10 was obtained in a yield of 5.1 g. The analysis results are shown below.

Average molecular weight: 950 MS m/z 69 (CF3), 119
(CF3CF2), 121 (S i(OCH3)
3) 601 ((CH30)3S-jCHCH2CH
5x (OCH3)3)CGFl.

"H-NMR (CDC13) δ 1°59~
1.79 (-CH,-), 3.60 (CH,-),
3.30-3.90 (-CH<)”9F-NMR(
CDC:13. External standard CF, C02H) δ -2
,5 (3F), -29,0 (2F).

-43,3 (2F), -4,4,1 (2F).

-44,9 (2F), -48,2 (2F) IR (an-
1) 1235 (CF2), 134.0 (C
p3)

Claims (1)

[Claims] 1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [In the formula, R, X and Y are each the same or different groups, It represents an alkyl group, an alkoxy group, or an alkylcarbonyloxy group having 1 to 10 carbon atoms. Furthermore, R_F
indicates (CF_2)n_1X or ▲There is a mathematical formula, chemical formula, table, etc.▼ (However, X represents a hydrogen atom, fluorine atom, or chlorine atom, n_1 is an integer from 1 to 10, and n_2 is an integer from 0 to 8. ). Furthermore, n is an integer from 1 to 3, m_1 is 1
m_2 is an integer of 0 to 10.] A fluoroalkyl group-containing organosilicon oligomer. 2) The following general formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) [In the formula, R indicates (CF_2)n_1X or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, 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)] and the following general formula (III) ▲ Formula, There are chemical formulas, tables, etc. ▼...(III) (In the formula, R, , n is an integer of 1 to 3, and m_2 is an integer of 0 to 10. manufacturing method.