JPH05209055A - Production of organopolysiloxane having aminosilyl group - Google Patents

Abstract

PURPOSE:To provide the subject compd. useful as a surface-treating agent for metal, a resin modifier, etc., by polymerizing a specific organopolysiloxane with a specific cyclic siloxane in the presence of a basic polymn. catalyst. CONSTITUTION:An organopolysiloxane of formula I (wherein R<1> and R<2> are each H or an optionally substd. 1-10C monovalent hydrocarbon group; R<3> to R<6> are each an optionally substd. 1-8C monovalent hydrocarbon group; (a) and (b) are each 0-2; and (m) is 0-10) is copolymerized with a cyclic siloxane of formula II (wherein R<7> and R<8> are each an optionally substd. 1-20C monovalent hydrocarbon group; and (n) is 2 or higher) in the presence of a basic polymn. catalyst (e.g. potassium siliconate) to give the objective compd. of formula III (wherein (p) is (m); and (q) is 20 or higher).

Description

Detailed Description of the Invention

[0001]

The present invention relates to a metal, glass, inorganic substance, plastic,
The present invention relates to a method for producing an organopolysiloxane represented by the following general formula (3), which can be applied to various substrates such as fibers and woven fabrics, surface treatment agents such as powders, resin modifiers and room temperature curable silicone rubber. ..

[0002]

[Chemical 4] (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 from each other, which are unsubstituted or substituted and have 1 carbon atom.
~ 8 monovalent hydrocarbon groups, R ⁷ and R ⁸ are the same or different from each other and are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms. In addition, a and b are 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 Conventionally, the problems to be solved by the invention
The organopolysiloxane having a reactive substituent directly bonded to silicon has a hydroxyl group (≡
Si-OH) and alkoxy groups (≡Si-OR; R is a hydrocarbon group) are well known, but these groups have poor reactivity, and therefore, the above organopolysiloxane is used as a metal or glass. , Inorganic, plastic, fiber,
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 high temperature,
When the addition of a catalyst adversely affects these substrates, there is a problem that the above-mentioned organopolysiloxane having a reactive substituent cannot be used.

Therefore, in order to solve such a problem, an organopolysiloxane having an aminosilyl group which easily reacts with a hydroxyl group (-OH) of a base material at room temperature to form a siloxane bond has been desired.

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

[0006]

[Chemical 5] (In the formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and q have the same meanings as described above, and c is 0, 1 or 2.)

As another method for producing an organopolysiloxane having an aminosilyl group, a diorganopolysiloxane having a molecular chain terminal blocked with a halogen atom and an amine (HNR ¹ R ² ) are represented by the following reaction formula. There is a manufacturing method of reacting. This method is a by-product (impurity)
However, it is difficult to completely remove the amine salt from the polysiloxane by a method such as distillation. Therefore, when the polysiloxane is used in the electric and electronic fields, impurities may cause adverse effects. May affect. In addition, this manufacturing method has a problem that it is difficult to manufacture a high molecular weight organopolysiloxane due to the manufacturing method.

[0008]

[Chemical 6] (In the formula, R ¹ , R ² , R ³ , R ⁷ , R ⁸ and q have the same meanings as 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 that has an aminosilyl group and that can easily produce an organopolysiloxane having a desired degree of polymerization (viscosity).

[0010]

Means and Actions for Solving the Problems As a result of intensive studies for achieving the above object, the present inventor has found that a low molecular weight organopolysiloxane having an aminosilyl group represented by the following general formula (1) and the following general formula By polymerizing the cyclic siloxane represented by the formula (2) in the presence of a basic polymerization catalyst, a reactive aminosilyl group represented by the following general formula (3) is present at both ends and desired polymerization is performed. It was found that an organopolysiloxane having a certain degree can be easily produced, and the present invention has been completed.

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

[0012]

[Chemical 7] (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.)

Therefore, 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. Provided is a method for producing an organopolysiloxane represented by the general formula (3).

The present invention will be described in more detail below. 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 the first raw material.

[0015]

[Chemical 8]

Here, R ¹ and R ² are hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups 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 thereof include alkenyl groups such as vinyl group and allyl group, aryl groups such as phenyl group, tolyl group and benzyl group.

R ³ , R ⁴ , R ⁵ and R ⁶ are the same or different monovalent hydrocarbon groups having 1 to 8 carbon atoms, and such monovalent hydrocarbon groups include R ¹ , R ² and The same thing is mentioned. 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]

[Chemical 9]

The organopolysiloxane having an aminosilyl group represented by the above general formula (1) is obtained by reacting a siloxane compound having an ≡Si—Cl group with an amine compound as shown in the following reaction formulas A and B. Obtainable. Distillable low molecular weight siloxanes are preferred because amine salts are by-produced in these synthetic methods.

[0022]

[Chemical 10] (In the formula, R ¹ , R ² and R ³ have the same meanings as described above. D
Is 0, 1 or 2. )

[0023]

[Chemical 11] (In the formula, R ¹ , R ² , R ³ , R ⁵ , and R ⁶ have the same meanings as described above. E is 0, 1 or 2, and r is 3 or 4.)

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

[0025]

[Chemical 12]

Here, R ⁷ and R ⁸ are the same or different and are 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, a vinyl group. , Alkenyl groups such as allyl groups, cycloalkyl groups such as cyclohexyl groups and cyclopentyl groups, aryl groups such as phenyl groups and naphthyl groups, and the hydrogen atoms of these groups are partially halogen atoms, cyano groups, and any other organic groups A group substituted with is 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).
Examples thereof include cyclotetrasiloxane.

In 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. The amount of these catalysts used can be a catalytic amount.

When the above-mentioned low molecular weight organopolysiloxane and cyclic siloxane are reacted, they are mixed and 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 kind and amount of the catalyst, but 100
It is preferable to carry out the reaction at ˜200 ° C., especially at 120˜170 ° C. for usually 8 to 24 hours. If the reaction temperature is lower than 100 ° C., polymerization may not occur, and if it exceeds 200 ° C., the organic substituent engaged with the silicon atom may be decomposed. After completion of the reaction, a polymerization terminator such as ethylene chlorohydrin and trimethyl chlorosilane is added to terminate the polymerization, and stripping is performed under reduced pressure to obtain the above formula (1).
The organopolysiloxane having a silyl group represented by can be easily obtained.

According to the production method of the present invention, it is possible to easily obtain an organopolysiloxane having a desired degree of polymerization and having a highly reactive aminosilyl group bonded to the terminal. The organopolysiloxane is a metal or a glass. Room temperature by combining with various base materials such as inorganics, plastics, fibers and textiles, surface treatment agents such as powders, resin modifiers, synthesis of modified polysiloxane with compounds that react with aminosilyl groups, and combination with reactive crosslinking agents The present invention can be applied to applications such as curable silicone rubber, and expands the application range of organopolysiloxanes having an aminosilyl group.

[0031]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

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

[0033]

[Chemical 13]

Next, 0.78 of potassium siliconate containing 10% by weight of potassium and consisting of dimethylsiloxy units.
g, polymerized at 150 ° C. for 12 hours, then cooled to room temperature, added with 0.34 g of trimethylchlorosilane and 0.68 g of hexamethyldisilazane, stirred for 2 hours to terminate the polymerization, and under reduced pressure. Strip at 150 ° C, filter,
1220 g of polysiloxane represented by the following general formula (5)
Got

[0035]

[Chemical 14] 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 to separate into an aqueous layer and an organic layer. As a result of measuring the amount of aminosilyl groups of polysiloxane (5) by performing neutralization titration, 0.01
42 mol / 100 g (theoretical value 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
6g was used and manufactured in the same manner as in Example 1 to obtain 2268g of a polysiloxane represented by the following general formula (7).

[0037]

[Chemical 15] The viscosity of the obtained polysiloxane (7) is 3200 cs, and the amount of aminosilyl group is 0.0072 mol / 100 g.
(Theoretical value 0.0068 g mol / 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 similar to those of Example 1 were used. Siliconate 0.78 g, trimethylchlorosilane 0.34 g, hexamethyldisilazane 0.68
g was produced in the same manner as in Example 1 and the following general formula (8)
1300 g of polysiloxane represented by

[0039]

[Chemical 16] The obtained polysiloxane (8) has a viscosity of 910 cs and an aminosilyl group amount of 0.0129 mol / 100 g.
(Theoretical value 0.0128 mol / 100 g).

[0040]

INDUSTRIAL APPLICABILITY According to the present invention, it has a highly reactive aminosilyl group at both ends and is used for various base materials such as metal, glass, inorganic materials, plastics, fibers and fabrics, and surface treating agents such as powders and resins. An organopolysiloxane that can be applied to the production of a modifier, room temperature curable silicone rubber, etc. can be easily produced by adjusting the degree of polymerization thereof.

Claims (1)

[Claims] 1. An organopolysiloxane represented by the following general formula (1) and a cyclic siloxane represented by the following general formula (2) are polymerized in the presence of a basic polymerization catalyst. A method for producing an aminosilyl group-containing organopolysiloxane represented by 3). [Chemical 1] (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 from each other, which are unsubstituted or substituted and have 1 carbon atom.
~ 8 monovalent hydrocarbon group, a and b are 0, 1 or 2, respectively, m is an integer of 0-10. ) [Chemical 2] (In the formula, R ⁷ and R ⁸ are the same or different and are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms, and n is an integer of 2 or more.) (In the formula, R ^{1 to} R ⁸ have the same meanings as described above, and p is 0 to
An integer of 10 and q is an integer of 20 or more. )