JPH10182829A - Method for producing organopolysiloxane - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing an organopolysiloxane having a narrow molecular weight distribution and having amino groups at both ends of a molecular chain. SOLUTION: A siloxane compound having a silicon atom-bonded hydrogen atom at a molecular chain terminal and a silicon atom-bonded halogen atom at another molecular chain terminal and an aliphatic unsaturated carbon-carbon bond-containing amine compound are dehydrohalogenated. A condensation reaction is carried out to prepare a siloxane compound in which a hydrogen atom is bonded to a silicon atom at the terminal of the molecular chain and an amino group containing an aliphatic unsaturated carbon-carbon bond is bonded to the silicon atom at the other terminal of the molecular chain. The compound is subjected to addition polymerization using a catalyst for hydrosilylation reaction to obtain a compound represented by the general formula: Preparing a silicon-containing polymer represented by the formula: and then hydrolyzing the silicon-containing polymer, characterized by the general formula: A method for producing an organopolysiloxane represented by the formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an organopolysiloxane, and more particularly, to a method for efficiently producing an organopolysiloxane having a narrow molecular weight distribution and having amino groups at both ends of a molecular chain.

[0002]

2. Description of the Related Art As a method for producing an organopolysiloxane having amino groups at both ends of a molecular chain, tetramethyldisiloxane having 3-aminopropyl at both ends of a molecular chain and octamethylcyclotetrasiloxane are prepared by using a basic catalyst. Equilibrium polymerization method (JP-A-58-10492)
6), a method of equilibrium polymerizing a mixture of a cyclic organopolysiloxane and a disiloxane having an aminoalkyl group at both molecular terminals with a basic catalyst in the presence of a cyclic polyether (JP-A-3-95227). In addition, a silicon-bonded hydrogen atom at one end of an aliphatic unsaturated carbon-carbon bond-containing amine compound and a siloxane compound having silicon-bonded hydrogen atoms at both ends of a molecular chain is treated with a platinum-based hydrosilylation reaction catalyst. A siloxane compound in which a hydrogen atom is bonded to a silicon atom at the end of a molecular chain through a dehydrocondensation reaction and an amino group containing an aliphatic unsaturated carbon-carbon bond is bonded to a silicon atom at the other end of the molecular chain. After the preparation, this siloxane compound is subjected to addition polymerization using a hydrosilylation reaction catalyst, so that the main skeleton has a siloxane bond and a silazane. To produce a silicon-containing polymer and a case and silalkylene bond, then the silicon-containing polymer The method for hydrolyzing is known (see Japanese Patent Laid-Open No. 2-49793).

However, Japanese Patent Application Laid-Open No. 58-104926
In the production method proposed in Japanese Patent Application Laid-Open No. HEI 5-95227 and Japanese Patent Application Laid-Open No. 3-95227, a reaction must be carried out at a high temperature for a long time in order to cleave bis (3-aminopropyl) tetramethyldisiloxane. Due to the reaction, there is a problem that the molecular weight distribution of the obtained organopolysiloxane is widened. On the other hand, JP-A-2-4979
In the production method proposed by the publication No. 3, a hydrogen atom is bonded to a silicon atom at a molecular chain terminal, and an aliphatic unsaturated carbon-carbon bond-containing amino group is bonded to a silicon atom at the other molecular chain terminal. When preparing a siloxane compound,
This is dangerous because hydrogen gas is generated, and the silicon-bonded hydrogen atoms at the molecular chain terminals of the siloxane compound further undergo a dehydrocondensation reaction with the amine compound, so that the yield of the target siloxane compound is extremely high. And the yield of the amino group-containing organopolysiloxane is very low, which is not suitable for mass production.

[0004]

The inventor of the present invention has intensively studied to solve the above-mentioned problems, and has reached the present invention. That is, an object of the present invention is to provide a method for efficiently producing an organopolysiloxane having amino groups at both ends of a molecular chain having a narrow molecular weight distribution.

[0005]

The invention according to claim 1 of the present application has a general formula:

Embedded image (Wherein, R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, X is a halogen atom, and a is an integer of 1 or more). Siloxane compound and general formula:

Embedded image (Wherein, R ² is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom, and R ³ is a divalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. ,
R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. ) Is subjected to a dehydrohalogenation condensation reaction to give a general formula:

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , and a are the same as those described above), and the siloxane compound is subjected to addition polymerization with a hydrosilylation reaction catalyst. And the general formula:

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , and a are the same as above, and b is an integer of 1 or more). Wherein the silicon-containing polymer is hydrolyzed;

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and a are the same as those described above).

The invention according to claim 2 of the present application has a general formula:

Embedded image (Wherein, R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, X is a halogen atom, and a is an integer of 1 or more). The siloxane compound represented by the general formula:

Embedded image (Wherein, R ¹ is the same as described above, and n is an integer of 3 or more.) A cyclic siloxane compound represented by the general formula:

Embedded image (Wherein R ¹ and X are the same as described above), which is a compound obtained by a ring-opening reaction with a siloxane compound represented by the following formula: It relates to a manufacturing method.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The method for producing the organopolysiloxane of the present invention will be described in detail. In the production method of the present invention,
First, the general formula:

Embedded image A siloxane compound represented by the general formula:

Embedded image Is subjected to a dehydrohalogenation condensation reaction.

The above siloxane compound is a raw material for forming the skeleton of the target siloxane compound. R ¹ in the above formula is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. The monovalent hydrocarbon group of R ¹ is preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a phenyl group or a tolyl group. ,
An aryl group such as a xylyl group; an aralkyl group such as a benzyl group and a phenethyl group; and a halogenated alkyl group such as a 3,3,3-trifluoropropyl group. Further, R ¹ is preferably an alkyl group or a phenyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. Further, X in the above formula is a halogen atom, and is exemplified by a chlorine atom and a bromine atom, and is particularly preferably a chlorine atom. A in the above formula is an integer of 1 or more, preferably an integer in the range of 1 to 50, more preferably an integer in the range of 3 to 50, and particularly preferably 3 to 50. It is an integer in the range of 20.

The following compounds are exemplified as such siloxane compounds.

Embedded image

The method for preparing such a siloxane compound is not limited, but may be represented by the general formula:

Embedded image Wherein R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and n is an integer of 3 or more. formula:

Embedded image (Wherein, R ¹ is the same as described above, and X is a halogen atom.). R ¹ and X in the above formula are the same as described above. Further, n in the above formula is an integer of 3 or more, preferably an integer in the range of 3 to 10, more preferably an integer in the range of 3 to 6, and particularly preferably 3 is there. Examples of such a cyclic siloxane compound include hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, and in particular, hexamethylcyclotrisiloxane is preferable. Examples of such a silane compound include dimethylchlorosilane and methylphenylchlorosilane, and dimethylchlorosilane is particularly preferable. In this ring opening reaction, the amount of the silane compound added is preferably equal to or less than the molar amount of the cyclic siloxane compound.

The above amine compound is a raw material for introducing an aliphatic unsaturated carbon-carbon bond-containing amino group into a target siloxane compound. R ² in the above formula is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. As the monovalent hydrocarbon group for R ² ,
It is preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms, and examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group and a t-butyl group; and an aryl group such as a phenyl group and a tolyl group. Further, R ² is preferably an alkyl group or a hydrogen atom, particularly preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. R ³ in the above formula is a divalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. The divalent hydrocarbon group for R ³ is preferably a divalent hydrocarbon group having 1 to 50 carbon atoms, such as an alkylene group such as a methylene group, an ethylene group, a propylene group, or a butylene group; a phenylene group or a tolylene group. And an arylene group such as a xylylene group. Further, R ³ is preferably an alkylene group, particularly preferably an alkylene group having 1 to 4 carbon atoms. Also,
R ⁴ in the above formula is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. The monovalent hydrocarbon group of R ⁴ is preferably a monovalent hydrocarbon group having 1 to 50 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group, and a propyl group; a phenyl group, a tolyl group, and a xylyl group. And an aralkyl group such as a benzyl group and a phenethyl group. Further, R ⁴ is preferably an alkyl group or a hydrogen atom, particularly preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

The following compounds are exemplified as such amine compounds.

Embedded image

In the production method of the present invention, the siloxane compound and the amine compound are subjected to a dehydrohalogenation condensation reaction. In this condensation reaction, it is preferable to use the amine compound in an equimolar amount or more with respect to the siloxane compound. . Further, in this condensation reaction, it is preferable to add a hydrogen halide scavenger for trapping by-produced hydrogen halide. Examples of the hydrogen halide scavenger include triethylamine, pyridine, diethylamine, ethylamine, and N, N-dimethylaminopyrudine. The use of an organic solvent in this condensation reaction is optional. The organic solvent that can be used is not limited as long as it is inert to the above-mentioned raw materials, but a solvent having low solubility of the generated salt is desirable, and n-hexane and n-hexane are preferable.
Heptane, toluene, xylene and the like are preferred. The temperature of the condensation reaction is not limited, but is preferably in the range of 0 ° C to 60 ° C.

The siloxane compound obtained by such a dehydrohalogenation condensation reaction has a general formula:

Embedded image Wherein R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ² is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. R ³ is a divalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. And a is an integer of 1 or more.)
R ¹ , R ² , R ³ , R ⁴ and a in the above formula are the same as described above.

The following compounds are exemplified as such siloxane compounds.

Embedded image

Embedded image

Next, in the production method of the present invention, the above-mentioned siloxane compound is subjected to addition polymerization using a hydrosilylation reaction catalyst. Examples of the hydrosilylation reaction catalyst for addition polymerization of the siloxane compound include a platinum catalyst, a rhodium catalyst, and a palladium catalyst.
In particular, the catalyst for hydrosilylation reaction is preferably a platinum-based catalyst because of its good reactivity. Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, and a carbonyl complex of platinum. The amount of the catalyst for the hydrosilylation reaction is sufficient to promote the addition polymerization of the siloxane compound. When a platinum-based catalyst is used as the catalyst, 1,000,000 parts by weight of the siloxane compound is used. For
It is preferable that the amount of platinum metal in the catalyst is in the range of 2 to 100 parts by weight. This is because if the amount of the catalyst is less than this range, the above addition polymerization tends not to proceed sufficiently, while if it exceeds this range, a side reaction is likely to occur.

In this addition polymerization, the reaction temperature is not limited, but is preferably in the range of 50 to 220 ° C., particularly preferably in the range of 100 to 180 ° C. This addition polymerization may be performed in an organic solvent. As an organic solvent that can be used, any solvent that does not inhibit the addition polymerization may be used, and toluene, xylene and the like are preferable.

The silicon-containing polymer obtained by such addition polymerization has a general formula:

Embedded image Wherein R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ² is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. R ³ is a divalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. And a is an integer of 1 or more, and b is an integer of 1 or more.) R ¹ , R ² , R ³ in the above formula,
R ⁴ and a are the same as described above. Also, b in the above equation
Is an integer of 1 or more, preferably an integer in the range of 1 to 1000, and particularly preferably an integer in the range of 1 to 500.

Examples of such a silicon-containing polymer include a silicon-containing polymer having a linear molecular structure, a silicon-containing polymer having a cyclic molecular structure, and a mixture of polymers having these molecular structures. Is exemplified. The silicon-containing polymer having a linear molecular structure has, for example, the general formula:

Embedded image Wherein R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ² is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. R ³ is a divalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. And a is an integer of 1 or more, and b is an integer of 1 or more.) R ¹ , R ² , R ³ in the above formula,
R ⁴ , a and b are the same as described above. Examples of the silicon-containing polymer having such a linear molecular structure include the following polymers. Note that b in the formula is an integer of 1 or more.

Embedded image

Embedded image

Examples of the silicon-containing polymer having a cyclic molecular structure include the following polymers. In addition,
B in the formula is an integer of 1 or more.

Embedded image

The production method of the present invention is characterized in that the silicon-containing polymer thus prepared is hydrolyzed to prepare an organopolysiloxane having amino groups at both molecular chain terminals. The water for hydrolyzing the silicon-containing polymer may be an amount sufficient to hydrolyze the above-mentioned silicon-containing polymer, and is usually 1 mol per 1 mol of the above-mentioned silicon-containing polymer. It is preferable that the amount exceeds this. The temperature of this hydrolysis is not limited, but is preferably in the range of 0 to 150 ° C. It is preferable to add a small amount of an alkali metal hydroxide in order to promote this hydrolysis. In hydrolyzing the silicon-containing polymer, a polymer obtained by dissolving the polymer in an organic solvent such as xylene or toluene may be used.

The organopolysiloxane prepared by the production method of the present invention has a general formula:

Embedded image Wherein R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ² is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. R ³ is a divalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, and R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. And a is an integer of 1 or more.)
R ¹ , R ² , R ³ , R ⁴ and a in the above formula are the same as described above. Examples of such an organopolysiloxane include the following organopolysiloxanes.

Embedded image The organopolysiloxane prepared as described above has a feature of a narrow molecular weight distribution, and thus can be used as a modifier for an organic resin.

[0023]

EXAMPLES The method for producing the organopolysiloxane of the present invention will be described in detail with reference to examples.

REFERENCE EXAMPLE 1 In a nitrogen atmosphere, 222.5 hexamethylcyclotrisiloxane was placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer.
g, 94.6 g of dimethylchlorosilane, 6.7 g of dimethylformamide, and 67 g of acetonitrile, and the mixture was stirred at room temperature for 1 hour. After the completion of the reaction, low-boiling substances are distilled off.
formula:

Embedded image The siloxane compound represented by was prepared.

Next, under a nitrogen atmosphere, 102.8 g of allylamine and 100 ml of hexane were placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer.
00 ml of the solution was added dropwise over 20 minutes. After stirring at room temperature for 1 hour, the generated salt was filtered using a glass filter. After distilling off low-boiling substances from the filtrate, the mixture is further distilled under reduced pressure to give 73-78 ° C / 4
As a fraction of mmHg, the formula:

Embedded image Was prepared.

REFERENCE EXAMPLE 2 Under a nitrogen atmosphere, 222.5 hexamethylcyclotrisiloxane was placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer.
g, 47.3 g of dimethylchlorosilane, 6.1 g of dimethylformamide and 61 g of acetonitrile, and the mixture was stirred at room temperature for 10 hours. After the completion of the reaction, low-boiling substances are distilled off.
formula:

Embedded image The siloxane compound represented by was prepared.

Next, under a nitrogen atmosphere, 52 g of allylamine and 100 ml of hexane were placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer.
The total amount of the above siloxane compound and hexane 100m
of solution was added dropwise over 20 minutes. After stirring at room temperature for 1 hour, the generated salt was filtered using a glass filter. After distilling off low-boiling substances from the filtrate, the mixture was further distilled under reduced pressure to give 125 to 130 ° C./1 mm
As the Hg fraction, the formula:

Embedded image 45 g of a silicon-containing compound represented by the formula was prepared.

REFERENCE EXAMPLE 3 In a nitrogen atmosphere, 222.5 hexamethylcyclotrisiloxane was placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer.
g, 157 g of methylphenylchlorosilane, 6.7 g of dimethylformamide, and 67 g of acetonitrile, and the mixture was stirred at room temperature for 3 hours. After the completion of the reaction, low-boiling substances are distilled off to obtain the formula:

Embedded image The siloxane compound represented by was prepared.

Next, 103 g of allylamine and 100 ml of hexane were placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer under a nitrogen atmosphere.
0 ml of the solution was added dropwise over 20 minutes. After stirring at room temperature for 1 hour, the generated salt was filtered using a glass filter. After distilling off low-boiling substances from the filtrate, the mixture was further distilled under reduced pressure to obtain 82-87 ° C./3.
As a fraction of mmHg, the formula:

Embedded image 125 g of a silicon-containing compound represented by the formula was prepared.

REFERENCE EXAMPLE 4 Under a nitrogen atmosphere, 222.5 hexamethylcyclotrisiloxane was placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer.
g, 94.6 g of dimethylchlorosilane, 6.7 g of dimethylformamide, and 67 g of acetonitrile, and the mixture was stirred at room temperature for 1 hour. After the completion of the reaction, low-boiling substances are distilled off.
formula:

Embedded image The siloxane compound represented by was prepared.

Next, 128 g of methallylamine and 100 ml of hexane were placed in a 1-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer under a nitrogen atmosphere.
0 ml of the solution was added dropwise over 20 minutes. After stirring at room temperature for 1 hour, the generated salt was filtered using a glass filter. After distilling off the low-boiling substances from the filtrate, the mixture is further distilled under reduced pressure to give 79-84 ° C / 4.
As a fraction of mmHg, the formula:

Embedded image 217 g of a silicon-containing compound represented by the formula was prepared.

Example 1 In a nitrogen atmosphere, 30 ml of xylene and 100 g of the silicon-containing compound prepared in Reference Example 1 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer. This was mixed with a platinum 1,3-divinyl-tetramethyldisiloxane complex (with 100 parts by weight of the silicon-containing compound, the platinum metal in this complex was 0.1% by weight).
0005 parts by weight). Then 130
After heating and stirring at 1.5 ° C. for 1.5 hours, low-boiling substances were distilled off.
100 g of reaction product was obtained.

Analysis of the reaction product showed that ²⁹ Si
From a nuclear magnetic resonance spectrum analysis (hereinafter, NMR), a signal of a nitrogen-bonded silicon atom was −12.59 ppm.
Has a signal of an alkylene group-bonded silicon atom of 7.7.
At 3 ppm, the signal of another silicon atom is -2.171 pp
m and -22.71 ppm are observed with the same integral values, respectively.
The signal of hydrogen atom-bonded silicon atoms (−6.99 ppm) observed in the silicon-containing compound of the raw material is greatly reduced,
The ratio of the integrated value to the signal of the other silicon atom was 1/20. From these analytical results, the reaction product was represented by the general formula:

Embedded image And a linear silicon-containing polymer represented by the general formula:

Embedded image It was confirmed that the mixture was a mixture composed of a cyclic silicon-containing polymer represented by the following formula: The degree of polymerization of the silicon-containing polymer
About (b), it was confirmed that it was about 20 from the ratio of the integrated value of the signal of the hydrogen-bonded silicon atom and the signal of the other silicon atom observed by ¹³ C-NMR.

Next, in a nitrogen atmosphere, 30 ml of toluene and the above-mentioned silicon-containing polymer 10 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer.
After adding 0 g, 30 ml of a 2N-NaOH aqueous solution was added thereto, and the mixture was heated and stirred at 100 ° C. for 2 hours. After completion of the reaction, a low-boiling substance was distilled off under reduced pressure from the water-washed toluene solution to obtain 99.6 g of a hydrolyzate.

When the hydrolyzate was analyzed by ¹³ C-NMR, the signal of the carbon atom of the propyl group was 14.
It was observed at 6 ppm, 27.1 ppm, and 44.8 ppm, respectively. When the hydrolyzate was analyzed by ²⁹ Si-NMR, the signal of the aminopropyl group-bonded silicon atom was 7.71 ppm, −21.46 ppm, −2
All three signals of 1.92 ppm and -22.06 ppm were observed with the same integrated value, and no other signals were observed. Further, this hydrolyzate is a single compound from the analysis by gas chromatography, and the molecular weight distribution Mw / Mn = from the analysis by gel permeation chromatography.
It turned out to be 1.05. The content of the dimethylsiloxane oligomer having no amino group was 0%. The amino group equivalent determined by neutralization titration was 4.45%. From these analytical results, this hydrolyzate has the formula:

Embedded image Was confirmed to be a dimethylpolysiloxane having amino groups at both ends of the molecular chain.

Example 2 Under a nitrogen atmosphere, 30 ml of xylene and 100 g of the silicon-containing compound prepared in Reference Example 2 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer. This was mixed with a platinum 1,3-divinyl-tetramethyldisiloxane complex (with 100 parts by weight of the silicon-containing compound, the platinum metal in this complex was 0.1% by weight).
0005 parts by weight). Then 130
After heating and stirring at 1.5 ° C. for 1.5 hours, low-boiling substances were distilled off.
100 g of reaction product was obtained.

The reaction product was treated with ²⁹ Si in the same manner as in Example 1.
As a result of analysis by -NMR, this reaction product was represented by the following general formula:

Embedded image And a linear silicon-containing polymer represented by the general formula:

Embedded image It was confirmed that the mixture was a mixture composed of a cyclic silicon-containing polymer represented by the following formula: The degree of polymerization of the silicon-containing polymer
(b) was confirmed to be approximately 20 by ¹³ C-NMR.

Next, 30 ml of toluene and the above-mentioned silicon-containing polymer 10 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen atmosphere.
After adding 0 g, 30 ml of a 2N-NaOH aqueous solution was added thereto, and the mixture was heated and stirred at 100 ° C. for 2 hours. After completion of the reaction, a low-boiling substance was distilled off under reduced pressure from the water-washed toluene solution to obtain 99.6 g of a hydrolyzate. As a result of analyzing this hydrolyzate in the same manner as in Example 1, this hydrolyzate was
formula:

Embedded image Was confirmed to be a dimethylpolysiloxane having amino groups at both ends of the molecular chain. The molecular weight distribution Mw / Mn of this dimethylpolysiloxane was 1.05, and the content of the dimethylsiloxane oligomer having no amino group was 0%. The amino group equivalent of this dimethylpolysiloxane by neutralization titration was 2.70%.

Example 3 Under a nitrogen atmosphere, 30 ml of xylene and 100 g of the silicon-containing compound prepared in Reference Example 3 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer. This was mixed with a platinum 1,3-divinyl-tetramethyldisiloxane complex (with 100 parts by weight of the silicon-containing compound, the platinum metal in this complex was 0.1% by weight).
0005 parts by weight). Then 130
After heating and stirring at 1.5 ° C. for 1.5 hours, low-boiling substances were distilled off.
100 g of reaction product was obtained.

This reaction product was treated with ²⁹ Si in the same manner as in Example 1.
As a result of analysis by -NMR, the reaction product was represented by the following general formula:

Embedded image And a linear silicon-containing polymer represented by the general formula:

Embedded image It was confirmed that the mixture was a mixture composed of a cyclic silicon-containing polymer represented by the following formula: The degree of polymerization of the silicon-containing polymer
(b) was confirmed to be approximately 20 by ¹³ C-NMR.

Next, 30 ml of toluene and the above-mentioned silicon-containing polymer 10 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer under a nitrogen atmosphere.
After adding 0 g, 30 ml of a 2N-NaOH aqueous solution was added thereto, and the mixture was heated and stirred at 100 ° C. for 2 hours. After completion of the reaction, low-boiling substances were distilled off under reduced pressure from the toluene solution washed with water to obtain 99.5 g of a hydrolyzate. When the hydrolyzate was analyzed in the same manner as in Example 1, the hydrolyzate was
formula:

Embedded image Was confirmed to be a dimethylsiloxane / methylphenylsiloxane copolymer having amino groups at both ends of the molecular chain represented by Molecular weight distribution Mw / Mn of this copolymer
= 1.05, and the content of the siloxane oligomer having no amino group was 0%. Further, the amino group equivalent of the copolymer by neutralization titration was 3.76%.

Example 4 In a nitrogen atmosphere, 30 ml of xylene and 100 g of the silicon-containing compound prepared in Reference Example 4 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel, and a thermometer. This was mixed with a platinum 1,3-divinyl-tetramethyldisiloxane complex (with 100 parts by weight of the silicon-containing compound, the platinum metal in this complex was 0.1% by weight).
0005 parts by weight). Then 130
After heating and stirring at 1.5 ° C. for 1.5 hours, low-boiling substances were distilled off.
100 g of reaction product was obtained.

This reaction product was treated with ²⁹ Si in the same manner as in Example 1.
As a result of analysis by -NMR, the reaction product was represented by the following general formula:

Embedded image And a linear silicon-containing polymer represented by the general formula:

Embedded image It was confirmed that the mixture was a mixture composed of a cyclic silicon-containing polymer represented by the following formula: The degree of polymerization of the silicon-containing polymer
(b) was confirmed to be approximately 25 by ¹³ C-NMR.

Next, under a nitrogen atmosphere, 30 ml of xylene and the above-mentioned silicon-containing polymer 100 were placed in a 0.3-liter four-necked flask equipped with a stirrer, a dropping funnel and a thermometer.
Then, 30 ml of a 2N-NaOH aqueous solution was added thereto, and the mixture was heated and stirred at 100 ° C. for 2 hours. After completion of the reaction, low-boiling substances were distilled off from the water-washed toluene solution under reduced pressure to obtain 99.7 g of a hydrolyzate. When this hydrolyzate was analyzed in the same manner as in Example 1, the hydrolyzate was found to have the formula:

Embedded image Was confirmed to be a dimethylpolysiloxane having amino groups at both ends of the molecular chain. The molecular weight distribution of this dimethylpolysiloxane was Mw / Mn = 1.05, and the content of the siloxane oligomer having no amino group was 0%. The amino group equivalent of the dimethylpolysiloxane obtained by neutralization titration was 4.31%.

[0045]

The method for producing an organopolysiloxane according to the present invention is characterized in that an organopolysiloxane having a narrow molecular weight distribution and having amino groups at both ends of a molecular chain can be efficiently produced.

[Brief description of the drawings]

FIG. 1 is a chart of ²⁹ Si-nuclear magnetic resonance spectrum analysis of dimethylpolysiloxane prepared in Example 1.

FIG. 2 is a chart of ¹³ C-nuclear magnetic resonance spectrum analysis of dimethylpolysiloxane prepared in Example 1.

FIG. 3 is a chart of gas chromatography of dimethylpolysiloxane prepared in Example 1.

Claims (2)

[Claims] 1. A compound of the general formula: (Wherein, R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, X is a halogen atom, and a is an integer of 1 or more). Siloxane compound and general formula: (Wherein, R ² is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom, and R ³ is a divalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond. ,
R ⁴ is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond or a hydrogen atom. ) Is subjected to a dehydrohalogenation condensation reaction to give a compound of the general formula: (Wherein R ¹ , R ² , R ³ , R ⁴ , and a are the same as those described above), and then the siloxane compound is subjected to addition polymerization with a hydrosilylation reaction catalyst. And the general formula: (Wherein R ¹ , R ² , R ³ , R ⁴ , and a are the same as above, and b is an integer of 1 or more). General formula: wherein the silicon-containing polymer is hydrolyzed. (Wherein R ¹ , R ² , R ³ , R ⁴ , and a are the same as described above). 2. A compound of the general formula: (Wherein, R ¹ is the same or different and is a monovalent hydrocarbon group having no aliphatic unsaturated carbon-carbon bond, X is a halogen atom, and a is an integer of 1 or more). The siloxane compound represented by the general formula: (Wherein, R ¹ is the same as described above, and n is an integer of 3 or more). (Wherein R ¹ and X are the same as described above), which is a compound obtained by a ring-opening reaction with a silane compound represented by the following formula: Production method.