JPH10204180A - Polyorganosiloxane and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new polyorganosiloxane having a hindered phenol group bonded to a molecular terminal or a side chain through an amide group and being desirable as an additive for modifying lubricants and resins. SOLUTION: This polyorganosiloxane is represented by formula I [wherein R is a monovalent hydrocarbon group; X is formula II (R<1> to R<4> are each a 1-6C alkyl or H, provided that at least either of R<1> and R<2> is an alkyl; R<5> , R<7> and R<8> are each a 2-10C alkylene; R<6> is a 1-10C hydrocarbon group or H; and z is 0-50) or a hydrocarbon group; and m and n are each 0-500]. This is obtained by condensing a polyorganosiloxane represented by formula III [Y is an amino represented by the formula: -R<8> -(NR<6> -R<7> )z -NHR6 or a monovalent hydrocarbon group] with a phenol-group-containing carboxylic acid (derivative) represented by formula IV (R<9> is hydroxyl, an alkoxyl or a halogen) [e.g. 3-(3'-5'-t-butylhydroxyphenyl)propionic acid].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel polyorganosiloxane and a method for producing the same, and more particularly, to a novel polyorganosiloxane having a hindered phenol group at an end of a molecular chain or a side chain via an amide group and a method for producing the same. About the method.

[0002]

2. Description of the Related Art A polyorganosiloxane having a hindered phenol group having a sterically hindered group bonded thereto has the following formula:

Embedded image Polyorganosiloxane represented by the formula (JP-B-47-39)
No. 22), the formula:

Embedded image Polyorganosiloxane (JP-A-4-247)
No. 091) is known (Other Japanese Patent Publication No.
No. 42472). However, these polyorganosiloxanes have a hindered phenol group via an alkylene group, and a polyorganosiloxane having a hindered phenol group via an amide group has not been known.

[0003]

The present inventors have made intensive studies and arrived at the present invention. That is, the object of the present invention is to
It is an object of the present invention to provide a novel polyorganosiloxane having a hindered phenol group at the molecular chain terminal or side chain via an amide group, and a method for producing the same.

[0004]

The present invention provides a compound represented by the general formula:

Embedded image Wherein R is a substituted or unsubstituted monovalent hydrocarbon group, and X is of the formula:

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group. R ⁵ , R ⁷ and R ⁸ are an alkylene group having 2 to 10 carbon atoms, R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and z is an integer of 0 to 10. ) Or a substituted or unsubstituted monovalent hydrocarbon group, at least one of which is the above-mentioned phenol group. m and n are integers of 0 to 500. A polyorganosiloxane represented by｝, and (A) a general formula:

Embedded image In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, and Y is a formula: —R ⁸ — (NR ⁶ —R ⁷ ) _z —NHR ⁶ (wherein, R ⁶ has 1 to 1 carbon atoms) 10 is a monovalent hydrocarbon group or a hydrogen atom, R ⁷ and R ⁸ are an alkylene group having 2 to 10 carbon atoms, and z is an integer of 0 to 10.) Alternatively, it is an unsubstituted monovalent hydrocarbon group, at least one of which is the above-mentioned amino group. m and n are integers of 0 to 500. And a polyorganosiloxane represented by the general formula (B):

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group. R ⁵ Is an alkylene group having 2 to 10 carbon atoms, and R ⁹ is a group selected from the group consisting of a hydroxyl group, an alkoxy group and a halogen atom.) The present invention relates to a method for producing the above-mentioned polyorganosiloxane, characterized by reacting.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The polyorganosiloxane of the present invention has the general formula:

Embedded image Indicated by In the above formula, R is a substituted or unsubstituted monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; a phenyl group and a tolyl group Aryl groups such as benzyl, xylyl and the like; aralkyl groups such as benzyl and phenethyl;
Halogenated alkyl groups such as 3,3-trifluoropropyl group; and alkenyl groups such as vinyl group, propenyl group, butenyl group and hexenyl group. X is the formula:

Embedded image Or a substituted or unsubstituted monovalent hydrocarbon group, at least one of which must be the above-mentioned phenol group. Examples of the substituted or unsubstituted monovalent hydrocarbon group include the same groups as those described above for R. In the phenol group, R ¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group. is there. Specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
t-butyl groups, among which the formula: -C (R
¹⁰ ) ₃ (wherein, R ¹⁰ is an alkyl group having 1 to 3 carbon atoms), and particularly preferably a t-butyl group. R ⁵ , R ⁷ and R ⁸ are an alkylene group having 2 to 10 carbon atoms, examples of which include an ethylene group, a propylene group and a butylene group. R ⁶ is a monovalent hydrocarbon group or a hydrogen atom having 1 to 10 carbon atoms. Specific examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, and a propyl group; Groups. z is an integer of 0 to 10. m and n are integers of 0 to 500. For example, when n is 0, it is necessary that at least one of X bonded to the molecular chain terminal is the above-mentioned phenol group.

Examples of the polyorganosiloxane of the present invention include compounds represented by the following formula.

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The polyorganosiloxane of the present invention is, for example, a compound represented by the following general formula (A):

Embedded image And (B) a general formula:

Embedded image Can be produced by subjecting a phenol group-containing carboxylic acid represented by or a derivative thereof to a condensation reaction.

The polyorganosiloxane of the component (A) used in this production method is represented by the above general formula,
R is a substituted or unsubstituted monovalent hydrocarbon group, specifically, a methyl group, an ethyl group, a propyl group, a butyl group,
Alkyl groups such as pentyl group and hexyl; aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as benzyl group and phenethyl group; halogenated alkyl groups such as 3,3,3-trifluoropropyl group; vinyl And alkenyl groups such as a propenyl group, a butenyl group and a hexenyl group. Y is a formula: —R ⁸ — (NR ⁶ —R ⁷ ) _z —NHR
⁶ (wherein, R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R ⁷ and R ⁸ are each a group having 2 to 1 carbon atoms.
It is an alkylene group of 0, and z is an integer of 0-10. )) Or a substituted or unsubstituted monovalent hydrocarbon group, at least one of which must be the amino group. Specific examples of the monovalent hydrocarbon group for R ⁶ include an alkyl group such as a methyl group, an ethyl group, and a propyl group; and an aryl group such as a phenyl group. Examples of R ⁷ and R ⁸ include an ethylene group, a propylene group, and a butylene group. m and n are from 0 to 500
Is an integer.

The phenol group-containing carboxylic acid (B) or a derivative thereof is represented by the above general formula. In the above formula, R
¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group as described above. R ⁵ is an alkylene group having 2 to 10 carbon atoms, and specifically,
Examples include an ethylene group, a propylene group, and a butylene group.
R ⁹ is a group selected from the group consisting of a hydroxyl group, an alkoxy group and a halogen atom. The alkoxy group preferably has 6 or less carbon atoms, and the halogen atom is exemplified by chlorine, bromine and iodine. Among these, a phenol group-containing carboxylic acid in which R ⁹ is a hydroxyl group or a phenol group-containing carboxylic acid halide in which R ⁹ is a halogen atom is preferred. Such a phenol group-containing carboxylic acid can be produced by hydrolyzing a phenol group-containing carboxylic acid ester in which R ⁹ is an alkoxy group. Can be obtained.

In the production method of the present invention, a catalyst for a condensation reaction can be used as required. Specific examples include an acidic catalyst such as toluenesulfonic acid and a basic catalyst such as NaH (sodium hydride). Can be This condensation reaction is usually performed under heating.

The above-mentioned polyorganosiloxane of the present invention has excellent oxidation stability and is suitably used as a lubricant or a resin modifying additive.

[0012]

Next, the present invention will be described in detail with reference to examples. In addition, the viscosity in an Example is a value measured at 25 degreeC.

[0013]

Example 1 A 0.5-liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen stream was charged with 3-
29.8 g of methyl (3 ', 5'-di-t-butylhydroxyphenyl) propionate, 80 ml of ethanol and 6 g of sodium hydroxide were added thereto, and the mixture was stirred for 1 hour under heating and reflux conditions. After completion of the stirring, ethanol was distilled off, and concentrated hydrochloric acid was gradually added to neutralize the mixture. Next, 150 ml of a 1: 1 mixture of toluene and ethyl acetate was added, and the mixture was washed twice with water.
The solvent is distilled off from the organic layer thus washed, and 3
27.2 g of crystals of-(3 ', 5'-di-t-butylhydroxyphenyl) propionic acid were obtained. Next, under a nitrogen stream, a 0.2-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer was added with the formula:

Embedded image 25 g of polydimethylsiloxane having aminopropyl groups at both ends represented by the formula, 50 ml of xylene and 3- (3 ', 5'-di-t-butylhydroxyphenyl) obtained above
3.0 g of propionic acid was added, and 2 g was added under azeotropic dehydration conditions.
The mixture was stirred for an hour to react. After the completion of the reaction, the solvent was distilled off to obtain 27.6 g of a yellow-brown transparent viscous liquid. The viscosity of the resulting liquid was 2,100 centistokes. When this liquid was analyzed by IR spectrum and ¹³ C-NMR spectrum, 1650 cm ^-1 derived from the amide group was obtained.
And an absorption of 3650 cm ^-1 derived from a phenol group were confirmed. From these analysis results, it was found that the obtained liquid was a polyorganosiloxane having the following structural formula.

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[0014]

Example 2 In a nitrogen stream, a 0.3 liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer was charged with a compound represented by the formula

Embedded image Polydimethylsiloxane (NH ₂ content: 0.745%) having an aminopropyl group in the side chain represented were obtained by 25g of xylene 50ml Example 1 3- (3 ', 5'-di -
t-butylhydroxyphenyl) propionic acid 4.0 g
Was added, and the mixture was stirred and reacted under azeotropic dehydration conditions for 2 hours. After completion of the reaction, the solvent was distilled off to obtain 9.2 g of a yellow-brown transparent viscous liquid. The viscosity of the resulting liquid was 200,000 centistokes. When this liquid was analyzed by IR spectrum and ¹³ C-NMR spectrum, it was found to be a polyorganosiloxane having the following structural formula.

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[0015]

The polyorganosiloxane of the present invention is a novel compound having a hindered phenol group at the molecular chain terminal or side chain via an amide group, and the production method of the present invention provides a method for producing the polyorganosiloxane with high productivity. It has the feature that it can be manufactured well.

[Brief description of the drawings]

FIG. 1 is an IR spectrum chart of the polyorganosiloxane produced in Example 1.

FIG. 2 is an IR spectrum chart of the polyorganosiloxane produced in Example 2.

Claims (4)

[Claims] 1. A compound of the general formula: In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, and X is a compound represented by the formula: (Wherein R ¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group. R ⁵ , R ⁷ and R ⁸ are an alkylene group having 2 to 10 carbon atoms, R ⁶ is a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and z is an integer of 0 to 10. ) Or a substituted or unsubstituted monovalent hydrocarbon group, at least one of which is the above-mentioned phenol group. m and n are integers of 0 to 500. Polyorganosiloxane represented by｝. ^{2. At} least one of R ¹ and R ² has the formula:
-C (R ¹⁰⁾ ₃ (wherein, R ¹⁰ is an alkyl group having 1 to 3 carbon atoms.) Is a group represented by the polyorganosiloxane according to claim 1, wherein. 3. At least one of R ¹ and R ² is t-
The polyorganosiloxane according to claim 1, which is a butyl group. (A) a general formula: In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group, and Y is a formula: —R ⁸ — (NR ⁶ —R ⁷ ) _z —NHR ⁶ (wherein, R ⁶ has 1 to 1 carbon atoms) 10 is a monovalent hydrocarbon group or a hydrogen atom, R ⁷ and R ⁸ are an alkylene group having 2 to 10 carbon atoms, and z is an integer of 0 to 10.) Alternatively, it is an unsubstituted monovalent hydrocarbon group, at least one of which is the above-mentioned amino group. m and n are integers of 0 to 500. A polyorganosiloxane represented by｝, and (B) a general formula: (Wherein R ¹ , R ² , R ³ and R ⁴ are an alkyl group having 1 to 6 carbon atoms or a hydrogen atom, and at least one of R ¹ and R ² is an alkyl group. R ⁵ Is an alkylene group having 2 to 10 carbon atoms, and R ⁹ is a group selected from the group consisting of a hydroxyl group, an alkoxy group and a halogen atom.) Characterized by reacting
A method for producing the polyorganosiloxane according to claim 1.