JPH0551462A - Organosilicon compound and its production - Google Patents

Abstract

PURPOSE:To obtain the title new compound useful as an improver for various organic resins such as polyimide resin and an adhesive for bonding an organic resin to an inorganic resin, comprising plural Si atom bond-containing organic functional groups and plural Si atom bond-containing hydrolyzable group. CONSTITUTION:An organosilicon compound shown by formula I (R<1> is monofunctional hydrocarbon containing no aliphatic unsaturated bond; R<2> is bifunctional hydrocarbon; A is amino or epoxy functional organic group, etc.; X is hydrolyzable group; n and p are 0 or 1; m is 0-100). The compound is obtained by subjecting an organosilicon compound shown by formula II and an aliphatic unsaturated hydrocarbon compound (e.g. allyl glycidyl ether) containing an organic functional group such as amino group or epoxy functional organic group to addition reaction preferably at 50-200 deg.C. Preferably an equimolar amount of the aliphatic unsaturated hydrocarbon compound is used based on Si atom-bonded H atom in the compound shown by formula II. Chloroplatinic acid, for example, is used as the catalyst utilized in the reaction.

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 and a method for producing the same.
The present invention relates to an organosilicon compound having one or more silicon atom-bonded organic functional groups and two or more silicon atom-bonded hydrolyzable groups at the other molecular chain end, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, trialkoxysilane has been known as an organosilicon compound having a silicon atom-bonded hydrogen atom and a silicon atom-bonded hydrolyzable group. In addition, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, and the like, which are derivatives of this trialkoxysilane, are known, and these are called silane coupling agents. By interposing between the resin and the inorganic substance, it is said to be useful for improving the compatibility, adhesiveness, etc. of both, and is widely used as an additive for improving physical properties of various organic resins, an adhesive, a primer. There is. Furthermore, the present inventors previously proposed a novel heterobifunctional organosilicon compound having a siloxane spacer (Japanese Patent Application No. 3-27920). However, since the silane coupling agent and these organosilicon compounds contain two or more hydrolyzable groups in one molecule, they contain only one organic functional group.
Depending on the application, the characteristics could not be fully exhibited. For example, when an amino group-containing trialkoxysilane is used as a modifier for a polyimide resin, there is a problem that a hydrolyzable group can be introduced only at the terminal of the polyimide resin and a sufficient modifying effect cannot be obtained. ..

[0003]

The present inventors have arrived at the present invention as a result of intensive research to solve the above problems. That is, an object of the present invention is to provide a novel organosilicon compound having two or more organic functional groups and two or more silicon atom-bonded hydrolyzable groups in one molecule, and a method for producing the same.

[0004]

The present invention has the general formula:

[Chemical 4] (Wherein R ¹ is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, R ² is a divalent hydrocarbon group, A is an amino group, an epoxy functional organic group, or a hydroxy group. Or an organic functional group in which active hydrogen of these functional groups is substituted with a triorganosilyl group, X is a hydrolyzable group, n is an integer of 0 or 1, m is an integer of 0 to 100, p Represents an integer of 0 or 1.) and an organic silicon compound (I) represented by the general formula:

[Chemical 5] (In the formula, R ¹ , R ² , X, n, m and p are the same as above.), Selected from an amino group, an epoxy functional organic group and a hydroxy group. Characterized in that an aliphatic unsaturated hydrocarbon compound containing an organic functional group or active hydrogen of these organic functional groups is subjected to an addition reaction with an aliphatic unsaturated hydrocarbon compound substituted with a triorganosilyl group , General formula:

[Chemical 6] (In the formula, R ¹ , R ² , A, X, n, m and p are the same as described above.) The present invention relates to a method for producing an organosilicon compound (I).

The present invention will be described in detail below. The organosilicon compound of the present invention has the general formula:

[Chemical 7] Indicated by. In the above formula, R ¹ is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group; a phenyl group, a tolyl group, Examples thereof include aryl groups such as xylyl group; substituted alkyl groups such as chloromethyl group and perfluoromethyl group. R ² is a divalent hydrocarbon group, and specific examples thereof include alkylene groups such as methylene group, ethylene group, propylene group and butylene group. A is an amino group, N (2
-Aminoethyl) amino group, amino group such as N-cyclohexylamino group; glycidoxy group, epoxy functional organic group such as 3,4 epoxycyclohexyl group; organic functional group selected from hydroxy group or active hydrogen thereof. It is a group substituted with a triorganosilyl group. Examples of the organic functional group in which the organic functional group A and the above R ² are bonded are shown below.

[Chemical 8]

[Chemical 9]

[Chemical 10]

[Chemical 11]

[Chemical formula 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18] X is a hydrolyzable group, and examples thereof include an alkoxy group such as a methoxy group and an ethoxy group, an acetoxy group, an oxime group, an amide group and the like. n is an integer of 0 or 1, and when n is 0, it is an organosilicon compound having 3 organic functional groups, and when n is 1, it is an organosilicon compound having 2 organic functional groups. .. Here, the numerical value of n is a characteristic of the present invention. When n is an integer of 0 or 1, the organosilicon compound of the present invention is an organic compound having 2 or 3 silicon atoms bonded in one molecule. An organosilicon compound having a functional group can be provided. m is 0 to 1
00 is an integer between, m has hydrolyzable groups bonded silicon atom directly bonded to R ² is 0, each time m is increased by one between R ² and hydrolyzable groups bonded silicon atoms , R ^{1 in} which two R ¹ are bonded are increased by one unit. p
Is an integer of 0 or 1, and when p is 0, it is an organosilicon compound having 3 hydrolyzable groups, and p is 1
In this case, the organosilicon compound has two hydrolyzable groups.

The method for producing the organosilicon compound of the present invention will be described below. The organosilicon compound (II) used in the production method of the present invention has the general formula:

[Chemical 19] It is represented by. In the above formula, R ¹ , R ² , X, n, m and p are the same as above. When n is 0, it is an organosilicon compound having 3 silicon-bonded hydrogen atoms, and when n is 1, it is an organosilicon compound having 2 silicon-bonded hydrogen atoms. The following routes are mentioned as an example of the synthetic route of such an organosilicon compound.

[Chemical 20]

In the present invention, the organosilicon compound (II)
Amino group, epoxy functional organic group,
An aliphatic unsaturated hydrocarbon compound having an organic functional group selected from a hydroxy group or an aliphatic unsaturated hydrocarbon compound in which active hydrogen of these organic functional groups is substituted with a triorganosilyl group (hereinafter referred to as compound (III) (Collectively referred to), the following compounds may be mentioned.

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

Organosilicon compound (II) and compound (III)
The catalyst used in the reaction with is that used in the hydrosilylation reaction. Specific examples include platinum catalysts such as chloroplatinic acid, alcohol solutions of chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, etc .; Wilkinson complexes, rhodium-carbonyl complexes, and other rhodium catalysts. To be done. The amount of the catalyst used in this hydrosilylation reaction is in the range of 1 to 100 parts by weight as a catalyst atom based on 1 million parts by weight of the total amount of the organosilicon compound (II) and the compound (III). , Preferably 1
The amount is 50 parts by weight. This is because when the amount of the catalyst added is less than 1 part by weight as a catalyst atom with respect to the total amount of the organosilicon compound (II) and the compound (III) of 1 million parts by weight, the addition reaction may not proceed. This is because even if the amount is more than parts by weight, the addition reaction rate is not accelerated in proportion to the amount used, and it is uneconomical to use such an expensive catalyst in a large amount.

The addition reaction temperature is not particularly limited,
It is usually in the range of 25 to 250 ° C., preferably 50.
Is in the range of up to 200 ° C. This is because if the reaction temperature is lower than 25 ° C., the reaction rate is slow and the productivity is lowered, and if the reaction temperature exceeds 250 ° C., a side reaction caused by the addition reaction catalyst may occur.

The use of an organic solvent in this addition reaction is optional as long as the object of the present invention is not impaired. Examples of such an organic solvent include aromatic solvents such as benzene, toluene and xylene, aliphatic solvents such as hexane and heptane, ether solvents such as tetrahydrofuran and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, and ethyl acetate. , Ester solvents such as butyl acetate, etc.

What is important here is to use the compound (III) in the equimolar amount or more with the silicon atom-bonded hydrogen atom in the organosilicon compound (II) for the addition reaction. After completion of the addition reaction, the unreacted compound (II
By distilling off I) under reduced pressure, the desired organosilicon compound (I) can be obtained.

The organosilicon compound of the present invention has two or more silicon atom-bonded organic functional groups and silicon atom-bonded hydrolyzable groups in one molecule, and is a modifier for various organic resins such as polyimide resins. It is also useful as an adhesive or a primer for adhering various organic resins and inorganic substances.

[0013]

The present invention will be described in more detail with reference to the following examples. In the examples, Me represents a methyl group.

[0014]

Example 1 A four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was charged with the compound 10 represented by the following formula.
8.7 grams (0.261 moles) of chloroplatinic acid and 1,3
47.3 milligrams of platinum vinyl siloxane complex (platinum concentration 4.6 weight percent) prepared with divinyl-1,1,3,3-tetramethyldisiloxane was added.

[Chemical 32] These mixtures were heated to 90 ° C., and 80.9 g (0.626 mol) of N-trimethylsilylallylamine was added dropwise thereto for 1.2 hours. 90 after the dropping is completed
The reaction was carried out at 170 ° C. for 3.5 hours. The low boiling point substance was distilled off from the reaction mixture under reduced pressure at 190 ° C./3 mmHg for 3 hours,
155.8 g of the compound (A) represented by the following formula was obtained.
The yield of this compound was 89%.

[Chemical 33]

[0015]

Example 2 A compound 6 represented by the following formula was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
8.6 grams (0.0962 moles) of chloroplatinic acid and 1,
15.0 milligrams of a platinum vinyl siloxane complex (platinum concentration 4.6 weight percent) prepared with 3-divinyl-1,1,3,3-tetramethyldisiloxane was added.

[Chemical 34] These mixtures were heated to 105 ° C., and 31.2 g (0.241 mol) of N-trimethylsilylallylamine was added dropwise thereto over 50 minutes. 120-
The reaction was carried out at 164 ° C for 2 hours. The low boiling point substance was distilled off from the reaction mixture under reduced pressure at 130 ° C./2 mmHg for 3 hours to obtain 89.0 g of a compound (B) represented by the following formula. The yield of this compound was 96%.

[Chemical 35]

[0016]

Example 3 A four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with the compound 1 represented by the following formula.
0.1 g (0.0242 mol) of chloroplatinic acid and 1,
A solution of a platinum vinyl siloxane complex in i-propanol prepared from 3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum concentration 4.7 weight percent) 7.0
I put in milligrams.

[Chemical 36] These mixtures were heated to 85 ° C. and 1 part of 6.91 grams (0.0605 mol) of allyl glycidyl ether was added thereto.
It was added dropwise over 0 minutes. 85-110 ° C after dropping
And reacted for 1.5 hours. Low boiling point substances from the reaction mixture at 140 ° C / 30 mmHg for 1 hour, then 180 ° C / 2
It was distilled off under reduced pressure at mmHg for 1 hour to obtain 14.5 g of the compound (C) represented by the following formula. The yield of this compound is 93
%Met.

[Chemical 37]

[0017]

Example 4 A four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel and a thermometer was charged with the compound 1 represented by the following formula.
2.0 g (0.0288 mol) of chloroplatinic acid and 1,
A solution of a platinum vinyl siloxane complex in i-propanol prepared from 3-divinyl-1,1,3,3-tetramethyldisiloxane (platinum concentration 4.7 weight percent) 7.0
I put in milligrams.

[Chemical 38] These mixtures were heated to 100 ° C., and 9.38 g (0.0720 mol) of allyltrimethylsilyl ether was added dropwise thereto over 10 minutes. After the dropping, 100 ~
The reaction was carried out at 120 ° C for 1 hour. Low boiling point substances from the reaction mixture at 100 ° C / 28mmHg for 1 hour, then 140 ° C
It was distilled off under reduced pressure at / 2 mmHg for 1 hour to obtain 18.4 g of the compound (D) represented by the following formula. The yield of this compound is 9
It was 4%.

[Chemical Formula 39]

[0018]

[Application example 1] Pyromellitic dianhydride was added to a four-necked flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer.
9 g (17.9 mmol), 0.41 g (2.75 mmol) of phthalic anhydride and 68.6 g of N-methyl-2-pyrrolidinone (hereinafter abbreviated as NMP) were added and completely dissolved. .. There, 18.8 g (19.3 mmol) of the compound (B) obtained in Example 2 and NMP were added.
18.6 grams of the mixture was added dropwise over 20 minutes. After completion of dropping, the reaction was carried out at room temperature for 1.5 hours. The obtained polyamic acid NMP solution was applied to a glass plate and heated in an oven at 200 ° C. for 3 hours to obtain a yellow polyimide resin. This polyimide resin showed excellent adhesion to the glass plate.

[0019]

INDUSTRIAL APPLICABILITY The organosilicon compound of the present invention is a novel organosilicon compound, and its production method is characterized in that such a novel organosilicon compound can be produced with high productivity.

[Brief description of drawings]

1 is an infrared absorption spectrum chart of the organosilicon compound (A) produced in Example 1. FIG.

FIG. 2 is an infrared absorption spectrum chart of the organosilicon compound (B) produced in Example 2.

FIG. 3 is an infrared absorption spectrum chart of the organosilicon compound (C) produced in Example 3.

FIG. 4 is an infrared absorption spectrum chart of the organosilicon compound (D) produced in Example 4.

Claims (2)

[Claims] 1. A general formula: (Wherein R ¹ is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond, R ² is a divalent hydrocarbon group, A is an amino group, an epoxy functional organic group, or a hydroxy group. Or an organic functional group in which active hydrogen of these functional groups is substituted with a triorganosilyl group, X is a hydrolyzable group, n is an integer of 0 or 1, m is an integer of 0 to 100, p Represents an integer of 0 or 1.) is an organosilicon compound (I). 2. A general formula: (In the formula, R ¹ , R ² , X, n, m and p are the same as above.), Selected from an amino group, an epoxy functional organic group and a hydroxy group. Characterized in that an aliphatic unsaturated hydrocarbon compound containing an organic functional group or active hydrogen of these organic functional groups is subjected to an addition reaction with an aliphatic unsaturated hydrocarbon compound substituted with a triorganosilyl group , The general formula: (In the formula, R ¹ , R ² , A, X, n, m and p are the same as described above.) A method for producing an organosilicon compound (I).