JPH06220199A - Organopolysiloxane and its production - Google Patents

Abstract

PURPOSE:To provide a new organopolysiloxane useful as a modifier for imparting lubricity, water repellency, flexibility, etc., to an organic resin such as anepoxy resin or a phenol resin. CONSTITUTION:An organopolysiloxane of formula I [R<1> is a univalent hydrocarbon; A is hydroxyl group, an epoxy-containing organic group, an amino group- containing organic group of formula II (R<2> is a hydroxyl group-containing divalent organic group; R<3> is a divalent organic group containing an aromatic ring bonded directly to N atom; R<4> is H or a univalent hydrocarbon), etc.; Provided that one or more of A are a group of formula II; (m) and (n) are each 0 or a positive integer]. This organoplysiloxane is synthesized by reacting an epoxy- containing organopolysiloxane of formula III (B is a univalent hydrocarbon, hydroxyl group or an epoxy-containing organic group; Provided that one or more of B are an epoxy-containing organic group) with a diamine compound (preferably 4,4'-methylenedianilne, etc.) of formula IV. This reaction is carried out preferably by raising the temperature up to >=100 deg.C or using a catalyst such as a phenol.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organopolysiloxane and a method for producing the same, more specifically, an organopolysiloxane having at least one special amino group-containing organic group at a molecular chain terminal and / or a molecular chain side chain. And a manufacturing method thereof.

[0002]

2. Description of the Related Art Organopolysiloxanes having amino group-containing organic groups such as aminoalkyl groups and N- (aminoalkyl) -aminoalkyl groups at the molecular chain ends or molecular chain side chains are epoxy resins, phenol resins and polyimide resins. It is used as a physical property modifier for organic resins.
As such an organopolysiloxane, a dimethylpolysiloxane having an N- (3-aminopropyl) -3-aminopropyl group in a side chain of a molecular chain (Japanese Patent Publication No. 4-338).
No. 90) has been proposed, and as an organopolysiloxane having a special amino group-containing organic group, a disiloxane having 3-amino-2-hydroxypropenoxypropyl groups at both ends of the molecular chain (Japanese Patent Application Laid-open No. Sho 60-96). 64-1679
No. 3 publication) is proposed.

[0003]

However, at the end of the molecular chain and / or the side chain of the molecular chain, the general formula:

[Chemical 5] (In the formula, R ² is a divalent organic group containing a hydroxyl group, R ³ is a divalent organic group having an aromatic ring directly bonded to a nitrogen atom in the formula, and R ⁴ is a hydrogen atom or a monovalent hydrocarbon. It is a base.)
Organopolysiloxanes having an amino group-containing organic group represented by are not known.

The present inventor has arrived at the present invention as a result of earnest research for solving the above problems.

That is, the object of the present invention is to provide at least one general formula at the chain end and / or side chain:

[Chemical 6] (In the formula, R ² is a divalent organic group containing a hydroxyl group, R ³ is a divalent organic group having an aromatic ring directly bonded to a nitrogen atom in the formula, and R ⁴ is a hydrogen atom or a monovalent hydrocarbon. It is a base.)
An organopolysiloxane having a special amino group-containing organic group represented by and a method for producing the same.

[0006]

The present invention has the general formula:

[Chemical 7] [Wherein R ¹ is the same or different monovalent hydrocarbon group, and A is a monovalent hydrocarbon group, a hydroxyl group, an epoxy group-containing organic group and the general formula:

[Chemical 8] (In the formula, R ² is a divalent organic group containing a hydroxyl group, R ³ is a divalent organic group having an aromatic ring directly bonded to a nitrogen atom in the formula, and R ⁴ is a hydrogen atom or a monovalent hydrocarbon. It is a base.)
Is a group selected from the group consisting of amino group-containing organic groups represented by, provided that at least one of A in the molecule is the amino group-containing organic group, and m is 0 or a positive number, n is 0 or a positive number. ] An organopolysiloxane represented by the following formula, and (A) a general formula:

[Chemical 9] (In the formula, R ¹ is the same or different monovalent hydrocarbon group, B is a group selected from the group consisting of a monovalent hydrocarbon group, a hydroxyl group and an epoxy group-containing organic group, provided that, in the molecule, And at least one of B is the epoxy group-containing organic group, m is 0 or a positive number, and n is 0 or a positive number. formula:

[Chemical 10] (In the formula, R ³ is a divalent organic group having an aromatic ring directly bonded to the nitrogen atom in the formula, and R ⁴ is a hydrogen atom or a monovalent hydrocarbon group.) The present invention relates to a method for producing an organopolysiloxane characterized by reacting.

First, the organopolysiloxane of the present invention will be described in detail.

The organopolysiloxane of the present invention has the general formula:

[Chemical 11] Indicated by. In the above formula, R ¹ is the same or different monovalent hydrocarbon group. Specific examples of the monovalent hydrocarbon group for R ¹ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group. Group; aryl group such as phenyl group, tolyl group, xylyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aralkyl group such as benzyl group, phenethyl group; 3, 3, 3
-A substituted alkyl group such as a trifluoropropyl group is exemplified.

In the above formula, A is a monovalent hydrocarbon group, a hydroxyl group, an epoxy group-containing organic group and a general formula:

[Chemical 12] Is a group selected from the group consisting of an amino group-containing organic group, provided that at least one of A in the molecule is the amino group-containing organic group. Specific examples of the monovalent hydrocarbon group of A include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group; aryl groups such as phenyl group, tolyl group and xylyl group; vinyl group, allyl group ，
Alkenyl groups such as butenyl, pentenyl and hexenyl groups; aralkyl groups such as benzyl and phenethyl groups;
Substituted alkyl groups such as 3,3,3-trifluoropropyl group are exemplified. As the epoxy group-containing organic group of A, specifically, 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2- (3,4-
Examples thereof include epoxycyclohexyl) ethyl group and 2,3-epoxypropyl group. The amino group-containing organic group of A has the general formula:

[Chemical 13] Indicated by. In the above formula, R ² is a hydroxyl group-containing divalent organic group, and the hydroxyl group-containing divalent organic group of R ² is specifically 3
-(2-hydroxypropyleneoxy) propylene group,
A 2- (3-hydroxycyclohexanylene) ethylene group and a 2-hydroxypropylene group are exemplified, and a 3- (2-hydroxypropyleneoxy) propylene group is preferable. Further, in the above formula, R ³ is a divalent organic group having an aromatic ring directly bonded to the nitrogen atom in the formula, and specific examples of the divalent organic group of R ³ include phenylene group, biphenylene group and naphthylene. Group, xylylene group, formula:

[Chemical 14] Or expression:

[Chemical 15] Examples of the divalent organic group represented by are preferably phenylene group, formula:

[Chemical 16] And expression:

[Chemical 17] Is a divalent organic group represented by. Further, in the above formula, R ⁴ is a hydrogen atom or a monovalent hydrocarbon group, and specific examples of the monovalent hydrocarbon group of R ⁴ include methyl group, ethyl group, propyl group, butyl group, pentyl group and the like. Alkyl group; aryl group such as phenyl group, tolyl group, xylyl group; vinyl group,
Aralkyl groups such as benzyl groups and phenethyl groups; allyl, butenyl, pentenyl group and hexenyl group a substituted alkyl group such as a 3,3,3-trifluoropropyl group are exemplified, preferably as R ⁴ It is a hydrogen atom. Specifically, such an amino group-containing organic group has the formula:

[Chemical 18] Or expression:

[Chemical 19] ,formula:

[Chemical 20] Or expression:

[Chemical 21] ,formula:

[Chemical formula 22] Or expression:

[Chemical formula 23] ,formula:

[Chemical formula 24] Or expression:

[Chemical 25] ,formula:

[Chemical formula 26] And expression:

[Chemical 27] The amino group-containing organic group represented by is exemplified.

In the organopolysiloxane of the present invention, in the formula, m is 0 or a positive number, and n is 0 or a positive number. The upper limit of these is not particularly limited, but the organopolysiloxane of the present invention is The molecular weight of the organic resin is preferably in the range of 1,000 to 1,000,000 for use as a modifier for physical and chemical properties of the organic resin.

Next, the manufacturing method of the present invention will be described in detail.

The production method of the present invention comprises (A) the general formula:

[Chemical 28] (In the formula, R ¹ is the same or different monovalent hydrocarbon group, B is a group selected from the group consisting of a monovalent hydrocarbon group, a hydroxyl group and an epoxy group-containing organic group, provided that, in the molecule, At least one of B is an epoxy group-containing organic group, m is 0 or a positive number, and n is 0 or a positive number), and (B) a general formula (B). :

[Chemical 29] (In the formula, R ³ is a divalent organic group having an aromatic ring directly bonded to the nitrogen atom in the formula, and R ⁴ is a hydrogen atom or a monovalent hydrocarbon group.) Characterized by reacting.

The component (A) is a main raw material in the production method of the present invention and has the general formula:

[Chemical 30] Is an organopolysiloxane represented by. In the above formula, R
¹ is the same or different monovalent hydrocarbon group, and the monovalent hydrocarbon group of R ¹ is specifically a methyl group, an ethyl group,
Alkyl group such as propyl group, butyl group, pentyl group; aryl group such as phenyl group, tolyl group, xylyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; benzyl group, phenethyl group Aralkyl groups such as; and substituted alkyl groups such as 3,3,3-trifluoropropyl group. Further, in the above formula, B is a group selected from the group consisting of a monovalent hydrocarbon group, a hydroxyl group and an epoxy-containing organic group, provided that at least one in the molecule is the epoxy group-containing organic group. Specific examples of the monovalent hydrocarbon group of B include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and pentyl group; aryl groups such as phenyl group, tolyl group and xylyl group; vinyl group,
Examples thereof include alkenyl groups such as allyl group, butenyl group, pentenyl group and hexenyl group; aralkyl groups such as benzyl group and phenethyl group; and substituted alkyl groups such as 3,3,3-trifluoropropyl group. Specific examples of the epoxy-containing organic group of B include 2-glycidoxyethyl group, 3-glycidoxypropyl group, 4-glycidoxybutyl group, 2-
(3,4-epoxycyclohexyl) ethyl group, 2,3
-Epoxypropyl groups are exemplified.

In the formula of the component (A), m is 0 or a positive number, and n is 0 or a positive number, and the upper limits thereof are not particularly limited, but the organopolypolyamide obtained by the production method of the present invention is not limited. In order to use siloxane as a modifier of physical and chemical properties of organic resin, its molecular weight is 1,
It is preferably in the range of 000 to 1,000,000.

In the production method of the present invention, the method for preparing the component (A) is not particularly limited. Specifically, as the method for producing the component (A), a silicon atom bond is formed at the molecular chain terminal and / or the molecular chain side chain. Method of addition reaction of an organopolysiloxane having a hydrogen atom with an epoxy group and a compound having an aliphatic unsaturated hydrocarbon bond in the presence of a catalyst for hydrosilylation reaction, and an aliphatic group at a molecular chain terminal and / or a side chain of a molecular chain Method for oxidizing organopolysiloxane having unsaturated hydrocarbon group in the presence of peroxide, hydrosilylation reaction of alkoxysilane having silicon atom-bonded hydrogen atom, epoxy group and compound having aliphatic unsaturated hydrocarbon bond After the addition reaction in the presence of a catalyst for use, the resulting alkoxysilane is hydrolyzed, and the epoxy group-containing organosiloxy obtained by the above method Emissions or a method of polymerizing an organopolysiloxane and cyclic siloxane in the presence of a basic catalyst or an acidic catalyst is exemplified. The organopolysiloxane of component (A) obtained by polymerizing an epoxy group-containing organosiloxane or organopolysiloxane and a cyclic siloxane in the presence of a basic catalyst or an acidic catalyst has some hydroxyl groups. However, if this hydroxyl group inhibits the reaction between the component (A) and the component (B), or significantly reduces the storage stability of the obtained organopolysiloxane of the present invention, the hydroxyl group is triorganochlorosilane. Or hexaorganodisilazane or the like.

The component (B) is used in the production method of the present invention.
Component (A) is a component for introducing a special amino group-containing organic group into the resulting organopolysiloxane by reacting with the epoxy group-containing organic group, and has the general formula:

[Chemical 31] Is a diamine compound represented by. In the above formula, R ³ is a divalent organic group having an aromatic ring directly bonded to the nitrogen atom in the formula, and specific examples of the divalent organic group of R ³ include a phenylene group, a biphenylene group, a naphthylene group, A xylylene group,
formula:

[Chemical 32] ,formula:

[Chemical 33] The divalent organic group represented by is exemplified. Also, in the above formula, R
⁴ is a hydrogen atom or a monovalent hydrocarbon group, and specific examples of the monovalent hydrocarbon group of R ⁴ include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group; a phenyl group and a tolyl group. Group, aryl group such as xylyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group; aralkyl group such as benzyl group, phenethyl group; 3,3,3-trifluoropropyl group, etc. Substituted alkyl groups are exemplified, and R ⁴ is preferably a hydrogen atom.

Specific examples of the diamine compound as the component (B) include 4,4'-diaminodiphenyl sulfone, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylamine and 4,4'-diamino. Diphenyl ether, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,3-diaminonaphthalene, 1,2-diamino-4-nitrobenzene, 4,4′-diaminobiphenyl, 2,4-diaminophenol, m- Phenylenediamine, o-phenylenediamine, p-phenylenediamine, 3,3'-dimethylnaphthidine, N, N-dimethyl-p-phenylenediamine, N, N'-dimethyl-6
-(Methylthio) -1,3,5-triazine-2,4-
Diamine, p-aminobenzenesulfonamide, 3,
3 ', 5,5'-tetramethylbenzidine, 6-chloro-N- (1,1-dimethylethyl) -N'-ethyl-
1,3,5-triazine-2,4-diamine, N-
(1,1-Dimethylethyl) -N'-ethyl-6- (methylthio) -1,3,5-triazine-2,4-diamine, N- (1,1-dimethylethyl) -N'-ethyl-
6-methoxy-1,3,5-triazine-2,4-diamine, 6-chloro-N, N, N'-triethyl-1,
3,5-triazine-2,4-diamine, 4-nitro-
Examples thereof include o-phenylenediamine, 4,4′-methylenedianiline, 2,2-diaminophenylpropane, 3,6-diaminoacridine and 4,4′-bis (dimethylamino) benzophenone, which are particularly easily available. Further, since they are relatively safe to handle, 4,4'-methylenedianiline and 4,4'-diaminodiphenylsulfone are preferred.

In the production method of the present invention, the blending amount of the component (B) is not particularly limited, but the component (B) is added to one epoxy group-containing organic group in the epoxy group-containing organopolysiloxane of the component (A). The content is preferably 1.5 times or more, and more preferably 2.0 times or more. This is because the content of the component (B) is less than 1.5 times the molar amount of the epoxy group-containing organic group in the epoxy group-containing organopolysiloxane of the component (A). This is because a part thereof acts as a cross-linking agent for the component (A), which may cause a problem that the obtained organopolysiloxane is significantly thickened or gelled.

In the production method of the present invention, the reaction temperature of the epoxy group-containing organopolysiloxane of the component (A) and the diamine compound of the component (B) is not particularly limited, but the reaction temperature is 100 ° C. or less and no catalyst is used. Since the reaction proceeds slowly, it is preferable that the reaction temperature is 100 ° C. or higher, or that a reaction catalyst such as phenols is used. Also,
The reaction atmosphere is not particularly limited, but when heating, it is preferable to carry out the reaction under reduced pressure or in an inert gas atmosphere.

In the method for producing the organopolysiloxane of the present invention, an organic solvent can be used. This is because, among the components (B), some diamine compounds are solid at room temperature, and when the compatibility with the epoxy group-containing organopolysiloxane of the components (A) is poor, the components (B) are previously prepared. It is preferable to use the diamine compound of 1) by dissolving it in an organic solvent. The organic solvent that can be used is not particularly limited as long as it does not inhibit the reaction between the epoxy group in the component (A) and the amino group in the component (B), and specific examples of such an organic solvent include toluene. , Aromatic solvents such as xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as hexane, heptane, octane; ether solvents such as diphenyl ether, diisopropyl ether; methyl benzoate,
An ester solvent such as ethyl acetate is exemplified.

In the production method of the present invention, when it is necessary to remove the excess diamino compound of the component (B) after the production, a method of crystallizing the component (B) and filtering it out or a method such as solvent extraction is used. Can be removed.

Since the organopolysiloxane of the present invention is a novel organopolysiloxane having a special amino group-containing organic group at the molecular chain terminal and / or the side chain of the molecular chain, the organopolysiloxane of the present invention is an epoxy resin. The physical and chemical properties of organic resins such as phenol resin, phenol-novolac resin, aniline resin, xylene resin, and acrylic resin are improved to make the organic resin lubricity, heat resistance, flame retardancy, water repellency, and water repellency. It can be used as a modifier to impart flexibility.

[0023]

EXAMPLES The present invention will be described in detail with reference to Examples. In the examples, the viscosity value is a value measured at 25 ° C.

[0024]

Example 1 A 500 ml four-necked flask equipped with a stirrer and a thermometer was charged with 300 g of the formula:

[Chemical 34] The dimethylsiloxane / methylphenylsiloxane copolymer represented by and 57 g of 4,4′-methylenedianiline (also called diaminodiphenylmethane) were added, and the mixture was heated with stirring at 150 ° C. for 2 hours under a nitrogen atmosphere. Then, it cooled, the unreacted 4,4'- methylene dianiline was crystallized and filtered. The obtained product was analyzed by infrared spectroscopy, ¹³ C-
As a result of nuclear magnetic resonance spectrum analysis (hereinafter referred to as NMR) and elemental analysis, it was found to be a dimethylsiloxane / methylphenylsiloxane copolymer represented by the following structural formula. Although this copolymer was not compatible with the epoxy resin as it was, it was possible to obtain a uniform resin at room temperature by heating and stirring this copolymer with the epoxy resin at 150 ° C. for 6 hours.

[0025]

[Chemical 35]

[0026]

Example 2 A 500 ml four-necked flask equipped with a stirrer and a thermometer was charged with 300 g of the formula:

[Chemical 36] The dimethylsiloxane / methylphenylsiloxane copolymer represented by and 73 g of 4,4′-diaminodiphenylsulfone were added, and the mixture was heated and stirred at 190 ° C. for 12 hours under a reduced pressure of 2 mmHg. Then, it cooled, the unreacted 4,4'- diamino diphenyl sulfone was crystallized and filtered. The obtained product was analyzed by infrared spectroscopy, ¹³ C-NMR and elemental analysis, and as a result, about 20% of all 3-glycidoxypropyl groups in the molecule reacted with 4,4′-diaminodiphenyl sulfone. It was confirmed that the mixture was a mixture containing a dityl siloxane / methylphenyl siloxane copolymer represented by the following structural formula. Although this copolymer was not compatible with the epoxy resin as it was, it was possible to obtain a uniform resin at room temperature by heating and stirring this copolymer with the epoxy resin at 150 ° C. for 6 hours.

[0027]

[Chemical 37]

[0028]

Example 3 In a 500 ml four-necked flask equipped with a stirrer and a thermometer, 300 g of the formula:

[Chemical 38] And a dimethylsiloxane / methylphenylsiloxane / methyl (3-glycidoxypropyl) siloxane copolymer whose both molecular chain ends are capped with trimethylsiloxy groups and 56 g of 4,4′-methylenedianiline (other name:
Diaminodiphenylmethane) was added, and the pressure was reduced to 2 mmHg.
The mixture was heated and stirred at 160 ° C for 6 hours. Then, it cooled, the unreacted 4,4'- methylene dianiline was crystallized and filtered. As a result of analyzing the obtained product by infrared spectroscopy, ¹³ C-NMR and elemental analysis, it was confirmed that the product was an organopolysiloxane copolymer having the following structural formula. Although this copolymer was not compatible with the epoxy resin as it was, it was not compatible with the epoxy resin.
By heating and stirring at 50 ° C. for 6 hours, a uniform resin could be obtained at room temperature.

[0029]

[Chemical Formula 39]

[0030]

INDUSTRIAL APPLICABILITY The organopolysiloxane of the present invention is a novel organopolysiloxane having a special amino group-containing organic group at the molecular chain end and / or the molecular chain side chain, and the production method of the present invention is as follows. The novel organopolysiloxane can be produced.

[Brief description of drawings]

FIG. 1 is an infrared spectrum chart of the dimethylsiloxane / methylphenylsiloxane copolymer prepared in Example 1.

2 is a ¹³ C-nuclear magnetic resonance spectrum chart of the dimethylsiloxane / methylphenylsiloxane copolymer prepared in Example 1. FIG.

3 is an infrared spectrum chart of the dimethylsiloxane-methylphenylsiloxane copolymer prepared in Example 2. FIG.

4 is a ¹³ C-nuclear magnetic resonance spectrum chart of the dimethylsiloxane / methylphenylsiloxane copolymer prepared in Example 2. FIG.

Claims (2)

[Claims] 1. A general formula: [Wherein R ¹ is the same or different monovalent hydrocarbon group, A is a monovalent hydrocarbon group, a hydroxyl group, an epoxy group-containing organic group and the general formula: (In the formula, R ² is a divalent organic group containing a hydroxyl group, R ³ is a divalent organic group having an aromatic ring directly bonded to a nitrogen atom in the formula, and R ⁴ is a hydrogen atom or a monovalent hydrocarbon. It is a base.)
Is a group selected from the group consisting of amino group-containing organic groups represented by, provided that at least one of A in the molecule is the amino group-containing organic group, and m is 0 or a positive number, n is 0 or a positive number. ] The organopolysiloxane shown by these. 2. (A) General formula: (In the formula, R ¹ is the same or different monovalent hydrocarbon group, B is a group selected from the group consisting of a monovalent hydrocarbon group, a hydroxyl group and an epoxy group-containing organic group, provided that, in the molecule, And at least one of B is the epoxy group-containing organic group, m is 0 or a positive number, and n is 0 or a positive number. Formula: (In the formula, R ³ is a divalent organic group having an aromatic ring directly bonded to the nitrogen atom in the formula, and R ⁴ is a hydrogen atom or a monovalent hydrocarbon group.) The method for producing an organopolysiloxane according to claim 1, wherein the organopolysiloxane is reacted.