JPH111560A - Organocyclosiloxane and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain the subject compound useful as a heat-resistant oil such as a hydraulic fluid with heat resistance as a requirement by binding a diorganopolysiloxane residue via an alkylene group to the silicon atom to a siloxane. SOLUTION: In the presence of (A) a catalyst for hydrosilylation (e.g. chloroplatinic acid), (B) a diorganopolysiloxane of formula I (R<1> and R<3> are each an alkyl, etc.; R<4> is an alkenyl; (m) is a number 5-1,000) and (C) an organocyclosiloxae of formula II ((n) is a number 3-8) (e.g. 1,3,5,7- tetramethylcyclotetrasiloxane) are subject to hydrosilylation in such an amount of the platinum in the component A at 0.1-1,000 ppm based on the components B and C at 40-150 deg.C to obtain the objective compound of formula III (R<2> is an alkylene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an organocyclosiloxane and a method for producing the same, and more particularly, to a novel organocyclosiloxane in which a diorganopolysiloxane residue is bonded to a silicon atom via an alkylene group,
And a method for efficiently producing the organocyclosiloxane.

[0002]

2. Description of the Related Art As an organocyclosiloxane, an organocyclosiloxane having an azido group bonded thereto (Japanese Patent Laid-Open No.
4-30300), an organocyclosiloxane having a perfluoroalkyl group bonded thereto (JP-A-60-1).
No. 63887), an organocyclosiloxane having a trimethoxysilylethyl group bonded thereto (JP-A-64-6).
No. 036).

[0003]

However, there is no known organocyclosiloxane in which a diorganopolysiloxane residue is bonded to a silicon atom via an alkylene group, and such an organocyclosiloxane has a high temperature. Reduction of molecular weight due to cleavage of siloxane bond under atmosphere,
That is, it has been expected as a heat-resistant oil having a reduced droop phenomenon and a reduced viscosity.

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, an object of the present invention is to provide a novel organocyclosiloxane in which a diorganopolysiloxane residue is bonded to a silicon atom via an alkylene group, and a method for efficiently producing the organocyclosiloxane. .

[0005]

The organocyclosiloxane of the present invention has a general formula:

Embedded image (Wherein, R ¹ is the same or different and is a group selected from the group consisting of an alkyl group and a phenyl group, R ² is an alkylene group, and R ³ is an alkyl group, an alkenyl group, a phenyl group, and a hydroxyl group. A group selected from the group consisting of: m is a number of 5 to 1,000, and n is 3 to
It is the number eight. ).

The process for producing an organocyclosiloxane of the present invention comprises the steps of: (A) in the presence of a catalyst for a hydrosilylation reaction;

Embedded image (Wherein, R ¹ is the same or different and is a group selected from the group consisting of an alkyl group and a phenyl group, and R ³ is a group selected from the group consisting of an alkyl group, an alkenyl group, a phenyl group, and a hydroxyl group. , R ⁴ is an alkenyl group, m is a number of 5 to 1,000), and (C) a general formula:

Embedded image (Wherein, R ¹ is a group selected from the group consisting of an alkyl group and a phenyl group, and n is a number of 3 to 8). .

[0007]

First, the organocyclosiloxane of the present invention will be described in detail. The organocyclosiloxane of the present invention is characterized in that a diorganopolysiloxane residue is bonded to a silicon atom via an alkylene group, as represented by the above general formula. R ¹ in the above formula
Are the same or different groups selected from the group consisting of an alkyl group and a phenyl group. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. R ² in the above formula is an alkylene group;
Examples include an ethylene group, a propylene group, and a butylene group.
R ³ in the above formula is a group selected from the group consisting of an alkyl group, an alkenyl group, a phenyl group, and a hydroxyl group. As the alkyl group of R ³ , the same alkyl group as R ¹ is exemplified. ^As the alkenyl group of ³ , a vinyl group,
An allyl group and a butenyl group are exemplified. Also, m in the above equation
Is a number from 5 to 1,000. This is because the effect of the diorganopolysiloxane residue, in which m is less than 5, is less likely to be exhibited, while the effect of the organocyclosiloxane, when m is more than 1,000, is obtained. Is difficult to develop. Also, n in the above equation
Is a number from 3 to 8. This is because there is no compound in which n is less than 3, while a compound in which n exceeds 8 is difficult to purify or hardly exhibit the effect as an organocyclosiloxane.

The organocyclosiloxane of the present invention has a general formula:

Embedded image (In the formula, m is a number of 5 to 1,000, and n is a number of 3 to 8.) An organocyclosiloxane represented by the general formula:

Embedded image (In the formula, m is a number of 5 to 1,000, and n is a number of 3 to 8.) An organocyclosiloxane represented by the general formula:

Embedded image (In the formula, n is a number of 3 to 8, p and q are each a positive number, and p + q is a number of 5 to 1,000.)
An organocyclosiloxane represented by the general formula:

Embedded image (In the formula, n is a number of 3 to 8, p and q are each a positive number, and p + q is a number of 5 to 1,000.)
Are exemplified.

As a method for efficiently producing such an organocyclosiloxane of the present invention, the production method of the present invention will be described in detail. The production method of the present invention is characterized in that the diorganopolysiloxane of the component (B) and the organocyclosiloxane of the component (C) are subjected to a hydrosilylation reaction in the presence of the hydrosilylation reaction catalyst of the component (A).

The catalyst for hydrosilylation reaction of the component (A) is as follows:
A catalyst for promoting a hydrosilylation reaction between an alkenyl group in the component (B) and a silicon-bonded hydrogen atom in the component (C). Examples of such a catalyst of the component (A) include a platinum-based hydrosilylation reaction catalyst, a rhodium-based hydrosilylation reaction catalyst, and a palladium-based hydrosilylation reaction catalyst, and particularly, a platinum-based hydrosilylation reaction catalyst. Is preferred. Examples of the platinum-based hydrosilylation reaction catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, a carbonyl complex of platinum, and an alkenylsiloxane complex of platinum.

In the production method of the present invention, the component (A) is added in an amount sufficient to promote the hydrosilylation reaction of the components (B) and (C). When a catalyst for the chemical reaction is used, the component (B) and the component (C)
The amount of platinum in component (A) is 0.1 to
Preferably, the amount is in the range of 1,000 ppm,
In particular, it is preferable that this amount is in the range of 0.1 to 500 ppm.

The diorganopolysiloxane of the component (B) is
It is a raw material for introducing a diorganopolysiloxane residue bonded via an alkylene group to a silicon atom in the siloxane forming the main skeleton of the organocyclosiloxane of the present invention, and is represented by the above general formula. R ¹ in the above formula is the same or different and is a group selected from the group consisting of an alkyl group and a phenyl group, and the same groups as described above are exemplified. R ³ in the above formula is an alkyl group, an alkenyl group,
It is a group selected from the group consisting of a phenyl group and a hydroxyl group, and the same groups as described above are exemplified. In addition, R in the above equation
⁴ is an alkenyl group, for example, an ethyl group, an allyl group, and a butenyl group. Also, m in the above equation is 5 to 1,000.
Is the number of

The organocyclosiloxane of the component (C) is
It is a component for forming the main skeleton of the organocyclosiloxane of the present invention, and is represented by the above general formula. R ¹ in the above formula is a group selected from the group consisting of an alkyl group and a phenyl group, and the same groups as described above are exemplified. Further, n in the above formula is a number of 3 to 8. Examples of the organocyclosiloxane of the component (C) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,
9-pentamethylcyclopentasiloxane is exemplified.

In the production method of the present invention, when the component (C) has two alkenyl groups in the component (B), the amount of the component (C) is calculated based on one alkenyl group in the component (B). It is preferable that the number of silicon-bonded hydrogen atoms in the component (C) is 0.5 or less, particularly preferably 0.3 or less. When the amount of the component (C) is one alkenyl group in the component (B), the silicon atom bond in the component (C) per one alkenyl group in the component (B) is used. It is preferred that the number of hydrogen atoms is 1.5 or less,
The number is preferably not more than 0.9, and particularly preferably not more than 0.9.

In the production method of the present invention, the conditions of the hydrosilylation reaction are not limited. However, the temperature is in the range of 40 to 150 ° C. because the hydrosilylation reaction proceeds rapidly and side reactions hardly occur. Is preferably within the range. The hydrosilylation reaction may be performed in an organic solvent. As the organic solvent, toluene,
It is preferably a non-polar organic solvent such as xylene. The production of the organocyclosiloxane of the present invention can be confirmed by nuclear magnetic resonance spectroscopy, infrared spectroscopy and the like.

Since the organocyclosiloxane of the present invention has a diorganopolysiloxane residue bonded to a silicon atom in the siloxane via an alkylene group, the viscosity of the organocyclosiloxane due to cleavage of the siloxane bond under a high temperature atmosphere is remarkable. The decrease can be suppressed. Therefore, the organocyclosiloxane of the present invention can be used as a heat-resistant oil such as a hydraulic oil that requires heat resistance.

[0017]

EXAMPLES The organocyclosiloxane of the present invention and a method for producing the same will be described in detail with reference to examples. In addition, the viscosity in an Example is a value in 25 degreeC.

Example 1 1 liter with a stirrer
In a round bottom flask, the viscosity is 100 centipoise, the average formula is:

Embedded image And 800 g (about 0.22 mol) of α-vinyl-ω-n-butyl-dimethylpolysiloxane and 0.008 g of chloroplatinic acid were charged and mixed well. Next, change this to 8
While heating to 0 ° C., the average formula:

Embedded image Methyl hydrogen cyclosiloxane 10 represented by
g (about 0.04 mol) was dropped from the dropping funnel over 30 minutes. The temperature of the reaction solution was 80 to 90 ° C. Thereafter, the reaction solution was kept at 80 to 100 ° C. and stirred for 1 hour. In order to confirm that no unreacted silicon-bonded hydrogen atoms remain in the added methylhydrogencyclosiloxane, a part of the reaction solution was sampled and added to 15 g of a 5% by weight-ethanol solution of the reaction solution. Three drops of an ethanol solution of saturated silver nitrate were added with a dropper, and it was confirmed that there was no coloring. Thereafter, the temperature of the reaction solution is set to 100
The solution was stripped at 1 ° C. and the degree of vacuum at 20 mmHg for 1 hour to remove low boiling components. After stripping, 805 g of a pale yellow transparent liquid having a viscosity of 250 centipoise
I got This liquid was analyzed by nuclear magnetic resonance spectroscopy to obtain an average formula:

Embedded image Was confirmed to be an organocyclosiloxane represented by the following formula:

Example 2 1 liter with a stirrer
In a round bottom flask, the average formula:

Embedded image And 800 g (about 0.11 mol) of α-vinyl-ω-n-butyl-dimethylpolysiloxane and 0.008 g of chloroplatinic acid were charged and mixed well. Next, while heating this to 80 ° C., the average formula:

Embedded image Methyl hydrogen cyclosiloxane 10 represented by
g (about 0.02 mol) was dropped from the dropping funnel over 30 minutes. The temperature of the reaction solution was 80 to 90 ° C. Thereafter, the reaction solution was kept at 80 to 100 ° C. and stirred for 1 hour. In order to confirm that no unreacted silicon-bonded hydrogen atoms remain in the added methylhydrogencyclosiloxane, a part of the reaction solution was sampled and added to 15 g of a 5% by weight-ethanol solution of the reaction solution. Three drops of an ethanol solution of saturated silver nitrate were added with a dropper, and it was confirmed that there was no coloring. Thereafter, the temperature of the reaction solution is set to 100
The solution was stripped at 1 ° C. and the degree of vacuum at 20 mmHg for 1 hour to remove low boiling components. After stripping, a light yellow transparent liquid material 80 having a viscosity of 5,000 centipoise
5 g were obtained. When this liquid was analyzed by nuclear magnetic resonance spectroscopy, the peak of Si-H disappeared and the peak of the vinyl group also disappeared.

Embedded image Was confirmed to be an organocyclosiloxane represented by the following formula:

Example 3 1 liter with a stirrer
In a round bottom flask, the viscosity is 360 centipoise and the average formula is:

Embedded image 900 g (about 0.081 mol) of α, ω-divinyl-dimethylpolysiloxane represented by the formula and 0.009 chloroplatinic acid
g was added and mixed well. Next, while heating this to 80 ° C., the average formula:

Embedded image 1. Methyl hydrogen cyclosiloxane represented by
25 g (about 0.0052 mol) was dissolved in 20 g of toluene, and this was added dropwise from the dropping funnel over 30 minutes. The temperature of the reaction solution was 80 to 90 ° C. Thereafter, the reaction solution was kept at 80 to 100 ° C. and stirred for 1 hour. In order to confirm that no unreacted silicon-bonded hydrogen atoms remain in the added methylhydrogencyclosiloxane, a part of the reaction solution was sampled and added to 15 g of a 5% by weight-ethanol solution of the reaction solution. Three drops of an ethanol solution of saturated silver nitrate were added with a dropper, and it was confirmed that there was no coloring. Thereafter, the temperature of the reaction solution was set to 100 ° C.
The mixture was stripped at 0 mmHg for 1 hour to remove low-boiling components. After stripping, 900 g of a pale yellow transparent liquid having a viscosity of 640 centipoise was obtained. When this liquid was analyzed by nuclear magnetic resonance spectrum,
Since the peak of Si-H has disappeared and the peak of the vinyl group has decreased, this liquid material has the average formula:

Embedded image Was confirmed to be a mixture of organocyclosiloxanes represented by

[Application Examples] The organocyclosiloxane obtained in Example 1 was (A), the organocyclosiloxane obtained in Example 3 was (B), the viscosity was 500 centipoise, and both ends of the molecular chain were trimethyl. Assuming that dimethylpolysiloxane blocked with a siloxy group is (C), 50 g of each of (A) to (C) is put into a 100 ml beaker,
These were left in an oven at 240 ° C. Assuming that the initial viscosity of these siloxanes is 100%, the rate of change in viscosity
(%) Was observed. The results are shown in Table 1.

[0022]

[Table 1]

From Table 1, it has been found that the organocyclosiloxane of the present invention has a small rate of change in viscosity under a high-temperature atmosphere and is hardly reduced in viscosity (droop phenomenon).

[0024]

According to the present invention, the organocyclosiloxane is
This is a novel compound in which a diorganopolysiloxane residue is bonded to a silicon atom in the siloxane via an alkylene group.The production method of the present invention makes it possible to efficiently produce such a novel organocyclosiloxane. There is a feature that can be.

[Brief description of the drawings]

FIG. 1 is a nuclear magnetic resonance spectrum chart of an organocyclosiloxane prepared in Example 1.

Claims (2)

[Claims] 1. A compound of the general formula: (Wherein, R ¹ is the same or different and is a group selected from the group consisting of an alkyl group and a phenyl group, R ² is an alkylene group, R ³ is an alkyl group, an alkenyl group,
A group selected from the group consisting of a phenyl group and a hydroxyl group, m is a number of 5 to 1,000, and n is a number of 3 to 8. The organocyclosiloxane represented by). (2) In the presence of (A) a catalyst for a hydrosilylation reaction, (B) a general formula: (Wherein, R ¹ is the same or different and is a group selected from the group consisting of an alkyl group and a phenyl group, and R ³ is a group selected from the group consisting of an alkyl group, an alkenyl group, a phenyl group, and a hydroxyl group. , R ⁴ is an alkenyl group, and m is a number of 5 to 1,000), and (C) a general formula: (Wherein, R ¹ is a group selected from the group consisting of an alkyl group and a phenyl group, and n is a number of 3 to 8). , The general formula: (Wherein, R ¹ is the same or different and is a group selected from the group consisting of an alkyl group and a phenyl group, R ² is an alkylene group, R ³ is an alkyl group, an alkenyl group,
A group selected from the group consisting of a phenyl group and a hydroxyl group, m is a number of 5 to 1,000, and n is a number of 3 to 8. )).