JP2666646B2 - Method for producing aminosilyl group-containing organopolysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a highly reactive aminosilyl group, and comprises metals, glasses, inorganic substances, plastics,
The present invention relates to a method for producing an organopolysiloxane represented by the following general formula (3) which can be applied to surface treatment agents such as various substrates such as fibers and woven fabrics and powders, resin modifiers, and room temperature curable silicone rubber. .

[0002]

Embedded image (Wherein, R ^1, R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ and R ² may be the same or different from one another .R ^3, R ⁴ , R ⁵ , R ⁶
Are the same or different, unsubstituted or substituted carbon atoms of 1
To 8 monovalent hydrocarbon groups, R ⁷ and R ⁸ , are the same or different and are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms. A and b are each 0, 1, or 2, p is an integer of 0 to 10, and q is an integer of 20 or more. )

[0003]

2. Description of the Related Art
As the organopolysiloxane having a reactive substituent directly bonded to silicon, a hydroxyl group (≡) may be used as the reactive substituent.
It is well known that those containing Si—OH) and an alkoxy group (≡Si—OR; R is a hydrocarbon group), but these groups are poor in reactivity. , Minerals, plastics, fibers,
When reacting with a substrate such as a woven fabric, it is necessary to heat at a high temperature or to react with a catalyst. Therefore, when using a substrate that cannot be heated at a high temperature,
When the addition of a catalyst adversely affects these substrates, there is a problem that the organopolysiloxane having the reactive substituent cannot be used.

In order to solve such problems, an organopolysiloxane having an aminosilyl group which easily reacts with a hydroxyl group (-OH) of a substrate at room temperature to form a siloxane bond has been desired.

[0005] As a method for producing this organopolysiloxane having an aminosilyl group, conventionally, as shown in the following reaction formula, a diorganopolysiloxane in which both ends of a molecular chain are blocked with hydroxyl groups and R ³ _c Si (NR ¹ R ² ) A method of reacting with a silicon compound having an aminosilyl group represented by _4-c is known. In this method, diorganopolysiloxanes may be bonded to each other, and therefore, the molecular weight of the organopolysiloxane ( Viscosity) is difficult to control.

[0006]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ , and q have the same meaning as described above, and c is 0, 1, or 2.)

As another method for producing an organopolysiloxane having an aminosilyl group, as shown in the following reaction formula, a diorganopolysiloxane whose molecular chain end is blocked with a halogen atom and an amine (HNR ¹ R ² ) Is produced. This method uses by-products (impurities)
However, it is difficult to completely remove the amine salt from the polysiloxane by a method such as distillation. Therefore, when this polysiloxane is used in the electric and electronic fields, impurities have an adverse effect. May have an effect. In addition, this production method has a problem that it is difficult to produce a high molecular weight organopolysiloxane due to the production method.

[0008]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ , and q have the same meanings as described above.)

The present invention has been made in view of the above circumstances,
An object of the present invention is to provide a method for producing an organopolysiloxane, which has an aminosilyl group and can easily produce an organopolysiloxane having a desired degree of polymerization (viscosity).

[0010]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a low molecular weight organopolysiloxane having an aminosilyl group represented by the following general formula (1) and By polymerizing the cyclic siloxane represented by the formula (2) in the presence of a basic polymerization catalyst, a highly reactive aminosilyl group represented by the following general formula (3) is provided at both ends, and the desired polymerization is carried out. The present inventors have found that organopolysiloxanes having a high degree can be easily produced, and have accomplished the present invention.

That is, by using a low molecular weight organopolysiloxane having an aminosilyl group of the formula (1),
The desired organopolysiloxane of the formula (3) has an aminosilyl group at both terminals, and the compound of the formula (2)
It has been found that a high molecular weight organopolysiloxane having an aminosilyl group at both ends can be easily produced by polymerizing the both, since the cyclic siloxane constitutes the siloxane unit of the main chain of the organopolysiloxane.

[0012]

Embedded image (In the formula, R ^{1 to} R ⁸ , a, b, p, and q have the same meanings as described above, m is an integer of 0 to 10, and n is an integer of 2 or more.)

Accordingly, the present invention is characterized in that the organopolysiloxane represented by the general formula (1) and the cyclic siloxane represented by the general formula (2) are polymerized in the presence of a basic polymerization catalyst. A method for producing an organopolysiloxane represented by the general formula (3) is provided.

Hereinafter, the present invention will be described in more detail. In the production method of the present invention, a low molecular weight organopolysiloxane having an aminosilyl group represented by the following general formula (1) is used as a first raw material.

[0015]

Embedded image

Wherein R ¹ and R ² are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms;
R ¹ and R ² may be the same or different from each other. Examples of such a monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group; a cycloalkyl group such as a cyclohexyl group and a cyclopentyl group;
Examples include an alkenyl group such as a vinyl group and an allyl group, and an aryl group such as a phenyl group, a tolyl group, and a benzyl group.

R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different and are monovalent hydrocarbon groups having 1 to 8 carbon atoms. Such monovalent hydrocarbon groups include R ¹ and R ² . And the like. a is 0, 1 or 2.

Note that m is an integer of 0 to 10, and a and b are 0, 1, or 2, respectively.

Specific examples of the organopolysiloxane of the formula (1) include those represented by the following formula.

[0020]

Embedded image

The organopolysiloxane having an aminosilyl group represented by the above general formula (1) can be obtained by reacting a siloxane compound having a ≡Si—Cl group with an amine compound as shown in the following reaction formulas A and B, for example. Obtainable. In these synthesis methods, a distillable low molecular weight siloxane is preferable because an amine salt is formed as a by-product.

[0022]

Embedded image (Wherein, R ¹ , R ² and R ³ have the same meaning as described above. D
Is 0, 1 or 2. )

[0023]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁵ , and R ⁶ have the same meaning as described above. E is 0, 1 or 2, and r is 3 or 4.)

Next, a cyclic siloxane represented by the following general formula (2) is used as the second raw material in the production method of the present invention.

[0025]

Embedded image

Here, R ⁷ and R ⁸ are the same or different unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group and a butyl group, and a vinyl group. Alkenyl groups such as aryl, allyl group, cycloalkyl groups such as cyclohexyl group and cyclopentyl group; aryl groups such as phenyl group and naphthyl group; and hydrogen atoms of these groups are partially halogen atoms, cyano groups, and any other organic groups Are exemplified. In addition, n is an integer of 2 or more, and preferably an integer of 3 to 5.

Specific examples of such a cyclic siloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and trimethyltri (trifluoropropyl).
And cyclotetrasiloxane.

According to the present invention, the low molecular weight organopolysiloxane represented by the general formula (1) and the cyclic siloxane represented by the general formula (2) are polymerized in the presence of a basic polymerization catalyst. Examples of the basic polymerization catalyst include cesium siliconate, potassium siliconate, sodium siliconate, tetrabutyl phosphate, and the like. In addition, the amount of these catalysts used can be a catalytic amount.

When reacting the low molecular weight organopolysiloxane with the cyclic siloxane, they are mixed, preferably heated in an inert gas such as nitrogen, and then a basic polymerization catalyst is added and heated. In this case, the reaction conditions can be appropriately adjusted depending on the type and amount of the catalyst.
The reaction is preferably performed at a temperature of from 200 to 200 ° C, particularly from 120 to 170 ° C, for usually from 8 to 24 hours. When the reaction temperature is lower than 100 ° C., the polymerization may not be performed, and when the reaction temperature is higher than 200 ° C., the organic substituent engaged with the silicon atom may be decomposed. After completion of the reaction, the polymerization is stopped by adding a polymerization terminator such as ethylene chlorohydrin or trimethylchlorosilane, and stripping is performed under reduced pressure, whereby the above formula (1) is obtained.
An organopolysiloxane having a silyl group represented by formula (1) can be easily obtained.

According to the production method of the present invention, an organopolysiloxane having a desired degree of polymerization and having a highly reactive aminosilyl group bonded to the terminal can be easily obtained. Surface treatment agents for various substrates such as inorganics, plastics, fibers, fabrics and the like, powders and other surface treatment agents, resin modifiers, and synthesis of modified polysiloxanes with compounds that react with aminosilyl groups, and room temperature in combination with reactive crosslinking agents The present invention can be applied to applications such as curable silicone rubber, and expands the range of applications of organopolysiloxane having an aminosilyl group.

[0031]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1 36.8 g of an aminosilyl group-containing siloxane represented by the following general formula (4) and 1450 g of octamethylcyclotetrasiloxane were charged into a 2 liter flask and heated to 110 ° C. in a nitrogen stream. did.

[0033]

Embedded image

Next, 0.78% of potassium siliconate containing 10% by weight of potassium and comprising dimethylsiloxy units.
g was added, polymerization was carried out at 150 ° C. for 12 hours, then cooled to room temperature, 0.34 g of trimethylchlorosilane and 0.68 g of hexamethyldisilazane were added, and the mixture was stirred for 2 hours to stop the polymerization. Strip at 150 ° C., filter,
1220 g of a polysiloxane represented by the following general formula (5)
I got

[0035]

Embedded image The viscosity of the obtained polysiloxane (5) was 640 cs. In addition, 20 g of this polysiloxane (5) was dissolved in 40 g of toluene, housed in a closed container together with 50 g of pure water, shaken for 16 hours, and allowed to stand still to separate into an aqueous layer and an organic layer. By performing a neutralization titration, the amount of aminosilyl groups in the polysiloxane (5) was measured.
42 mol / 100 g (theory 0.0135 g / 100
g).

Example 2 39.7 g of a siloxane having an aminosilyl group represented by the following general formula (6), 2664 g of octamethylcyclotetrasiloxane, 1.56 g of potassium siliconate similar to that of Example 1, and 0 of trimethylchlorosilane 0.68 g, hexamethyldisilazane 1.3
Using 6 g, it was produced in the same manner as in Example 1 to obtain 2268 g of a polysiloxane represented by the following general formula (7).

[0037]

Embedded image The viscosity of the obtained polysiloxane (7) was 3,200 cs, and the amount of aminosilyl group was 0.0072 mol / 100 g.
(Theoretical value: 0.0068 gmol / 100 g).

Example 3 39.7 g of the siloxane (6) having an aminosilyl group used in Example 2, 1361.6 g of octamethylcyclotetrasiloxane, 198 g of octaphenylcyclotetrasiloxane, and potassium as in Example 1 0.78 g of siliconate, 0.34 g of trimethylchlorosilane, 0.68 of hexamethyldisilazane
g, using the following general formula (8)
1300 g of a polysiloxane represented by the formula was obtained.

[0039]

Embedded image The viscosity of the obtained polysiloxane (8) is 910 cs, and the amount of aminosilyl group is 0.0129 mol / 100 g.
(Theoretical value: 0.0128 mol / 100 g).

[0040]

According to the present invention, various base materials such as metals, glasses, inorganic substances, plastics, fibers, and fabrics, surface treatment agents such as powders, resins having a highly reactive aminosilyl group at both ends. Organopolysiloxanes that can be applied to the production of modifiers, room-temperature-curable silicone rubbers, and the like can be easily produced by adjusting the degree of polymerization.

Claims (1)

(57) [Claims] 1. A method of polymerizing an organopolysiloxane represented by the following general formula (1) and a cyclic siloxane represented by the following general formula (2) in the presence of a basic polymerization catalyst: A method for producing an aminosilyl group-containing organopolysiloxane represented by 3). Embedded image (Wherein, R ^1, R ² is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ and R ² may be the same or different from one another .R ^3, R ⁴ , R ⁵ , R ⁶
Are the same or different, unsubstituted or substituted carbon atoms of 1
And 8 are monovalent hydrocarbon groups, a and b are each 0, 1 or 2, and m is an integer of 0 to 10. ) (In the formula, R ⁷ and R ⁸ are the same or different and are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 2 or more.) (Wherein, R ^{1 to} R ⁸ have the same meaning as described above, and p is 0 to
An integer of 10 and q is an integer of 20 or more. )