JPH06239876A - Fluorine-containing organic silicon compound - Google Patents

Abstract

(57) [Summary] [Structure] General formula: (In the formula, R ¹ and R ² are each an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is 0 to
Rf is a divalent perfluoropolyether group. ) A fluorine-containing organosilicon compound represented by [Effect] When it is used as an adhesive, it is possible to improve the wettability to the base material and the solvent resistance and chemical resistance of the adhesive interface.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel fluorine-containing organosilicon compound, and more particularly to a fluorine-containing organosilicon compound useful as an adhesive between a rubber material and a base material.

[0002]

2. Description of the Related Art Conventionally, an organosilicon compound having a hydrolyzable group and an alkenyl group in one molecule has been conventionally used as an adhesive or the like between a rubber material and a base material. Development of a novel organosilicon compound capable of satisfactorily improving the wettability and the solvent resistance and chemical resistance of the adhesive interface is desired.

[0003]

An object of the present invention is to provide a hydrolyzable group in one molecule which can satisfactorily improve wettability to a substrate and solvent resistance and chemical resistance of an adhesive interface. An object is to provide an organosilicon compound having an alkenyl group.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have introduced a base material by introducing a fluorine-containing group into an organosilicon compound having a hydrolyzable group and an alkenyl group in one molecule. It has been found that the wettability with respect to solvent and the solvent resistance and chemical resistance of the adhesive interface can be satisfactorily improved.

The present invention has the general formula (1):

[Chemical 3] [In the formula, R ¹ and R ² are each an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and when a plurality of R ^1's are present, they may be the same or different;
^{When two} or more are present, they may be the same or different. a is an integer of 0 to 3, and Rf is a general formula (2):

[0006]

[Chemical 4] (In the formula, k is an integer of 0 to 6, j and m may be the same or different and are integers of 1 to 5, and i and n may be the same or different and are integers of 0 to 1. ) 2
It is a valent perfluoropolyether group. ] The fluorine-containing organosilicon compound represented by these is provided.

Novel Fluorine-Containing Organosilicon Compound The fluorine-containing organosilicon compound of the present invention has an alkoxysilyl group as a hydrolyzable group and an allyl group as an alkenyl group in one molecule and is represented by the above general formula (1). Is a compound.

In the above general formula (1), R ¹ and R ² are each an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, preferably having 1 to 8 carbon atoms.
Specific examples of R ¹ and R ² include an alkyl group such as a methyl group, an ethyl group and a propyl group, a cycloalkyl group such as a cyclohexyl group, an alkenyl group such as a vinyl group, an allyl group and an isopropenyl group, and a phenyl group. , Aryl groups such as tolyl groups and 3,3,3-trifluoropropyl groups in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms, 6,6,6,5,5,4,4 Examples thereof include groups such as a 3,3,3-nonafluorohexyl group, a chloromethyl group, and a 3-chloropropyl group.
Further, when there are a plurality of R ¹ , they may be the same or different, and when there are a plurality of R ² , they may be the same or different.

Rf in the general formula (1) is a divalent perfluoropolyether group represented by the general formula (2). Specifically, Rf

[Chemical 5] Examples include groups represented by R ¹ and R exemplified above
² and Rf are typical examples, and the fluorine-containing organosilicon compound of the present invention is not limited to these.

Production The fluorine-containing organosilicon compound of the present invention can be produced, for example, as follows. Manufacturing method 1 The following formula (3):

[0011]

[Chemical 6] (In the formula, Rf is as described above, and two R ³ may be the same or different and each is an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond.) A compound having an alkoxycarbonyl group at the terminal is added to room temperature (usually
10-50 ° C. same as below. ), Allylamine in the same number of moles as the compound represented by the above formula (3) is added dropwise and reacted. The compound of formula (4):

[0012]

[Chemical 7] A compound represented by The compound represented by the formula (4) and the following formula (5):

[0013]

[Chemical 8] (Wherein R ¹ , R ² and a are as described above) and the aminopropyl group-containing silane compound at room temperature to
The compound of the present invention represented by the above general formula (1) is obtained by reacting at 70 ° C. and distilling off the alcohol and the like generated by the reaction under reduced pressure.

In the above production, R ³ OH (wherein R ³ is as described above) as a by-product by the reaction of the compound represented by the above formula (4) with the compound represented by the above formula (5). The alcohol represented by When R ^{3 of the} alcohol and R ^{2 of the} compound represented by the above formula (5) are different from each other, an exchange reaction between R ³ and R ² occurs, so that only a group represented by —OR ² is used as an alkoxysilyl group. In addition to the compound having the above, a compound having an alkoxysilyl group represented by —OR ³ is also produced. Therefore, when a compound having only a group represented by —OR ² as an alkoxy group is produced, R ³ in the compound represented by the above formula (3) and the compound represented by the above formula (5) It is desirable that the R ^{2 s} of the same are the same groups.

Production Method 2 To a compound represented by the above formula (3) having an alkoxycarbonyl group at both ends, at room temperature, a double molar amount of allylamine as compared with the compound represented by the above formula (3) is added dropwise. And react. The mixture thus obtained is washed with water and dehydrated with sodium sulfate or the like to obtain the formula (6):

[0016]

[Chemical 9] (In the formula, Rf is as described above.) A compound represented by the formula is obtained. The compound represented by the formula (6) is usually added in the presence of an addition reaction catalyst at 50 to 150 ° C., preferably 70 to 120 ° C. in the same mole number as the compound represented by the formula (6).
(7):

[0017]

[Chemical 10] (In the formula, R ¹ , R ² and a are as described above.) The silane represented by the formula is dropped to react. The compound of the present invention represented by the above general formula (1) can be produced by distilling and isolating from the obtained reaction solution.

The addition reaction catalyst used in the above reaction includes, for example, Group VIII elements of the periodic table and compounds thereof. Examples of such a compound include chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3220972), and a complex of chloroplatinic acid and an olefin (US Pat.
3159601, 3159662, 3775452),
Platinum black, palladium, etc., which are supported on a carrier such as alumina, silica, carbon, rhodium-olefin complex, chlorotris (triphenylphosphine) rhodium (Wilkinson catalyst), etc., and these compounds include, It is preferably used by dissolving it in a ketone-based, ether-based or hydrocarbon-based solvent.

Utility The fluorine-containing organosilicon compound of the present invention can be used for various purposes. That is, since the compound of the present invention has an alkoxysilyl group at one end and thus hydrolyzes by reacting with moisture in the air, SUS, iron, aluminum, tin plate, brass, glass, phenol resin, epoxy resin, polyurethane It can be bonded to a base material such as. Further, since it has an allyl group at the other end, for example,
It is possible to bond directly to the rubber when the addition-curable or peroxide-cured type rubber is cured. Therefore, the fluorine-containing organosilicon compound of the present invention can be used as an adhesive between a rubber material and a substrate. Further, when the compound of the present invention is used as the adhesive, the compound of the present invention has a perfluoropolyether group, and thus has excellent wettability to the substrate, and improves solvent resistance and chemical resistance of the adhesive interface. This is extremely useful because it can be done. Further, among the fluorine-containing organosilicon compounds of the present invention, compounds having a bifunctional alkoxysilyl group can be extended in chain length by hydrolysis and are useful for modifying silicone oil. Further, trifunctional compounds are useful for modifying silicone resins and silicone varnishes.

[0020]

EXAMPLES Examples of the present invention will be shown below. Example 1 100 equipped with a stirrer, thermometer, Dim funnel, dropping funnel
The following formula (8) in a ml three-necked flask:

[0021]

[Chemical 11] (In the formula, Rf ¹ is the following formula:

[0022]

[Chemical 12] Is a group represented by. 49.4 g of the compound represented by the formula (4) was charged and stirred, and 13.26 g of 3-aminopropyltriethoxysilane was added dropwise to the flask with a dropping funnel while maintaining the inside of the flask at 50 ° C. After completion of dropping, the mixture in the flask was aged at 50 ° C. for 2 hours. Then, the mixture
By distillation under reduced pressure under the conditions of 80 ° C./3 mmHg, by-products ethyl alcohol and unreacted 3-aminopropyltriethoxysilane were distilled off to obtain 56.9 g of a pale yellow transparent liquid. The liquid was analyzed by ¹ H-NMR, ¹⁹ F-NMR and IR, and further elementally analyzed by the formula:

[0023]

[Chemical 13] It was confirmed that the compound was a compound represented by the formula (wherein Rf ¹ is as described above). The above analysis results are shown below.

¹ H-NMR (TMS standard, ppm) [Formula:

[0025]

[Chemical 14] As a compound represented by: a: 0.62 (t, 2H) b: 1.24 (t, 9H) c: 1.66 (m, 2H) d: 3.30 (t, 2H) e: 3.45 (m, 6H) f: 3.87 (m, 2H) g: 4.89 to 5.24 (m, 3H) h: 7.65 (s, 2H)

¹⁹ F-NMR (CF ₃ COOH standard, ppm) [Formula:

[0027]

[Chemical 15] As a compound represented by] a: −3.60 b: −6.18 c: −9.36 d: −52.05 e: −67.87

[0028] · IR measurement (see FIG. _{^{1) 1100~1300cm -1 ν CF 1650cm -1}} ν C = C 1705cm -1 ν C = O 3340cm -1 ν NH

Elemental analysis C OH N F Si calculated value (%) 29.9 13.8 2.4 2.4 49.1 2.4 measured value (%) 30.4 13.7 2.3 2.6 48.5 2.5

Example 2 100 equipped with a stirrer, thermometer, Dim funnel, dropping funnel
The following formula (9) in a ml three-necked flask:

[0031]

[Chemical 16] (In the formula, Rf ² is the following formula:

[0032]

[Chemical 17] Is a group represented by. 40.4 g of the compound represented by the formula (4) was charged and stirred, and 9.78 g of 3-aminopropyldimethoxymethylsilane was added dropwise to the flask with a dropping funnel while maintaining the inside of the flask at 50 ° C. After completion of dropping, the mixture in the flask was aged at 50 ° C. for 2 hours. Next, the mixture was distilled under reduced pressure at 75 ° C./3 mmHg to distill off by-product ethyl alcohol and unreacted 3-aminopropyldimethoxymethylsilane to obtain 44.2 g of a pale yellow transparent liquid. . The liquid was analyzed by ¹ H-NMR, ¹⁹ F-NMR and IR, and further elementally analyzed by the formula:

[0033]

[Chemical 18] It was confirmed that the compound was a compound represented by the formula (in the formula, Rf ² is as described above). The above analysis results are shown below.

¹ H-NMR (TMS standard, ppm) [Formula:

[0035]

[Chemical 19] As a compound represented by: a: 0.33 (s, 3H) b: 0.63 (t, 2H) c: 1.68 (m, 2H) d: 3.32 (t, 2H) e: 3.48 (m, 9H) f: 3.87 (m, 2H) g: 4.89 to 5.24 (m, 3H) h: 7.66 (s, 2H)

¹⁹ F-NMR (CF ₃ COOH standard, ppm) [Formula:

[0037]

[Chemical 20] As a compound represented by] a: −3.90 b: −4.88 c: −9.35 d: −10.75 e: −43.12 f: −68.06

[0038] · IR measurement (see FIG. _{^{2) 1100~1300cm -1 ν CF 1650cm -1}} ν C = C 1705cm -1 ν C = O 3340cm -1 ν NH

Elemental analysis C OH N F Si Calculated value (%) 29.4 13.6 2.4 3.0 48.6 3.0 Measured value (%) 29.8 13.6 2.5 2.8 48.4 3.1

Example 3 100 equipped with a stirrer, thermometer, Dim funnel, dropping funnel
The following formula (10) in a ml three-necked flask:

[0041]

[Chemical 21] (In the formula, Rf ³ is the following formula:

[0042]

[Chemical formula 22] Is a group represented by. 41.6 g of the compound represented by the formula (1) and 0.05 g of a 2% by weight isopropyl chloroplatinate solution,
The mixture was stirred, and 8.20 g of triethoxysilane was dropped into the flask with a dropping funnel while maintaining the temperature of the flask at 100 ° C. After completion of dropping, the mixture in the flask was aged at 100 ° C. for 1 hour. The mixture is then vacuum distilled to give 1
20.7 g of a colorless and transparent liquid was obtained at 65 ° C./2 mmHg. The liquid was analyzed by ¹ H-NMR, ¹⁹ F-NMR and IR, and further elementally analyzed by the formula:

[0043]

[Chemical formula 23] It was confirmed to be a compound represented by the formula (in the formula, Rf ³ is as described above). The above analysis results are shown below.

¹ H-NMR (TMS standard) [Formula:

[0045]

[Chemical formula 24] As a compound represented by] a: 0.60 (t, 2H) b: 1.23 (t, 9H) c: 1.63 (m, 2H) d: 3.29 (t, 2H) e: 3.45 (m, 6H) f: 3.85 (m, 2H) g: 4.89 to 5.24 (m, 3H) h: 7.66 (s, 2H)

¹⁹ F-NMR (CF ₃ COOH standard, ppm) [Formula:

[0047]

[Chemical 25] As a compound represented by] a: −3.63 b: −6.16 c: −9.37 d: −52.10 e: −67.88

[0048] · IR measurement (see FIG. _{^{3) 1100~1300cm -1 ν CF 1650cm -1}} ν C = C 1705cm -1 ν C = O 3340cm -1 ν NH

Elemental analysis C OH N F Si Calculated value (%) 31.3 14.5 2.8 2.8 45.8 2.8 Measured value (%) 31.5 14.7 2.5 2.7 45.6 3.0

[0050]

The fluorine-containing organosilicon compound of the present invention can be used for various purposes. That is, since the compound of the present invention has an alkoxysilyl group and an allyl group, it can be used as an adhesive between a rubber material and a base material,
Moreover, since it has a perfluoroether group, it has excellent wettability to the substrate and can improve solvent resistance and chemical resistance at the adhesive interface. Further, among the fluorine-containing organosilicon compounds of the present invention, compounds having a bifunctional alkoxysilyl group can be extended in chain length by hydrolysis and are useful for modifying silicone oil. Further, trifunctional compounds are useful for modifying silicone resins and silicone varnishes.

[Brief description of drawings]

FIG. 1 is a view showing an IR chart of a fluorine-containing organosilicon compound of the present invention obtained in Example 1.

FIG. 2 is a view showing an IR chart of the fluorine-containing organosilicon compound of the present invention obtained in Example 2.

FIG. 3 is a view showing an IR chart of the fluorine-containing organosilicon compound of the present invention obtained in Example 3.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinichi Sato 1 Hitomi, Otomi, Matsuida-cho, Usui-gun, Gunma Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. General formula (1): [In the formula, R ¹ and R ² are each an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and when a plurality of R ^1's are present, they may be the same or different;
^{When two} or more are present, they may be the same or different. a is an integer of 0 to 3, and Rf is represented by the general formula (2): (In the formula, k is an integer of 0 to 6, j and m may be the same or different and are integers of 1 to 5, and i and n may be the same or different and are integers of 0 to 1. ) 2
It is a valent perfluoropolyether group. ] The fluorine-containing organosilicon compound represented by these.