JP2001122967A - Diorganopolysiloxane and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new diorganopolysiloxane blocked with a carboxylamino group at one end of the molecular chain and blocked with a various kinds of functional groups at the other end thereof and to provide a method for efficiently producing the diorganopolysiloxane. SOLUTION: The diorganopolysiloxane is represented by the general formula, wherein Rs are each a same or different kind of a monovalent hydrocarbon or a halogen-substituted monovalent hydrocarbon without containing an aliphatic unsaturated bond; R1s are H or a monovalent hydrocarbon; R2 is a divalent hydrocarbon or an alkylene oxyalkylene; R3s are a monovalent hydrocarbon without containing an aliphatic unsaturated bond; n is an integer of 11-1,000; and B is H or a monovalent organosilyl having various kinds of functional groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diorganopolysiloxane and a method for producing the same, and more particularly, to a novel diorganopolysiloxane having one end blocked with a carbonylamino group and the other end blocked with various functional groups. The present invention relates to a siloxane and a method for producing the same.

[0002]

2. Description of the Related Art A diorganopolysiloxane having a carbonylamino functional group at one end of a molecular chain has an acrylamide group or a methacrylamide group at one end and a non-reactive triorganosilyl group at the other end. Blocked diorganopolysiloxanes are known (JP-A-5-17577 and JP-A-9-12724).
Reference). However, a diorganopolysiloxane in which one end of a molecular chain is blocked with a carbonylamino group and the other end is blocked with various functional groups has not been known.
On the other hand, the present inventors have already disclosed in Japanese Patent Application Nos. 10-159947 and 10-159948 that one terminal of a molecular chain is blocked with a carbonylamino group and the other terminal is blocked with a silanol group or an acyloxysilyl group. The proposed diorganopolysiloxane and its production method were proposed. However, these diorganopolysiloxanes are limited to low-molecular-weight ones, and it has not been possible to produce diorganopolysiloxanes having a degree of polymerization exceeding 10 and having a relatively large molecular weight.

[0003]

The inventor of the present invention has made intensive studies on the above problems, and has reached the present invention. That is, an object of the present invention is to efficiently produce a novel diorganopolysiloxane and a diorganopolysiloxane in which one end of a molecular chain is blocked with a carbonylamino group and the other end is blocked with various functional groups. It is to provide a way to do it.

[0004]

According to the present invention, there is provided a compound represented by the general formula:

Embedded image(In the formula, R is the same species containing no aliphatic unsaturated bond or
Different monovalent hydrocarbon groups or halogen-substituted monovalent hydrocarbons
And R is¹Is a hydrogen atom or a monovalent hydrocarbon group
R^TwoIs a divalent hydrocarbon group or alkyleneoxy
A kylene group;^Three Is an aliphatic unsaturated bond-free
And n is an integer of 11 to 1000.
B is a hydrogen atom or an alkenyl group, acryloxy
Group, methacryloxy group, vinylphenyl group, silicon atom
Bonded hydrogen atom, primary amino group, secondary amino group, tertiary amino group
Groups, carboxyl groups, hydroxy groups, epoxy groups,
Monovalent organo having a functional group selected from phenolic groups
A silyl group. ) Characterized by the following:
The present invention relates to a ganopolysiloxane and a method for producing the same.

[0005]

DETAILED DESCRIPTION OF THE INVENTION First, the diorganopolysiloxane of the present invention in which one end of a molecular chain is blocked with a carbonylamino group and the other end is blocked with various functional groups will be described in detail. The diorganopolysiloxane of the present invention is represented by the above general formula, wherein R is the same or different monovalent hydrocarbon group containing no aliphatic unsaturated bond or a halogen-substituted monovalent hydrocarbon group. Specific examples of the unsubstituted monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group; an aryl group such as a phenyl group, a tolyl group and a xylyl group; a benzyl group and a phenethyl group An aralkyl group such as a group is exemplified. Examples of the halogen-substituted hydrocarbon group include a trifluoropropyl group, a nonafluorohexyl group, a chloropropyl group, and a chloromethylphenethyl group. Among these, a methyl group is preferred from the viewpoint of easiness of production and economy. R
¹ is a hydrogen atom or a monovalent hydrocarbon group, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group; an aryl group such as a phenyl group, a tolyl group, a xylyl group; Aralkyl groups such as benzyl group and phenethyl group; and alkenyl groups such as vinyl group, methallyl group and 1-propenyl group. The alkenyl group in R ¹ is preferably one in which an aliphatic unsaturated bond is directly connected to a carbonyl group in an adjacent amide group. Among them, methyl group,
It is preferably an ethyl group, a vinyl group or a methallyl group, more preferably a methyl group. R ² is a divalent hydrocarbon group or an alkyleneoxyalkylene group,
Examples of the divalent hydrocarbon group include an alkylene group such as an ethylene group, a methylethylene group, a propylene group, a 2-methylpropylene group, a butylene group, a pentylene group, and a hexylene group; a phenylene group, and a formula: —CH ₂ C ₆ H ₄ — the _{formula: -CH 2 C 6 H 4 CH} 2 - arylene radicals, such as the group represented by is exemplified. Examples of the alkyleneoxyalkylene group include an ethyleneoxyethylene group and a propyleneoxypropylene group. Among these, a propylene group and a 2-methylpropylene group are preferable from the viewpoint of ease of production and economy. R ³ is a monovalent hydrocarbon group containing no aliphatic unsaturated bond, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group; a phenyl group, a tolyl group, a xylyl group; And an aralkyl group such as a benzyl group and a phenethyl group. n is 11 to 100
Although it is an integer of 0, it is preferably in the range of 20 to 200, and more preferably in the range of 20 to 150, for ease of synthesis.
B is a hydrogen atom, an alkenyl group, an acryloxy group,
Monovalent organosilyl having a functional group selected from methacryloxy, vinylphenyl, silicon-bonded hydrogen, primary amino, secondary amino, tertiary amino, carboxyl, hydroxy, epoxy, and phenol groups Group. In the organosilyl group, various functional groups may be directly bonded to a silicon atom, or may be bonded to a silicon atom via a divalent organic group such as an alkylene group or an alkyleneoxyalkylene group. In particular, acryloxy, methacryloxy, primary amino, secondary amino, tertiary amino, carboxyl, hydroxy,
The epoxy group and the phenol group are preferably bonded to the silicon atom via the above-mentioned divalent organic group. Examples of such an organosilyl group include groups represented by the following general formula.

Embedded image In the above formula, R, R ² and m are the same as described above, and A is an alkenyl group, acryloxy group, methacryloxy group, vinylphenyl group, primary amino group, secondary amino group, tertiary amino group, carboxyl group, hydroxy group Is a functional group selected from a group, an epoxy group and a phenol group, and k is 0 or 1.
And p is an integer of 1 to 3.

A specific example of such a diorganopolysiloxane of the present invention in which one end of a molecular chain is blocked with a carbonylamino group and the other end is blocked with various functional group-containing silyl groups is represented by the following structural formula. Compounds to be used.

Embedded image

Embedded image

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Next, the manufacturing method of the present invention will be described in detail. The first production method of the present invention comprises (A) a general formula:

Embedded image (Wherein R is as defined above) represented by the general formula (B):

Embedded image Wherein R, R ¹ , R ² and R ³ are as described above.
m is an integer of 10 or less. (C) in the presence or absence of an organosilicon compound having a carbonylamino group and a silanol group in the same molecule represented by the following formula (C):

Embedded image (Wherein R, R ¹ , R ² , R ³ and m are the same as those described above), and the ring-opening polymerization is carried out by (D) acid, silicon atom Organic compound containing a bonded hydrogen atom and a halogenosilyl group, organic compound containing an alkenyl group and a halogenosilyl group, organic compound containing an acryloxy group and a halogenosilyl group, organic compound containing a methacryloxy group and a halogenosilyl group, vinyl Terminating with a terminating agent selected from organic compounds containing a phenyl group and a halogenosilyl group, the general formula:

Embedded image (Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ¹ is selected from a hydrogen atom or an alkenyl group, an acryloxy group, a methacryloxy group, a vinylphenyl group, and a silicon-bonded hydrogen atom. This is a method for producing a diorganopolysiloxane represented by the following formula:

[0008] The second production method of the present invention is the same as the first production method described above, except that an organic compound containing a silicon-bonded hydrogen atom and a halogenosilyl group is used as a terminator for the component (D). After synthesizing a diorganopolysiloxane in which one end of the chain is blocked with a carbonylamino group and the other end is blocked with a silyl group containing a silicon-bonded hydrogen atom, then, in the presence of a catalyst for a hydrosilylation reaction, (E) An aliphatic unsaturated compound having an epoxy functional group is subjected to an addition reaction to obtain a compound represented by the general formula:

Embedded image Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ² is a monovalent organosilyl group having an epoxy functional group. How to

The third production method of the present invention is the same as the above-mentioned first production method, wherein an organic compound containing a silicon-bonded hydrogen atom and a halogenosilyl group is used as a terminator for the component (D). After synthesizing a diorganopolysiloxane in which one end of the chain is blocked with a carbonylamino group and the other end is blocked with a silyl group containing a silicon-bonded hydrogen atom, then, in the presence of a catalyst for a hydrosilylation reaction, (F) An addition reaction of an aliphatic unsaturated compound having a group selected from a primary amino group, a secondary amino group, a carboxyl group, a hydroxy group, and a phenol group protected by a triorganosilyl group, After the silylation reaction, the general formula:

Embedded image Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ³ has a functional group selected from a primary amino group, a secondary amino group, a carboxyl group, a hydroxy group and a phenol group. This is a method for producing a diorganopolysiloxane represented by the following formula:

The fourth production method of the present invention is the same as the first production method described above, except that an organic compound containing a silicon-bonded hydrogen atom and a halogenosilyl group is used as a terminator for the component (D). After synthesizing a diorganopolysiloxane in which one end of the chain is blocked with a carbonylamino group and the other end is blocked with a silyl group containing a silicon-bonded hydrogen atom, then, in the presence of a catalyst for a hydrosilylation reaction, (G) An aliphatic unsaturated compound having a tertiary amino group is subjected to an addition reaction to obtain a compound represented by the general formula:

Embedded image (Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ⁴ is a monovalent organosilyl group having a tertiary amino group). How to

The cyclic trisiloxane of the component (A) used in the production method of the present invention is represented by the above general formula. Where:
R is as described above. Such cyclic trisiloxanes include hexamethylcyclotrisiloxane, hexaphenylcyclotrisiloxane, 1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane, 1,
3,5-trimethyl-1,3,5-tris (trifluoropropyl) cyclotrisiloxane is exemplified. In order to obtain the diorganopolysiloxane of the present invention having a small molecular weight distribution polydispersity (Mw / Mn), it is preferable to purify this component by performing recrystallization, distillation, or the like before ring-opening polymerization.

The organosilicon compound having a carbonylamino group and a silanol group in the same molecule as the component (B) used in the production method of the present invention is necessary for controlling the molecular weight of the diorganopolysiloxane of the present invention. It is a component used in accordance with the above general formula. Where R,
R ¹ , R ² and R ³ are as described above. m is an integer of 10 or less, including 0. This organosilicon compound can be produced, for example, by hydrolyzing an organosilicon compound having a carbonylamino group at one terminal of a molecular chain and having an acyloxysilyl group at the other terminal (Japanese Patent Application No. 10-284,197). -159948).

The lithium compound catalyst of the component (C) used in the production method of the present invention is a catalyst for subjecting the component (A) or the component (A) and the component (B) to a ring-opening polymerization reaction. It is represented by the general formula. Where R, R ¹ , R ² , R ³
And m are as described above. This lithium silanolate or lithium siloxanolate is, for example, (B)
It can be produced by reacting a silanol or siloxanol compound such as a component with a lithium compound and lithiation. At this time, a lithium compound having a smaller number of moles than the number of moles of the silanol group is reacted, and the resulting unreacted reaction mixture containing a silanol group or a siloxanol group is mixed with a mixture of the component (B) and the component (C). You may use as. The lithium compound used in the synthesis of this component includes alkyl lithium such as n-butyl lithium, s-butyl lithium, t-butyl lithium, and methyl lithium; aryl lithium such as phenyl lithium and xylyl lithium; vinyl lithium ,
Alkenyl lithium such as allyl lithium; and lithium amide such as lithium bis (diisopropyl) amide. Such a lithium compound catalyst may be present in an amount sufficient to cause a ring opening reaction of the cyclic trisiloxane of the component (A).

The polymerization reaction conditions in the production method of the present invention vary depending on the type of the cyclic trisiloxane of the component (A). For example, when hexamethylcyclotrisiloxane is used, the polymerization is carried out in a solvent at 0 to 30 ° C. The reaction is preferably performed for 1 to 50 hours. The solvent used here may be any aprotic solvent, and specific examples thereof include aliphatic hydrocarbons such as pentane, hexane, and heptane; aromatic hydrocarbons such as toluene, benzene, and xylene; Ethers such as diethyl ether; ketones such as acetone and methyl ethyl ketone; carbon tetrachloride;
Halogenated hydrocarbons such as trichloroethylene and chloroform; ketones such as acetone and methyl ethyl ketone; and acetonitrile, dimethylformamide, dimethylsulfoxide, and hexamethylphosphoric acid triamide are exemplified. One of these solvents may be used alone, but the use of a combination of two or more thereof often gives good results. For example, when a low-polarity solvent such as toluene is used, it is preferable to add a high-polarity solvent such as dimethylformamide, dimethylsulfoxide, and hexamethylphosphoric triamide for the purpose of accelerating the reaction. Reaction temperatures and times must be carefully controlled to minimize the rate of rearrangement reactions. This is because, when the degree of equilibrium polymerization due to rearrangement rather than non-equilibrium polymerization increases, one end of the molecular chain is blocked with a carbonylamino group, and the other end is blocked with a silanol group or lithium silanolate group. Not only diorganopolysiloxanes but also diorganopolysiloxanes whose molecular chain ends are blocked with carbonylamino groups and diorganopolysiloxanes whose molecular chain ends are blocked with silanol groups or lithium silanolate groups are present in large quantities. Because they will be born. In this polymerization reaction, the conversion of the cyclic trisiloxane of the component (A) is usually tracked by an analyzer such as gas chromatography, and when a certain value is reached, a terminator of the component (D) is added. Preferably, it is stopped. In order to suppress the above side reactions, the conversion is preferably 95% or less. Further, the yield is preferably in the range of 70 to 95% from the viewpoint of the yield of the obtained diorganopolysiloxane.
More preferably, it is in the range of 0 to 95%. By subjecting the component (A) to the ring-opening polymerization with the component (C), a diorganopolysiloxane having a small molecular weight distribution polydispersity (Mw / Mn) of 1.5 or less and a small degree of dispersion can be obtained.
Further, in the present invention, by selecting conditions, 1.3 is obtained.
The following diorganopolysiloxanes can be prepared. In the present invention, a low polydispersity means that the above-mentioned side reaction can be suppressed and a high-purity diorganopolysiloxane was obtained.

The degree of polymerization of the diorganopolysiloxane obtained by the production method of the present invention is based on the total number of moles of the component (B) and the component (C), and the dimol of the component (A) used in the polymerization reaction. It is determined by the number of moles of the organosiloxy group. The preferred ratio of these moles [the ratio of the number of moles of the diorganosiloxy group in the component (A) used in the polymerization reaction to the total moles of the components (B) and (C)] is 11 to 1
000. If the molecular weight is 10 or less, the molecular weight of the resulting diorganopolysiloxane is too small to control the ring-opening polymerization of the component (A).
If it exceeds 00, it is difficult to control the molecular weight of the resulting diorganopolysiloxane due to fluctuations in the total number of moles of the components (B) and (C). The mixing ratio of the component (B) and the component (C) is 0: 100 to 10 in molar ratio.
The range of 0: 0.01 is preferred.

The component (D) used in the production method of the present invention is a component for terminating the above-mentioned ring-opening polymerization, and reacts with lithium siloxanolate to form a stable lithium salt. Examples of such a terminator include an acid, an organic compound containing a silicon-bonded hydrogen atom and a halogenosilyl group,
Selected from organic compounds containing an alkenyl group and a halogenosilyl group, organic compounds containing an acryloxy group and a halogenosilyl group, organic compounds containing a methacryloxy group and a halogenosilyl group, and organic compounds containing a vinylphenyl group and a halogenosilyl group. Is used. Examples of the acid include mineral acids such as aqueous carbon dioxide, hydrochloric acid, and sulfuric acid; and carboxylic acids such as acetic acid, propionic acid, and acrylic acid. Examples of the organic compound containing a silicon-bonded hydrogen atom and a halogenosilyl group include hydridohalogenosilanes such as dimethylchlorosilane, diethylchlorosilane, diphenylchlorosilane, and dimethylbromosilane, and bis (dimethylsiloxy) halogeno represented by the following structural formula. Silethylene siloxane and tris (dimethylsiloxy) halogenosylethylene siloxane can also be used (see JP-A-4-353523).

Embedded image Examples of the organic compound containing an alkenyl group and a halogenosilyl group include vinyldimethylchlorosilane and 5-hexenyldimethylchlorosilane. Examples of the organic compound containing an acryloxy group and a halogenosilyl group include 3-acryloxypropyldimethylchlorosilane,
6-acryloxyhexyldimethylchlorosilane, acryloxyethyloxypropyldimethylchlorosilane, 3
-Acryloxypropyldimethylbromosilane is exemplified. Examples of the organic compound containing a methacryloxy group and a halogenosilyl group include 3-methacryloxypropyldimethylchlorosilane, 6-methacryloxyhexyldimethylchlorosilane, methacryloxyethyloxypropyldimethylchlorosilane, and 3-methacryloxypropyldimethylbromosilane. . Examples of the organic compound containing a vinylphenyl group and a halogenosilyl group include 4
-Vinylphenyldimethylchlorosilane, 4-vinylphenyldimethylbromosilane and 2-vinylphenyldimethylchlorosilane are exemplified.

When the ring-opening polymerization is terminated by using an acid such as hydrated carbon dioxide, mineral acid or carboxylic acid as the component (D), one end of the molecular chain is blocked with a carbonylamino group and the other end is closed. Are blocked with silanol groups to obtain the diorganopolysiloxane of the present invention. Further, when ring-opening polymerization is terminated using an organic compound containing various functional groups and a halogenosilyl group, one end of the molecular chain is blocked with a carbonylamino group, and the other end is terminated with a halogen atom from a terminator used. Thus, the diorganopolysiloxane of the present invention blocked with a silyl residue excluding is obtained. At this time, it is preferable to add a hydrogen halide scavenger such as an organic amine compound or ammonia. Also, instead of performing the ring-opening polymerization termination reaction and the functional group introduction reaction at the same time, using an acid as a terminator, one end of the molecular chain is blocked with a carbonylamino group, and the other end is blocked with a silanol group. Then, an organic compound containing a silicon-bonded hydrogen atom and a halogenosilyl group, an organic compound containing an alkenyl group and a halogenosilyl group, and an organic compound containing an acryloxy group and a halogenosilyl group. The diorganopolysiloxane of the present invention can also be obtained by a method of adding a compound, an organic compound containing a methacryloxy group and a halogenosilyl group, or an organic compound containing a vinylphenyl group and a halogenosilyl group to cause a dehydrohalogenation reaction. Can be manufactured. Also at this time, it is preferable to add a hydrogen halide scavenger such as an organic amine compound or ammonia, as described above.

When the ring-opening polymerization is terminated using an organic compound containing a silicon-bonded hydrogen atom and a halogenosilyl group as the component (D), one end of the molecular chain is blocked with a carbonylamino group, A diorganopolysiloxane in which the other end is blocked with a silicon-bonded hydrogen atom-containing silyl group is obtained.In addition, an aliphatic unsaturated compound having a functional group on the silicon-bonded hydrogen atom is converted to a platinum-based catalyst or the like. The diorganopolysiloxane of the present invention can also be produced by a method in which the addition reaction is carried out in the presence of a hydrosilylation reaction catalyst. Examples of the aliphatic unsaturated compound having such a functional group include (E) an aliphatic unsaturated compound having an epoxy functional group, (F) a primary amino group and a secondary amino group protected with a triorganosilyl group. An aliphatic unsaturated compound having a group selected from, a carboxyl group, a hydroxy group, and a phenol group; and (G) an aliphatic unsaturated compound having a tertiary amino group. Specific examples of the component (E) include allyl glycidyl ether and 3,4-epoxycyclohexylethene. Specific examples of the component (F) include aliphatic unsaturated compounds having an amino group protected with a triorganosilyl group, such as trimethylsilylallylamine, trimethylsilylallylcyclohexylamine, and trimethylsilylpropylallylamine;
Aliphatic unsaturated compounds having a carboxyl group protected by a triorganosilyl group, such as trimethylsilyl undecylenate, trimethylsilyl octenylene, and trimethylsilyl decanilenate; protected by a triorganosilyl group, such as trimethylallyloxysilane and trimethylisobutenyloxysilane Aliphatic unsaturated compounds having a hydroxy group; o-triorganosiloxyallylbenzene, o-
Examples thereof include aliphatic unsaturated compounds having a phenol group protected by a triorganosilyl group such as methoxy-p-triorganosiloxyallylbenzene. Specific examples of the component (G) include N, N-dimethylallylamine. When the component (F) is used, it is necessary to regenerate the functional group by performing a triorganosilylation reaction after the completion of the addition reaction. A conventionally known method can be used as a method for detriorganosilylation. (E) component, (F)
The amount of the aliphatic unsaturated compound used as the component or the component (G) is determined in the diorganopolysiloxane in which one end of the molecular chain is blocked with a carbonylamino group and the other end is blocked with a silyl group containing a silicon-bonded hydrogen atom. The amount is such that the aliphatic unsaturated bond is equivalent to or more than one silicon-bonded hydrogen atom. As the hydrosilylation reaction catalyst used in the addition reaction, known catalysts can be used, and a platinum-based catalyst is particularly preferable. Specific examples include chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, a complex of platinum and a siloxane containing a vinyl group, silica-supported platinum, and activated carbon-supported platinum. Although the addition reaction can be performed at room temperature, the reaction rate is good, and
It is preferably performed under a temperature condition of ° C. Further, this addition reaction can be performed without a solvent or in a solvent. Solvents that can be used include aliphatic hydrocarbons such as pentane, hexane and heptane; aromatic hydrocarbons such as toluene, benzene and xylene; ethers such as tetrahydrofuran and diethyl ether; ketones such as acetone and methyl ethyl ketone; Halogenated hydrocarbons such as carbon chloride, trichloroethylene and chloroform; ketones such as acetone and methyl ethyl ketone; and dimethylformamide;
Dimethyl sulfoxide is exemplified.

The diorganopolysiloxane of the present invention as described above has a hydrophilic carbonylamino group and a hydrophobic diorganosiloxane unit, and is therefore useful as a polymeric surfactant.

[0020]

The present invention will be described below with reference to examples.

[0021]

Reference Example 1 A flask equipped with a stirrer was charged with 35.7 g (350 mmol) of acetic anhydride, and cooled with ice water under a nitrogen atmosphere under 1,2,2,4-tetramethyl-1.
50 g (350 mmol) of aza-2-silacyclopentane were slowly added dropwise over 30 minutes. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes and distilled under reduced pressure to obtain 112 to 135 ° C / 1 mmHg.
74.5 g (84% yield) of a fraction were obtained. When this fraction was analyzed by nuclear magnetic resonance analysis (NMR) and infrared absorption analysis (IR), it was N- (3-acetoxydimethylsilyl) -2-methylpropyl-N-methylacetamide, Its purity was found to be 98.3%. On the other hand, 60 ml of toluene, 23.7 g (281.6 mmol) of sodium hydrogen carbonate and 120 ml of water were charged into a flask equipped with a stirrer, and these were stirred while cooling with water.
60 grams (244.9 mmol) of (3-acetoxydimethylsilyl) -2-methylpropyl-N-methylacetamide was slowly added dropwise over 45 minutes. Then, 1.2 grams of triethylamine was added and stirred at room temperature for 30 minutes. The organic layer is sampled from the reaction mixture, and GL is sampled.
As a result of analysis at C, the peak of N- (3-acetoxydimethylsilyl) -2-methylpropyl-N-methylacetamide as the raw material had disappeared, and the reaction was terminated. The lower aqueous layer was discarded. Further, the upper toluene layer was washed twice with water, and the reaction product dissolved in the lower aqueous layer was extracted with 60 ml of toluene. When a low boiling point substance was distilled off by heating under reduced pressure by adding a toluene layer to this extract, 25.2 g of a liquid was obtained. The liquid was analyzed by IR and NMR to find that it was N- (3-hydroxydimethylsilyl) -2-
Methylpropyl-N-methylacetamide, its purity was found to be 98.2%.

[0022]

Example 1 A four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser, and a water separation tube was charged with 75.8 g (341 mmol) of hexamethylcyclotrisiloxane and 56.8 g of toluene, and heated and azeotroped. Dehydration was performed for 1 hour. On the other hand, N- (3-hydroxydimethylsilyl) -2-methylpropyl-N-methylacetamide prepared in Reference Example 1 was placed in another four-necked flask equipped with a stirrer.
3 g (16.3 mmol) was added, and the mixture was stirred under water cooling under a nitrogen atmosphere while 0.128 mmol of an n-hexane solution of n-butyllithium was added and stirred for 5 minutes. To this mixture, the whole amount of the previously prepared toluene solution of hexamethylcyclotrisiloxane was added, and further, a mixture of 3.3 g of dimethylformamide and 18.8 g of acetonitrile was added, followed by stirring at 25 ° C. The progress of the polymerization reaction was monitored by gas chromatography while sampling periodically, and when the conversion of hexamethylcyclotrisiloxane reached 83% after 2.75 hours,
The polymerization was stopped by adding 0.015 grams (0.26 mmol) of acetic acid. Then, heat distillation under reduced pressure was performed to remove low-boiling substances,
The by-product salt was filtered to obtain 68.7 g of a clear polymer. When this was analyzed by gel permeation chromatography (GPC), NMR and IR,
It was found to be a diorganopolysiloxane represented by the following structural formula. GPC molecular weight distribution polydispersity (M
(w / Mn) was 1.11.

Embedded image

[0023]

Example 2 75.8 g (341 mmol) of hexamethylcyclotrisiloxane and 56.8 g of toluene were charged into a four-necked flask equipped with a stirrer, a thermometer, a Dimroth condenser and a water separation tube, and heated under azeotropy. Dehydration was performed for 1 hour. On the other hand, N- (3-hydroxydimethylsilyl) -2-methylpropyl-N-methylacetamide prepared in Reference Example 1 was placed in another four-necked flask equipped with a stirrer.
6 g (32.5 mmol) was added thereto, and while stirring under water cooling under a nitrogen atmosphere, 0.128 mmol of an n-hexane solution of n-butyllithium was added and stirred for 5 minutes. To this mixture, the whole amount of the previously prepared toluene solution of hexamethylcyclotrisiloxane was added, and further, a mixture of 3.3 g of dimethylformamide and 18.8 g of acetonitrile was added, followed by stirring at 25 ° C. The progress of the polymerization reaction was monitored by gas chromatography while sampling periodically, and when the conversion of hexamethylcyclotrisiloxane reached 83% after 2.75 hours,
The polymerization was stopped by adding 0.015 grams (0.26 mmol) of acetic acid. Then, heat distillation under reduced pressure was performed to remove low-boiling substances,
The by-product salt was filtered to obtain 68.7 g of a clear polymer. When this was analyzed by GPC, NMR and IR, it was found to be a diorganopolysiloxane represented by the following structural formula. The molecular weight distribution polydispersity (Mw / Mn) by GPC was 1.24.

Embedded image

[0024]

Example 3 Example 4 was prepared in a four-necked flask equipped with a stirrer.
The expression obtained with:

Embedded image 30 g of diorganopolysiloxane, 30 ml of toluene and 2.7 g of triethylamine (2
6.7 mmol). While stirring them under a nitrogen atmosphere, 1.7 g (18.0 mmol) of dimethylchlorosilane was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 14 hours, and the by-produced salts were removed by filtration under reduced pressure. Further, low-boiling substances were distilled off from the filtrate by heating under reduced pressure. A small amount of the salt thus precipitated was separated by filtration to obtain 29.3 g of a transparent polymer. When this was analyzed by GPC, NMR and IR, it was found that this was a diorganopolysiloxane represented by the following average structural formula. The molecular weight distribution polydispersity (Mw / Mn) by GPC was 1.18.

Embedded image

[0025]

Example 4 Example 3 was placed in a four-necked flask equipped with a stirrer.
The expression obtained with:

Embedded image 20 g of a diorganopolysiloxane represented by the formula and 10 ml of toluene were added thereto.
-A complex with divinyltetramethyldisiloxane, the amount of platinum metal is 10 ppm based on the above diorganopolysiloxane.
Was added so that These were heated to 80 ° C., and allyl glycidyl ether 1.
3 grams (11.4 mmol) were added dropwise. After dropping, 8
The mixture was heated and stirred at 0 ° C for 1 hour. When the reaction mixture was sampled and analyzed by IR, it was determined that the reaction was terminated because the characteristic absorption of Si-H had disappeared. Then, low boiling substances were removed by heating under reduced pressure to give 20.5 g of a transparent polymer. When this was analyzed by GPC, NMR and IR, it was found that this was a diorganopolysiloxane represented by the following average structural formula. The molecular weight distribution polydispersity (Mw / Mn) by GPC was 1.18.

Embedded image

[0026]

Example 5 Example 4 was prepared in a four-necked flask equipped with a stirrer.
The expression obtained with:

Embedded image 20 g of a diorganopolysiloxane represented by the formula and 10 ml of toluene were added thereto.
-A complex with divinyltetramethyldisiloxane in which the amount of platinum metal is 20 ppm with respect to the diorganopolysiloxane
Was added so that These were heated to 80 ° C., and 1.47 g (11.4 mmol) of trimethylsilylallylamine was added dropwise while stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at 80 ° C. for 5 hours. The reaction mixture was sampled and analyzed by IR. The reaction was determined to be complete because the characteristic absorption of Si-H had almost disappeared. Then, low-boiling substances were removed by distillation under reduced pressure with heating, and 1 g of methanol was added.
It was charged and heated and stirred at 50 ° C. for 3 hours. After 3 hours, the low-boiling substances were distilled off by heating under reduced pressure to obtain 20.0 g of a transparent polymer. When this was analyzed by GPC, NMR and IR, it was found that this was a diorganopolysiloxane represented by the following average structural formula. The molecular weight distribution polydispersity (Mw / Mn) by GPC was 1.19.

Embedded image

[0027]

Example 6 Example 4 was prepared in a four-necked flask equipped with a stirrer.
The expression obtained with:

Embedded image 20 g of a diorganopolysiloxane represented by the formula and 10 ml of toluene are added, and further, chlorotris
(Triphenylphosphine) rhodium (I) is added at a rhodium metal content of 150 ppm based on the diorganopolysiloxane.
Was added so that These were heated to 80 ° C., and 0.97 g (11.4 mmol) of N, N-dimethylallylamine was added dropwise with stirring under a nitrogen atmosphere. After completion of the dropwise addition, the mixture was heated and stirred at 80 ° C. for 5 hours. When the reaction mixture was sampled and analyzed by IR, it was determined that the reaction was terminated because the characteristic absorption of Si-H had disappeared. Then, the low-boiling substances were distilled off by heating under reduced pressure to obtain 20.3 g of a transparent polymer.
When this was analyzed by GPC, NMR and IR, it was found that this was a diorganopolysiloxane represented by the following average structural formula. The molecular weight distribution polydispersity (Mw / Mn) by GPC was 1.17.

Embedded image

[0028]

The diorganopolysiloxane of the present invention comprises
A novel polymer having a structure in which one terminal of a molecular chain is blocked with a carbonylamino group and the other terminal is blocked with various functional group-containing silyl groups, the production method of the present invention is directed to such a dimer. It has the feature that organopolysiloxane can be produced efficiently.

[Brief description of the drawings]

FIG. 1 is an IR chart of the diorganopolysiloxane prepared in Example 1.

FIG. 2 is an IR chart of the diorganopolysiloxane prepared in Example 2.

FIG. 3 is an IR chart of the diorganopolysiloxane prepared in Example 3.

FIG. 4 is an IR chart of the diorganopolysiloxane prepared in Example 4.

Claims (6)

[Claims] 1. A compound of the general formula:(In the formula, R is the same species containing no aliphatic unsaturated bond or
Different monovalent hydrocarbon groups or halogen-substituted monovalent hydrocarbons
And R is¹Is a hydrogen atom or a monovalent hydrocarbon group
R^TwoIs a divalent hydrocarbon group or alkyleneoxy
A kylene group;^Three Is an aliphatic unsaturated bond-free
And n is an integer of 11 to 1000.
B is a hydrogen atom or an alkenyl group, acryloxy
Group, methacryloxy group, vinylphenyl group, silicon atom
Bonded hydrogen atom, primary amino group, secondary amino group, tertiary amino group
Groups, carboxyl groups, hydroxy groups, epoxy groups,
Monovalent organo having a functional group selected from phenolic groups
A silyl group. ) Characterized by the following:
Ganopolysiloxane. 2. The diorganopolysiloxane according to claim 1, wherein R ¹ is an alkyl group. (A) General formula: (Wherein R is as defined above), and the cyclic trisiloxane represented by the general formula (B): (Wherein R, R ¹ , R ² and R ³ are as defined above,
m is an integer of 10 or less. (C) in the presence or absence of an organosilicon compound having a carbonylamino group and a silanol group in the same molecule, and (C) a compound represented by the following general formula: (Wherein R, R ¹ , R ² , R ³ and m are the same as those described above), and the ring-opening polymerization is carried out by (D) acid, silicon atom Organic compound containing a bonded hydrogen atom and a halogenosilyl group, organic compound containing an alkenyl group and a halogenosilyl group, organic compound containing an acryloxy group and a halogenosilyl group, organic compound containing a methacryloxy group and a halogenosilyl group, vinyl The terminating agent is a terminating agent selected from organic compounds containing a phenyl group and a halogenosilyl group, characterized by the following general formula: (Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ¹ is selected from a hydrogen atom or an alkenyl group, an acryloxy group, a methacryloxy group, a vinylphenyl group, and a silicon-bonded hydrogen atom. Which is a monovalent organosilyl group having a functional group represented by the formula: (A) a general formula: (Wherein R is as defined above), and (B) a general formula: (Wherein R, R ¹ , R ² , R ³ and m are as described above) in the presence or absence of an organosilicon compound having a carbonylamino group and a silanol group in the same molecule, C) General formula: (Wherein R, R ¹ , R ² , R ³ and m are as defined above), and the ring-opening polymerization is carried out by (D) silicon-bonded hydrogen. Terminating with an organic compound containing an atom and a halogenosilyl group to synthesize a diorganopolysiloxane in which one end of the molecular chain is blocked with a carbonylamino group and the other end is blocked with a silyl group containing a silicon-bonded hydrogen atom. And (E) an aliphatic unsaturated compound having an epoxy functional group, which is then subjected to an addition reaction in the presence of a catalyst for a hydrosilylation reaction, characterized by the following general formula: Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ² is a monovalent organosilyl group having an epoxy functional group. Method. (A) a general formula: (Wherein R is as defined above), and (B) a general formula: (Wherein R, R ¹ , R ² , R ³ and m are as described above) in the presence or absence of an organosilicon compound having a carbonylamino group and a silanol group in the same molecule, C) General formula: (Wherein R, R ¹ , R ² , R ³ and m are as defined above), and the ring-opening polymerization is carried out by (D) silicon-bonded hydrogen. Terminating with an organic compound containing an atom and a halogenosilyl group to synthesize a diorganopolysiloxane in which one end of the molecular chain is blocked with a carbonylamino group and the other end is blocked with a silyl group containing a silicon-bonded hydrogen atom. Then, in the presence of a catalyst for a hydrosilylation reaction, (F) a primary amino group, a secondary amino group, a carboxyl group, a hydroxy group protected by a triorganosilyl group,
An addition reaction of an aliphatic unsaturated compound having a group selected from a phenol group, followed by a deorganosilylation reaction, characterized by the following general formula: Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ³ has a functional group selected from a primary amino group, a secondary amino group, a carboxyl group, a hydroxy group and a phenol group. A method for producing a diorganopolysiloxane represented by the formula: (A) General formula: (Wherein R is as defined above), and (B) a general formula: (Wherein R, R ¹ , R ² , R ³ and m are as described above) in the presence or absence of an organosilicon compound having a carbonylamino group and a silanol group in the same molecule, C) General formula: (Wherein R, R ¹ , R ² , R ³ and m are as defined above), and the ring-opening polymerization is carried out by (D) silicon-bonded hydrogen. Terminating with an organic compound containing an atom and a halogenosilyl group to synthesize a diorganopolysiloxane in which one end of the molecular chain is blocked with a carbonylamino group and the other end is blocked with a silyl group containing a silicon-bonded hydrogen atom. Then, in the presence of a hydrosilylation reaction catalyst, (G) an aliphatic unsaturated compound having a tertiary amino group is subjected to an addition reaction, which is characterized by the following general formula: (Wherein R, R ¹ , R ² , R ³ and n are as described above, and B ⁴ is a monovalent organosilyl group having a tertiary amino group). Method.