JPH08157486A - Organosilicon compound - Google Patents

Abstract

PURPOSE: To obtain the new subject compound excellent in compatibility with a polymer having a high fluorine content and useful as a crosslinking agent, etc., for the rubber of a high fluorine content by reacting a polysiloxane containing SiH groups with a specific allylamide containing fluorine in the presence of a platinum catalyst. CONSTITUTION: This new organosilicon compound comprises a compound expressed by formula I (Rf is a perfluoroalkyl or a perfluoroalkyl ether; R<1> is a monovalent hydrocarbon; R<2> is an alkylene; a is 1-4 integer; b is 1-3 integer) c is 0-3 integer; 3<=a+b+c<=6) and excellent in compatibility with a fluorosilicone or fluoroethylene polymer having a high fluorine content and useful as a crosslinking agent, etc., for an addition curing-type silicone rubber composition or an addition curing-type fluorine rubber composition having a high fluorine content. This compound is obtained by the addition reaction of 1,3,5,7-tetramethylcyclotetrasiloxane with an allylamide containing fluorine expressed by formula II in the presence of a platinum catalyst in a solvent such as toluene.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organosilicon compound useful as a crosslinking agent for addition-curable silicone rubber compositions used for various purposes.

[0002]

2. Description of the Related Art Conventionally, various addition-curable silicone rubber compositions have been prepared in which an organopolysiloxane having an alkenyl group such as a vinyl group is used as a base polymer and an organohydrogenpolysiloxane having an SiH group is added as a crosslinking agent. Is used for. This type of curable silicone rubber composition is cured by an addition reaction (hydrosilylation reaction) between the SiH group of the crosslinking agent and the alkenyl group of the base polymer. However, when a fluorosilicone or fluoropolymer having a high fluorine content is used as the base polymer, even if a conventional organohydrogenpolysiloxane is used as a crosslinking agent, these crosslinking agents and fluorosilicones having a high fluorine content or Since the compatibility with the fluoropolymer is poor, it was not possible to obtain a good cured product with the silicone rubber composition comprising these combinations.

[0003]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide an addition-curable silicone rubber composition or an addition-curable fluororubber which has excellent compatibility with fluorosilicones and fluoropolymers having a high fluorine content and has a high fluorine content. An object of the present invention is to provide an organosilicon compound useful as a crosslinking agent for a composition.

[0004]

The present invention provides the following general formula (1):

[0005]

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(In the formula, Rf is independently a perfluoroalkyl group or a perfluoroalkylether group, and R ¹
Are independently monovalent hydrocarbon groups, R ² is an alkylene group, a is an integer of 1 to 4, b is an integer of 1 to 3, c is an integer of 0 to 3, and , A, b and c are 3
Satisfies ≦ a + b + c ≦ 6. ) Is an organosilicon compound. Hereinafter, the present invention will be described in detail.

Organosilicon Compound The organosilicon compound of the present invention is represented by the above general formula (1). In the formula, the perfluoroalkyl group represented by Rf has the following general formula: —C _n F _{2n + 1} ( wherein, n is exemplified those represented by a is) integer from 1 to 15, they can be linear, or may be branched, for _{example, -CF 3, -CF 2 CF 3} , -CF ₂ CF
_{2 CF 3, -CF 2 CF 2} CF 2 CF 3, -CF 2 (C
_{F 2) 4 CF 3, -CF} 2 (CF 2) 5 CF 3, -CF
_{(CF 3) 2, -CF 2} CF (CF 3) 2, -CF
_{2 (CF 2) 4 CF (} CF 3) 2, -CF 2 CF 2 CF
_{(CF 3) 2, -CF 2} (CF 2) 5 CF (C
F ₃ ) ₂ , etc. can be mentioned, preferably a perfluoroalkyl group having 1 to 10 carbon atoms, particularly preferably —CF ₃ , —CF ₂ CF ₂ CF ₂ C.
_{F 3, -CF 2 (CF 2} ) 5 CF 3, -CF (CF 3)
₂ In the general formula (1), examples of the perfluoroalkyl ether group represented by Rf include the following general formula:

[0008]

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(Wherein, X is each independently a fluorine atom or a trifluoromethyl group, L and n are each independently 1, 2 or 3, m is an integer of 1-10,
-C _L F _2L - can be exemplified those represented by a straight-chained or may be branched). As a specific example,
For example, -C (CF ₃₎ F- [OCF ₂ C (CF ₃₎ F] _n -F [wherein, n represents an integer of 1 to 5]
_{, -C (CF 3) FOCF 2} C (CF 3) FOC 3 F 7
_{, -C (CF 3) FOC 3} F 7, -CF 2 CF 2 OCF 2 C (CF 3) FOC 3 F 7 -CF 2 CF 2 - (OCF 2 CF 2 CF 2) n -F [wherein, n Is an integer from 1 to 5]
_{, -CF 2 CF 2 - (OCF} 2 CF 2 CF 2) 2 -F -CF 2 CF 2 OC 3 F 7, -CF 2 - (OCF 2 CF 2) n -F [wherein, n represents 1-8 Integer)
, —CF ₂ OCF ₂ CF ₃ , —CF ₂ — (OCF ₂ CF ₂ ) ₃ —F, and the like, and preferably have 5 to 5 carbon atoms.
17 perfluoroalkyl ether groups, particularly preferably —C (CF ₃ ) F— [OCF ₂ C (CF ₃ ) F] _n —F [where n is an integer of 1 to 5]
_{, -C (CF 3) FOCF 2} C (CF 3) FOC 3 F 7
_{, -C (CF 3) FOC 3} F 7, -CF 2 CF 2 OCF 2 C (CF 3) is an FOC ₃ F _7.

In the general formula (1), examples of the monovalent hydrocarbon group represented by R ¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group and a tert group.
-Alkyl group such as butyl group, hexyl group, cyclohexyl group, octyl group; alkenyl group such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group; phenyl group, tolyl group, An aryl group such as a xylyl group and a naphthyl group; an aralkyl group such as a benzyl group and a phenylethyl group can be exemplified, and a preferable monovalent hydrocarbon group has 1 to 10 carbon atoms containing no aliphatic unsaturated bond. And more preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Also,
For use as a crosslinking agent, an alkyl group having 1 to 6 carbon atoms is particularly preferable, and a methyl group is most preferable.

In the general formula (1), examples of the alkylene group represented by R ² include alkylene groups such as methylene, ethylene, trimethylene, methylethylene, tetramethylene, hexamethylene and the like, and preferred alkylene groups. Has 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, and most preferably a trimethylene group. In the general formula (1), a
Is an integer of 1 to 4, b is an integer of 1 to 3, c is an integer of 0 to 3, and a, b and c are 3 ≦ a + b.
+ C ≦ 6 is satisfied. From the viewpoint of use as a crosslinking agent, a is preferably 2 or 3, b is 1 or 2, c is 0 or 1, and a + b + c is preferably 3, 4 or 5. Examples of the organosilicon compound of the present invention include, but are not limited to, the followings.

[0012]

[Chemical 4]

(Wherein a'is 2 or 3 in the above formula) Method for Producing Organosilicon Compound The organosilicon compound of the present invention can be produced, for example, by the following general formula (2):

[0014]

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A cyclic hydrogen siloxane represented by the formula (wherein R ¹ , a, b and c have the same meanings as described above) and the following general formula (3): Rf-CO-N (CH ₂ CH _{2 Rf) - (CH 2) m} -CH = CH 2 (3) ( in the formula, m is an integer of 0 to 4, Rf is unsaturated group-containing fluorine-containing represented by the same meanings as defined above) It can be produced by subjecting an amide compound to a partial addition reaction in the presence of a catalyst. The reaction is usually 50 to 15
It can be carried out at a temperature of 0 ° C, preferably 60 to 120 ° C.

The catalyst is a platinum group metal-based catalyst well known as a catalyst used in hydrosilylation reaction, such as chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,220,972), Complex of chloroplatinic acid and olefin (US Pat. No. 3,159,
No. 601, No. 3,159,662, No. 3,775,452), platinum black or palladium supported on a carrier such as alumina, silica or carbon, rhodium -Olefin complex, chlorotris (triphenylphosphine) rhodium [Wilkinson catalyst], etc. can be mentioned. Of these, those of the complex type are preferably used by dissolving them in an organic solvent of alcohol type, ketone type, ether type or the like. In the general formula (1), the numerical value represented by b is determined by the addition reaction amount of the fluorine-containing amide compound. Therefore, the amount of the fluorinated amide compound used is
Depending on the amount of SiH groups in the cyclic hydrogen siloxane to be reacted, the amount is set to be within the range of b defined by the general formula (1). For example, the amount of the fluorine-containing amide compound represented by the general formula (3) may be set to about 1/5 to 3/4 times the molar amount of the SiH group in the cyclic hydrogen siloxane.

The amount of the catalyst used may be a so-called catalyst amount,
For example, in terms of platinum group metal, it is 1 to 1,000 ppm, preferably 10 to 5 per cyclic hydrogen siloxane.
It is 00 ppm. The organosilicon compound of the present invention thus obtained is useful as a crosslinking agent for addition reaction type silicone rubber compositions. A curable silicone rubber composition using the organosilicon compound of the present invention as a cross-linking agent may be prepared, for example, by adding an organosilicon compound to an organopolysiloxane base polymer having an alkenyl group and having an SiH group content of 0. It can be obtained by mixing 5 to 5 mol, preferably 0.8 to 3 mol, and further mixing a curing catalyst, a filler and the like.
The resulting curable silicone rubber composition can be used in various applications, and in particular, a composition containing a base polymer having a fluorine-containing group introduced has an excellent adhesiveness to various substrates when cured. Is excellent.

[0018]

EXAMPLES The present invention will be described in more detail below with reference to examples. Example 1 1, 3 , 5, 7-in a 500 ml four-necked flask equipped with a stirrer
67.2 g of tetramethylcyclotetrasiloxane (0.
28 mol), chloroplatinic acid and 1,3-divinyl-1,1,
0.44 g of a toluene solution (0.5% by weight in terms of platinum) of 4% by weight of 3,3-tetramethyldisiloxane complex was charged and heated to 80 ° C. In this flask the following structural formula:

[0019]

[Chemical 6]

Fluorine-containing allylamide 218.
6 g (0.28 mol) was added dropwise over 1 hour. 80 this
After reacting at 0 ° C for 1 hour, the reaction mixture was distilled under reduced pressure to obtain a distillate having a boiling point of 130 to 133 ° C / 2 mmHg.
99.5 g (yield 34.8%) of a compound having a refractive index of 1.3498 (25 ° C.) was obtained. This compound was analyzed by ¹ H-NMR, ¹⁹
The compound having the following structure was confirmed by F-NMR, IR, and elemental analysis. In addition, ¹ H-NMR, ¹⁹ F
-NMR, IR, and elemental analysis are shown below, and an IR chart is shown in Fig. 1.

[0021]

[Chemical 7]

¹ H-NMR (CHCl ₃ standard) δ 0.37 ppm (S, Si—CH ₃ , 12H) δ 0.53 to 0.93 ppm (m, Si—CH ₂ , 2H) δ 1.57 to ₂ . 27 ppm (m, C-CH 2 -C, 2H) δ1.27~3.07 ppm (m, CF 2 -CH 2, 2H) δ3.37~3.70 ppm (m, N-CH 2, 2H ) Δ 3.50 to 4.00 ppm (q, N-CH ₂ , 2H) δ 4.87 ppm (S, Si-H, 3H)

¹⁹ F-NMR (CF ₃ COOH standard) Φ-3.71 (a, 3F) Φ-5.10 (b, 13F) Φ-37.68 (c, 2F) Φ-47.90 (d , 2F) Φ-49.41 (e, 3F) Φ-52.96 (f, 2F) Φ-67.95 (g, 1F)

[0024]

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IR (see FIG. 1) Characteristic absorption 2,170 cm ^-1 (Si-H) 1,685 cm ^-1 (C = O)

Elemental analysis C H O Si Measured value 25.61% 2.49% 10.96% 10.85% * Calculated value 25.86% 2.45% 10.97% 10.97% * C ₂₂ H _{As 25} F ₂₆ NO ₇ Si ₄

Example 2 Instead of the fluorine-containing allyl amide used in Example 1, the following structural formula:

[0028]

[Chemical 9]

Fluorine-containing allyl amide represented by 195.
The same operation as in Example 1 was performed except that 7 g (0.28 mol) was used, and the boiling point was 134 to 138 ° C / 2 as a fraction.
Compound 5 with mmHg and refractive index of 1.3554 (25 ° C)
7.3 g (yield 21.8%) was obtained. This compound is ¹ H
-NMR, ¹⁹ F-NMR, IR, and elemental analysis confirmed that the compound had the following structure. In addition, ¹ H-N
MR, ¹⁹ F-NMR, IR, and elemental analysis are shown below, and an IR chart is shown in FIG. 2.

[0030]

[Chemical 10]

¹ H-NMR (CHCl ₃ standard) δ 0.38 ppm (S, Si—CH ₃ , 12H) δ 0.53 to 0.97 ppm (m, Si—CH ₂ , 2H) δ 1.73 to ₂ . 07 ppm (m, C-CH 2 -C, 2H) δ2.20~3.07 ppm (m, CF 2 -CH 2, 2H) δ3.33~4.27 ppm (m, N-CH 2, 4H ) Δ 4.88 ppm (S, Si-H, 3H)

¹⁹ F-NMR (CF ₃ COOH standard) Φ-4.51 (a, 6F) Φ-34.48 (b, 2F) Φ-37.36 (c, 2F) Φ-43.86 (d , 4F) Φ-45.49 (e, 4F) Φ-47.57 (f, 2F) Φ-49.15 (g, 4F)

[0033]

[Chemical 11]

IR (see FIG. 1) Characteristic absorption 2,170 cm ^-1 (Si-H) 1,695 cm ^-1 (C = O)

Elemental analysis CH 2 O 5 Si measured value 26.75% 2.69% 8.50% 11.88% * calculated value 26.84% 2.66% 8.52% 11.93% * C ₂₁ H _{As 25} F ₂₄ N ₁ O ₅ Si ₄

[0036]

INDUSTRIAL APPLICABILITY The organosilicon compound of the present invention has an excellent compatibility with fluorosilicones and fluoropolymers having a high fluorine content, and is an addition-curable silicone rubber composition or an addition-curable fluororubber composition having a high fluorine content. It is useful as a cross-linking agent.

[Brief description of drawings]

FIG. 1 is the IR of the organosilicon compound obtained in Example 1.
It is a chart.

2 is an IR of the organosilicon compound obtained in Example 2. FIG.
It is a chart.

Front page continuation (72) Koichi Ishida Inoue Koichi Ishida, Gunma Prefecture Usida-gun Matsuida-cho 1 Hitomi 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. The following general formula (1): (In the formula, Rf is independently a perfluoroalkyl group or a perfluoroalkyl ether group, R ¹ is independently a monovalent hydrocarbon group, R ² is an alkylene group, and a is 1
Is an integer from 4 to 4, b is an integer from 1 to 3, and c is 0.
Is an integer of 3, and a, b and c are 3 ≦ a + b + c
Satisfies ≦ 6. ) An organosilicon compound represented by: