JP2938303B2 - Fluorine-containing organosilicon compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel organosilicon compound not described in any literature, and particularly useful as a raw material for a solvent-resistant and chemical-resistant rubber material and a release agent material. The present invention relates to a fluorine-containing organosilicon compound.

[0002]

2. Description of the Related Art Conventionally, various fluorine-containing organosilicon compounds are known, and these are also used as raw materials such as a material for a solvent-resistant and chemical-resistant rubber material or a material for a release agent. .

[0003]

However, the conventionally known fluorine-containing organosilicon compounds do not have a very high fluorine content, and the solvent resistance, chemical resistance, and mold release of various rubber materials formed therefrom are not so high. Sex was not yet satisfactory. Accordingly, an object of the present invention is to provide a fluorine-containing organosilicon compound having a very high fluorine content.

[0004]

According to the present invention According to an aspect of the following general formula _{(1): Vi-CH 2} NHCO- (Y) a -Rf 1 -CONHCH 2 -Vi (1) wherein, Vi is A is a vinyl group, a is an integer of 1 or more, and Rf ¹ is the following formula (1a):

[0005]

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(1 is an integer of 0 to 8, k and m are integers of 0 to 20, j and n are integers of 0 or 1, and j + k + 1 +
m + n ≧ 1), a divalent perfluoroalkylene group or a divalent perfluoroalkyl ether group, Y is
The following formula (1b): -Rf ¹ -CONH (CH ₂ ) ₃ -Q- (CH ₂ ) ₃ NHCO- (1b) (Rf ¹ is the same as above, and Q is the following formula (1c):

[0007]

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Here, R ¹ and R ² each represent an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond;
Rf ² is a divalent group represented by Rf ¹ , wherein k or m is a divalent group having 0 to 5), and a fluorine-containing organosilicon compound represented by the formula: Provided.

In the above general formula (1), Rf ¹ is
(1a) is a divalent perfluoroalkylene group or a divalent perfluoroalkyl ether group represented by
Representative examples of Rf ¹ include, but are not limited to, the following groups.

[0010]

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In the general formula (1), Y is the above-mentioned formula (1)
b) a divalent organic group represented by the formula (1b)
Is a group represented by the above formula (1c), in which two silethylene groups are linked by a divalent fluorine-containing organic group Rf ² . In the formula (1c), typical examples of the monovalent hydrocarbon group R ¹ and R ² having no aliphatic unsaturated bond include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group. Cycloalkyl groups such as cyclohexyl groups, phenyl groups, aryl groups such as tolyl groups, benzyl groups, aralkyl groups such as phenylethyl groups, and groups in which part or all of the hydrogen atoms of these groups have been substituted with halogen atoms, Examples thereof include a chloromethyl group, a 3,3,3-trifluoropropyl group, a perfluorobutylethyl group, and the like. Representative examples of such Q include, but are not limited to, the following groups (where Ph represents a phenyl group).

[0012]

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Production Method The fluorine-containing organosilicon compound of the present invention can be prepared, for example, by the following formula (2): Vi-CH ₂ NHCO-Rf ¹ -CONHCH ₂ -Vi (2) (where Vi and Rf ¹ are as defined above) A fluorine-containing compound having an allyl group at both terminals represented by the same formula) and a compound represented by the following formula (3): HQH (3) (wherein Q is the same as described above). And a fluorine-containing organosilicon compound having a hydrosilyl group to be reacted in the presence of an addition reaction catalyst.

In this reaction, the charged amounts of the allyl group-containing fluorine-containing compound of the formula (2) and the fluorine-containing organosilicon compound of the formula (3) are usually as follows: 1 <the compound (mol) of the formula (2) / It is set so as to satisfy the compound (mol) of the formula (3) ≦ 2. If the molar ratio is set to a large value close to 2, a fluorine-containing organosilicon compound of the present invention having a relatively small molecular weight is synthesized. When the molar ratio is close to 1, a compound having a large molecular weight is synthesized (generally, a in the general formula (1) is about 20 at the maximum).

The reaction is carried out at 50-180 ° C., especially at 80-150 ° C.
It is preferable to carry out in. Also, as an addition reaction catalyst,
Platinum group metals, such as platinum alone, chloroplatinic acid, alcohol-modified chloroplatinic acid (see US Pat. No. 3,209,972), and complexes of chloroplatinic acid with olefins (US Pat. Nos. 3,159,601, 3,159,662, No. 3775452), platinum black or palladium supported on a carrier such as alumina, silica or carbon.
Olefin complexes, chlorotris (triphenylphosphine) rhodium [Wilkinson's catalyst] and the like can be mentioned. Of these, it is preferable to use the complex-type ones by dissolving them in solvents such as alcohol-based, ketone-based, ether-based, and hydrocarbon-based ones. These addition reaction catalysts may be used in a so-called catalytic amount, for example, in an amount of 10 ^-5 to 10 ^-2 times the molar amount of the terminal allyl group.

[0016]

[Use] The fluorine-containing organic silicon compound of the present invention can be used for various uses. For example, since the fluorine-containing organosilicon compound of the present invention has allyl groups at both ends of the molecular chain, it reacts with a compound having three or more hydrosilyl groups in one molecule in the presence of an addition reaction catalyst. By doing so, an elastomer cured product of a rubber elastic body can be obtained. Since this elastomer has a high fluorine content, it has excellent solvent resistance and chemical resistance, and has low surface energy and excellent releasability and water repellency.
Widely applied to applications such as extruded parts and coating materials.

[0017]

EXAMPLES In the following examples, viscosity values are measured at 25 ° C. Example 1 200 m with a stir bar, thermometer, Dim funnel, dropping funnel
l In a four-necked Separa flask, the following formula:

[0018]

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Allyl compound at both terminals represented by the formula (viscosity: 29
30cP) 30.89 g and meta-xylene hexafluoride 30.0 g are charged and heated to 120 ° C. with stirring, and 0.04 g of a 2% solution of chloroplatinic acid in isopropyl alcohol is added. Then, with a dropping funnel, the following formula:

[0020]

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Both ends hydrosilyl compound 4.02
g was added dropwise and reacted. After the dropwise addition, the disappearance of the hydrosilyl compound (ν _Si-H = 2140 cm ⁻¹ ) was confirmed by gas chromatography and IR while aging, and then cooled to room temperature, activated carbon 1.5 g was added, and the mixture was stirred for 2 hours. This was filtered under pressure with a filter plate, and the obtained filtrate was stripped under reduced pressure at 200 ° C./3 mmHg to obtain 28.7 g of a pale yellow transparent liquid. The viscosity of this liquid was measured and found to be 11,200 cP. This was measured by NMR to find that 0.24 ppm of Si-CH ₃
Was observed. The following results were obtained by IR measurement and elemental analysis.

IR measurement; chart is shown in FIG. 1100-1300cm ^-1 ν _CF 1705cm ^-1 ν _{C = O} 3340cm ^-1 ν _NH elemental analysis COHNFSi calculated value (%) 23.4 9.7 0.5 0.5 65.3 0.6 Actual value (%) 23.8 9.8 0.4 0.5 64.9 0.6

The amount of vinyl groups in this polymer was determined to be 0.0113 mol / 100 g.
The obtained polymer was confirmed to be a polymer having the following structural formula.

[0024]

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Example 2 200 m equipped with a stir bar, thermometer, Dim funnel and dropping funnel
l In a four-necked Separa flask, the following formula:

[0026]

Embedded image All terminal allyl compound represented by (viscosity: 3050CP) 41.98
g and 40.0 g of meta-xylene hexafluoride were heated to 120 ° C. while stirring, and 0.05 g of a 2% solution of chloroplatinic acid in isopropyl alcohol was added. Then, with a dropping funnel, the following formula:

[0027]

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Both ends hydrosilyl compound 5.03
g was added dropwise and reacted. After dropping and aging, the above hydrosilyl compound (ν _Si-H
= 2140 cm ^-1 ), and after cooling to room temperature, 1.8 g of activated carbon was added and stirred for 2 hours. This was filtered under pressure through a filter plate, and the obtained filtrate was stripped under reduced pressure at 200 ° C./3 mmHg to obtain 37.2 g of a pale yellow transparent liquid. The viscosity of this liquid was 14,400 cP. NMR analysis of this product revealed a Si-CH ₃ peak at 0.26 ppm. The following results were obtained by IR measurement and elemental analysis.

IR measurement; chart is shown in FIG. 1100-1300cm ^-1 ν _CF 1705cm ^-1 ν _{C = O} 3340cm ^-1 ν _NH elemental analysis COHNFSi calculated value (%) 23.5 9.5 0.5 0.5 65.3 0.7 Actual value (%) 23.6 9.4 0.5 0.5 65.1 0.9

The amount of vinyl groups in this polymer was determined to be 0.0085 mol / 100 g.
The obtained polymer was confirmed to be a polymer having the following structural formula.

[0031]

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[0032]

The novel fluorine-containing organosilicon compound of the present invention has an extremely high fluorine content and has allyl groups at both ends of the molecular chain, so that it undergoes an addition reaction with the organosilicon compound having a hydrosilyl group. A silicone elastomer can be formed. Thus, the compounds of the present invention
It is extremely useful as a raw material for synthesizing silicone rubber having excellent solvent resistance, chemical resistance, release properties and the like.

[Brief description of the drawings]

FIG. 1 is a view showing an IR chart of the 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.

────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Shinichi Sato 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory (56) References JP-A-61-12751 ( JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) C08G 65/32 C08G 77/60-77/62 CA (CAS)

Claims (1)

(57) [Claims] 1. The following general formula (1): Vi—CH ₂ NHCO— (Y) _a —Rf ¹ —CONHCH ₂ —Vi (1) wherein Vi is a vinyl group, and a is 1 or more. Rf ¹ is represented by the following formula (1a): (1 is an integer of 0 to 8, k and m are integers of 0 to 20, j and n are integers of 0 or 1, and j + k + 1 + m + n ≧ 1)
In divalent perfluoroalkylene group or divalent perfluoroalkyl ether group represented, Y is represented by the following formula ^{(1b): -Rf 1 -CONH (} CH 2) 3 -Q- (CH 2) 3 NHCO- (1b) (Rf ¹ is the same as described above, and Q is the following formula (1c): Here, R ¹ and R ² are each an unsubstituted or substituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and Rf ² is
K or m of Rf ¹ is a divalent group which is 0 to 5,
Or a divalent group represented by the formula :).