JP2000044579A - Carbosiloxane dendrimer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having low viscosity and low glass transition temperature and difficult to crystallize, and useful e.g. as a releasant by introducing a highly branched structure wherein siloxane linkages and silalkylene linkages are alternately arranged with a polysiloxane structure as the nucleus. SOLUTION: This polymer has, as a nucleus, a polysiloxane structure having a silicon atom number of >=2 and having a siloxane unit of the formula X1 R1aSiO(3-a)/2 R1 is a 1-10C alkyl or aryl; (a) is 0-2; X1 is a silylalkyl of formula I, in the case of (i)=1, [R2 is a 2-10C alkylene; R3 is a 1-10C alkyl; Xi+1 is a silylalkyl, 1-30C hydrocarbon (R4); (i) is a number of silylalkyl stratum of 1-10; (bi) is 0-3]} and also have a group of formula II. This dendrimer is obtained e.g. by subjecting a polysiloxane having a unit of HR1aSiO(3-a)/2 and a compound having one intramolecular non-conjugated alkenyl to addition reaction in the presence of a platinum-based transition metal catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel carbosiloxane dendrimer and, more particularly, to a novel carbosiloxane dendrimer having a highly branched structure in which a siloxane bond and a silalkylene bond are alternately arranged with a polysiloxane structure as a nucleus, and a narrow molecular weight distribution. It relates to a carbosiloxane dendrimer.

[0002]

2. Description of the Related Art A polymer having a highly branched structure radially from one core and having a narrow molecular weight distribution is called a dendrimer, and is characterized by low viscosity, high reactivity, high solubility, and low glass transition temperature. And its application has attracted attention. As the organosilicon dendrimer, for example, siloxane dendrimer Perevlov et al., Dokl. Aka
d.Nauk. SSSR 309, 367 (1989); Masamune et al., J. Am. Chem.
Soc. 112, 7077 (1990)｝, carbosiloxane dendrimer ｛Kakimoto et al., Macromolecules 24, 3469 (1991);
JP-A-7-17981, Shaiko et al., Macromol.
Rapid Commun. 17,283 (1996)), carbosilane dendrimer ｛Luvers et al., Macromolecules 26, 963 (1
993); Japanese Patent Application Laid-Open No. 8-31205 is known. Among these, carbosiloxane dendrimers in which siloxane bonds and silalkylene bonds are alternately arranged are also disclosed {JP-A-7-17981; Shaiko et al., Macromol. Rapid Commun. 17, 283 (1)
996), these are limited to those using a silane compound in which a plurality of vinyl groups or allyl groups are bonded to one silicon atom as a core material of the dendrimer, and
There is a disadvantage that only a low molecular weight dendrimer having a small number of layers can be obtained. Further, the synthesis of a highly branched polymer in which siloxane bonds and silalkylene bonds are alternately arranged by a one-step polymerization method has also been disclosed.
See Am. Chem. Soc. 113, 4043 (1991). This method has a disadvantage that a dendrimer having a narrow molecular weight distribution cannot be obtained. That is, a carbosiloxane dendrimer having a highly branched structure in which siloxane bonds and silalkylene bonds are alternately arranged, capable of increasing the molecular weight, and having a narrow molecular weight distribution has not been known.

[0003]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention.
That is, an object of the present invention is to provide a novel carbosiloxane having a highly branched structure in which siloxane bonds and silalkylene bonds are alternately arranged with a polysiloxane structure as a nucleus, capable of increasing the molecular weight, and having a narrow molecular weight distribution. It is to provide a dendrimer.

[0004]

The present invention, in order to solve the problem] has the general formula: X ¹ R ¹
_a SiO _{(3-a) / 2 where} R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, a is an integer of 0 to 2, and X ¹ is i = 1 Is a silylalkyl group represented by the following formula:

Embedded image (Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group, R ² is an alkylene group having 2 to 10 carbon atoms, and R ³ is an alkyl group having 1 to 10 carbon atoms. X ^{i + 1} is the above silylalkyl group or 1 to 1 carbon atoms
30 hydrocarbon groups. i is an integer from 1 to 10, which shows the hierarchy of the silylalkyl group, b ⁱ is an integer of 0 to 3. ) Having a polysiloxane structure having two or more silicon atoms containing a siloxane unit represented by に as a nucleus;
formula:

Embedded image Wherein R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, and R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms. It relates to a siloxane dendrimer.

[0005]

Carbosiloxane dendrimer of the embodiment of the present invention have the general ^{_{formula: X 1 R 1 a SiO (}} 3-a) / 2 silicon atoms containing siloxane units of the same type or different represented by 2
It is a compound having the above-mentioned polysiloxane structure at its core.
In the above formula, R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group and a cyclopentyl group. , A cyclohexyl group, and an aryl group includes a phenyl group,
An example is a naphthyl group. Among these, a methyl group is preferred. a is an integer of 0 to 2. X ¹ is a silylalkyl group represented by the following formula when i = 1.

Embedded image In the above formula, R ² is an alkylene group having 2 to 10 carbon atoms, and a linear alkylene group such as ethylene group, propylene group, butylene group, hexylene group; methylmethylene group, methylethylene group, 1-methylpentene Examples thereof include a branched alkylene group such as a ren group and a 1,4-dimethylbutylene group. Among them, ethylene group, methylmethylene group,
Hexylene, 1-methylpentylene and 1,4-dimethylbutylene are preferred. R ³ is an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group,
A butyl group, a pentyl group and an isopropyl group are exemplified.
Among these, a methyl group or an ethyl group is preferable. R ¹
Is the same as above. X ^{i + 1} is the silylalkyl group or an unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group. Alkyl groups such as phenyl, isopropyl, isobutyl, cyclopentyl and cyclohexyl groups; aryl groups such as phenyl, naphthyl, tolyl and xylyl groups; vinyl groups, allyl groups, butenyl groups, pentenyl groups and hexenyl groups An alkenyl group; an aralkyl group such as a benzyl group and a phenethyl group; i represents an integer of 1 to 10, b ⁱ is an integer of 0 to 3. Here, i is the number of levels of the silylalkyl group,
That is, it indicates the number of repetitions of the silylalkyl group.
Therefore, when the number of levels is 1, the silylalkyl group has the general formula:

Embedded image In the case where the number of levels is 2, the silylalkyl group is represented by the general formula:

Embedded image In the case where the number of classes is 3, the silylalkyl group is represented by the general formula:

Embedded image Indicated by In the above ^{formulas, R 1, R 2, R} 3, b 1, b 2, b 3 are as defined above, R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms, in the X ^{i + 1} The same groups as exemplified above can be mentioned.
The carbosiloxane dendrimer of the present invention has the formula:

Embedded image (In the formula, R ¹ and R ⁴ are the same as described above.)

The polysiloxane structure which is the core of the carbosiloxane dendrimer of the present invention has the above general formula: X ¹ R ¹ _a SiO
_{(3-a) / 2} (wherein X ¹ , R ¹ and a are the same as described above) as long as it is a siloxane structure having two or more silicon atoms containing a siloxane unit, and represented by the general formula: X ¹ R ¹
_a SiO _{(3-a) / 2} (wherein X ¹ , R ¹ and a are the same as those described above), and a siloxane unit represented by the general formula. General formula: R ¹ _c SiO _{(4-c) / 2} (wherein, R ¹ is the same as described above, and c
Is an integer of 0 to 3. )), A polysiloxane structure comprising a siloxane unit represented by the following formula: The siloxane units that constitute the nucleus of the carbosiloxane dendrimer of the present invention, the general formula: X ¹ R ¹ ₂ SiO _1/2 or R ¹
Monofunctional siloxane unit (M unit) represented by ₃ SiO _1/2 ,
General formula: X ¹ R ¹ SiO _2/2 or R ¹ ₂ 2 functional siloxane unit represented by SiO _2/2 (D unit), the general formula: X ¹ SiO _3/2 or R ¹
_{Trifunctional} siloxane unit (T unit) represented by SiO _3/2 , Si
There is a tetrafunctional siloxane unit (Q unit) represented by O _4/2 . The carbosiloxane dendrimer of the present invention having a polysiloxane structure having such a siloxane unit bonded as a nucleus and having a highly branched structure radially from the nucleus includes a compound represented by the following general formula. In the formula, X ¹ and R ¹ are the same as described above, and m, n, x, y, z,
p, q, r, s, and t are 1 or more indicating the number of siloxane units present in one molecule, (p + q) is 5 or more, and (s + t)
Is 6 or more.

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Embedded image (X ¹ R ¹ ₂ SiO _1/2 ) _p (R ¹ SiO _3/2 ) _q (X ¹ SiO _3/2 ) _r (X ¹ R ¹ ₂ SiO _1/2 ) _s (SiO _4/2 ) _t The carbosiloxane dendrimer of the present invention is a single compound or a mixture thereof, and preferably has a polydispersity-based molecular weight dispersion index, that is, the quotient (Mw / Mn) of the weight average molecular weight and the number average molecular weight of 2 or less.

Specific examples of the carbosiloxane dendrimer of the present invention include polymers represented by the following average molecular formula.

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The carbosiloxane dendrimer of the present invention has, for example, the general formula: HR ¹ _a SiO _{(3-a) / 2} (wherein R ¹ and
a is the same as above. ), The starting material is a silicon-bonded hydrogen atom-containing polysiloxane having 2 or more silicon atoms, and any one of the following steps (x) to (w) is performed at least once, and finally the step (z) or It can be manufactured by performing the step (w). Specifically, a method in which only the step (z) is performed, a step (x) and a step (y) are alternately performed at least once, and then the step (z) is performed after the step (y), or (x )) Followed by the step (w). Step (x): the starting material or a silicon-bonded hydrogen atom-containing carbosiloxane dendrimer produced in the following step (y) and a general formula: R ⁵ Si (OR ³ ) ₃ (wherein R ³ is the same as described above) R ⁵ is an alkenyl group having 2 to 10 carbon atoms.) In the presence of a platinum-based transition metal catalyst. Step (y): the alkoxy group-containing carbosiloxane dendrimer obtained in the above step (x) and a general formula:

Embedded image (Wherein R ¹ is the same as defined above) under the acidic condition. Step (z): adding the starting material or the carbosiloxane dendrimer obtained in step (y) and a compound having one non-conjugated alkenyl group in one molecule in the presence of a platinum-based transition metal catalyst The step of reacting. Step (w): the alkoxy group-containing carbosiloxane dendrimer obtained in the above step (x) and a general formula:

Embedded image Wherein R ¹ and R ⁴ are as defined above, under acidic conditions.

Examples of the platinum-based transition metal catalyst used in the steps (x) and (z) include chloroplatinic acid, alcohol-modified chloroplatinic acid, an olefin complex of platinum, and a diketonate complex of platinum. When performing an addition reaction using this platinum-based transition metal catalyst, it is preferable to react a slightly excessive alkenyl group-containing compound in order to completely react the silicon-bonded hydrogen atoms in the raw material. After the reaction, an excess amount of the alkenyl group-containing compound can be separated and recovered by distillation under reduced pressure or the like. This addition reaction can be performed at room temperature or under heating conditions, and can also be performed using a solvent that does not interfere with the reaction. The alkenyl group-containing alkoxysilane used in the step (x) includes
Examples of vinyltrimethoxysilane, vinyltriethoxysilane, hexenyltrimethoxysilane, and hexenyltriethoxysilane include compounds having one non-conjugated alkenyl group in one molecule used in the step (z), such as butene; Isobutene, hexene, octene, styrene, α-methylstyrene, vinyltris (trimethylsiloxy) silane, and vinylbis (trimethylsiloxy) methoxysilane are exemplified.

The acidic substance used to create the acidic conditions in the above steps (y) and (w) includes hydrochloric acid,
Sulfuric acid, carboxylic acids, sulfonic acids or mixtures thereof are preferred. In the step (y), the carbosiloxane dendrimer of the present invention may contain a small amount of a monoalkoxysiloxy group represented by the following formula due to alcohol decomposition of the silicon-bonded hydrogen atom.

Embedded image (In the formula, R ¹ and R ³ are the same as described above.)

The carbosiloxane dendrimer of the present invention as described above has a highly branched structure in which a siloxane bond and a silalkylene bond are alternately arranged with a polysiloxane structure as a nucleus. It has the characteristic that the distribution is narrow. Further, since the carbosiloxane dendrimer of the present invention has an unsubstituted hydrocarbon group at all terminals of the branched structure, it has a low viscosity despite having a highly branched structure, and has a glass transition as low as linear polysiloxane. It has a characteristic that it has a temperature and hardly causes crystallization. Therefore, the carbosiloxane dendrimer of the present invention is useful as a release agent, a lubricant, and a resin additive.

[0012]

The present invention will be described below with reference to examples. In the examples, the carbosiloxane dendrimer of the present invention was identified by ²⁹ Si-nuclear magnetic resonance analysis and gel permeation chromatography analysis (solvent: toluene).

[0013]

Example 1 Into a 100 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel were charged 35.5 g of vinyltris (trimethylsiloxy) silane and 0.04 g of a 3% solution of chloroplatinic acid in isopropanol. These were heated to 100 ° C. with stirring. To this, 8.2 g of tetrakis (dimethylsiloxy) silane was slowly added dropwise using a dropping funnel so that the reaction temperature was kept at 100 ° C. After the addition was completed, the reaction solution was heated at 120 ° C. for 1 hour. After cooling, the mixture was concentrated under reduced pressure to obtain 40.5 g of a slightly brown liquid. The viscosity of the obtained liquid at 25 ° C. is 9
It was 8 centistokes, the glass transition temperature determined by a differential scanning calorimeter was -85.1 ° C, and it was confirmed that crystallization, which is usually found in linear polydimethylsiloxane, did not occur. This reaction product was converted to ²⁹ Si-
Analysis by nuclear magnetic resonance analysis revealed that it was a carbosiloxane dendrimer represented by the following average molecular formula. The carbosiloxane dendrimer had a polystyrene reduced number average molecular weight of 2180 as determined by gel permeation chromatography and a dispersity index of 1.0.
It was confirmed to be 6.

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[0014]

Example 2 107 g of vinyltrimethoxysilane and 0.04 g of a 3% solution of chloroplatinic acid in isopropanol were charged into a 200 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. While heating to 100 ° C. To this, 49.4 g of tetrakis (dimethylsiloxy) silane was slowly added dropwise using a dropping funnel so that the reaction temperature was kept at 100 ° C. After the addition was completed, the reaction solution was heated at 120 ° C. for 1 hour. After cooling,
Upon concentration under reduced pressure, 138 g of a light brown liquid was obtained. This was designated as Intermediate A. Next, a stirrer, thermometer,
In a 2-liter four-necked flask equipped with a reflux condenser and a dropping funnel, 210 g of 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 67.6 g of acetic acid and 0.20 g of trifluoromethanesulfonic acid were placed. The temperature was raised to 50 ° C. while stirring and stirring. To this, 120 g of the intermediate A obtained above was slowly dropped over 1 hour using a dropping funnel. After completion of the dropwise addition, the reaction solution was heated at
Stirred for hours. After cooling, transfer the reaction solution to a separatory funnel,
2 times with 200 ml of water, 1 aqueous saturated sodium hydrogen carbonate solution
Washed once with 00 ml and dried over anhydrous magnesium sulfate. The generated solids were separated by filtration, and the obtained solution was concentrated under reduced pressure to obtain 212 g of a colorless transparent liquid. When this reaction product was analyzed by ²⁹ Si-nuclear magnetic resonance analysis, it was found that one molecule per molecule represented by the following average molecular formula was obtained.
It was found to be a carbosiloxane dendrimer having two vinyl groups. The carbosiloxane dendrimer was found to have a polystyrene reduced number average molecular weight of 1211 by gel permeation chromatography and a dispersity index of 1.28.

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[0015]

EXAMPLE 3 182 g of vinyltrimethoxysilane and 0.28 g of a 3% solution of chloroplatinic acid in isopropanol were charged into a 300 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. While heating to 100 ° C. To this, 100 g of methyltris (dimethylsiloxy) silane was slowly added dropwise using a dropping funnel so that the reaction temperature was kept at 100 ° C. After the addition was completed, the reaction solution was heated at 120 ° C. for 1 hour. After cooling,
When the reaction solution was concentrated under reduced pressure, 266 g of a slightly brown liquid was obtained. This was designated as Intermediate E. Next, a stirring device,
500m equipped with thermometer, reflux condenser and dropping funnel
In a four-necked flask, 127 g of 1,1,3,3-tetramethyldisiloxane, 33 ml of concentrated hydrochloric acid, 66 ml of water
And 66 ml of isopropanol were charged and stirred. Next, 100 g of the intermediate E obtained above was slowly added dropwise over 1 hour using a dropping funnel. After the addition was completed, the reaction solution was stirred at room temperature for 1 hour. After the reaction solution was transferred to a separating funnel and the lower layer was separated, the remaining upper layer solution was washed twice with 30 ml of water and saturated aqueous sodium hydrogen carbonate solution 3 times.
It was washed once with 0 ml and dried over anhydrous sodium sulfate. The solid was filtered off, and the obtained solution was concentrated under reduced pressure to obtain 156 g of a colorless transparent liquid. This was designated as Intermediate F. Finally, 30.0 g of the intermediate F obtained above and 0.03 g of a 3% chloroplatinic acid isopropanol solution were charged into a 100 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. Heat to 100 ° C. with stirring. Add 24.6 g of hexene
Was slowly added dropwise using a dropping funnel so that the reaction temperature was maintained at 100 ° C. After completion of the dropwise addition, the reaction solution is heated to 100 ° C.
For 1 hour. After cooling, the reaction solution was concentrated under reduced pressure to obtain 44.4 g of a slightly brown liquid. When the reaction product was analyzed by ²⁹ Si-nuclear magnetic resonance analysis,
It was found to be a carbosiloxane dendrimer represented by the following average molecular formula. The carbosiloxane dendrimer was confirmed to have a number average molecular weight in terms of polystyrene of 2476 by gel permeation chromatography and a dispersity index of 1.08.

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[0016]

EXAMPLE 4 121 g of vinyltrimethoxysilane and 0.2 g of a 3% solution of chloroplatinic acid in isopropanol were charged into a 200 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. While 1
Heated to 00 ° C. To this, 50 g of 1,1,3,3-tetramethyldisiloxane was slowly added dropwise using a dropping funnel so that the reaction temperature was maintained at 100 ° C. After the addition was completed, the reaction solution was heated at 120 ° C. for 1 hour. After cooling, the reaction solution was concentrated under reduced pressure to obtain 158 g of a slightly brown liquid. This was used as Intermediate G. Next, 180 g of 1,1,3,3-tetramethyldisiloxane, 50 ml of concentrated hydrochloric acid, 100 ml of water, and 100 ml of isopropanol were placed in a 1-liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. These were charged and stirred. To this, 158 g of the intermediate G obtained above was slowly dropped over 1 hour using a dropping funnel. After dropping,
The reaction solution was stirred at room temperature for 1 hour. After the reaction solution was transferred to a separating funnel and the lower layer was separated, the remaining upper layer solution was washed with 100 ml of water.
twice with saturated sodium bicarbonate solution 100ml
And dried over anhydrous sodium sulfate. The solid was separated by filtration, and the obtained solution was concentrated under reduced pressure.
3 g of a clear, colorless liquid were obtained. This was designated as Intermediate H. Finally, 133 g of vinyltris (trimethylsiloxy) silane and 0.09 g of a 3% solution of chloroplatinic acid in isopropanol were charged into a 200 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. While heating to 100 ° C. To this, 40.0 g of the intermediate H obtained above was slowly added dropwise using a dropping funnel so that the reaction temperature was maintained at 100 ° C. After the addition was completed, the reaction solution was heated at 120 ° C. for 1 hour. After cooling, the mixture was concentrated under reduced pressure to obtain 127 g of a slightly brown liquid.
The reaction product was analyzed by ²⁹ Si-nuclear magnetic resonance analysis and found to be a carbosiloxane dendrimer represented by the following average molecular formula. The carbosiloxane dendrimer was confirmed to have a polystyrene reduced number average molecular weight of 2911 by gel permeation chromatography and a dispersity index of 1.08.

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[0017]

EXAMPLE 5 49.4 g of vinyltrimethoxysilane and 0.04 g of a 3% chloroplatinic acid isopropanol solution were charged into a 100 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. Heat to 100 ° C. with stirring. In addition, the average molecular formula:

Embedded image Was slowly added dropwise using a dropping funnel so that the reaction temperature was maintained at 100 ° C. After the addition was completed, the reaction solution was heated at 120 ° C. for 1 hour. After cooling, the reaction solution was concentrated under reduced pressure to give 63.1.
g of a light brown liquid was obtained. This was designated as Intermediate K. Next, 33.9 g of 1,1,3,3-tetramethyldisiloxane, 13 ml of concentrated hydrochloric acid were placed in a 200 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel.
27 ml of water and 27 ml of isopropanol were charged and stirred. This is then added to the intermediate K obtained above
40.0 g was slowly added dropwise over 1 hour using a dropping funnel. After the addition was completed, the reaction solution was stirred at room temperature for 1 hour. After transferring the reaction solution to a separating funnel to separate the lower layer,
The remaining upper layer solution was washed twice with 20 ml of water and once with 20 ml of a saturated aqueous solution of sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. The solid was filtered off, and the obtained solution was concentrated under reduced pressure to obtain 45.4 g of a colorless transparent liquid.
This was designated as Intermediate L. Finally, 65.5 g of α-methylstyrene and 0.04 g of a 3% solution of chloroplatinic acid in isopropanol were charged into a 100 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. While heating to 100 ° C. To this, 24.0 g of the intermediate L obtained above was slowly added dropwise using a dropping funnel so that the reaction temperature was maintained at 100 ° C. After the addition was completed, the reaction solution was heated at 120 ° C. for 1 hour. After cooling, the mixture was concentrated under reduced pressure to obtain 35.1 g of a slightly brown liquid. The reaction product was analyzed by ²⁹ Si-nuclear magnetic resonance analysis and found to be a carbosiloxane dendrimer represented by the following average molecular formula. The carbosiloxane dendrimer had a polystyrene reduced number average molecular weight of 3830 as determined by gel permeation chromatography.
And the dispersity index was confirmed to be 1.75.

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[0018]

Example 6 In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 214 g of vinyltrimethoxysilane and 0.16 g of a 3% solution of chloroplatinic acid in isopropanol were charged and stirred. While heating to 100 ° C. In addition, the average composition formula: {H (CH ₃ ) ₂ Si
100 g of a polysiloxane represented by O _1/2 } ₁₀ (SiO _4/2 ) ₅
Was slowly added dropwise using a dropping funnel so that the reaction temperature was maintained at 100 ° C. After completion of the dropwise addition, the reaction solution was heated to 120 ° C.
For 1 hour. After cooling, the mixture was concentrated under reduced pressure.
4 g of a light brown liquid were obtained. This was designated as Intermediate M.
Then, 1,1,3,3 was placed in a 1000 ml four-necked flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel.
468 g of tetramethyldisiloxane, 75 m of concentrated hydrochloric acid
l, 150 ml of water and 150 ml of isopropanol were charged and stirred. To this, the intermediate obtained above
M220g was slowly dripped over 1 hour using the dropping funnel. After the addition was completed, the reaction solution was stirred at room temperature for 1 hour. After transferring the reaction solution to a separating funnel to separate the lower layer,
The remaining upper layer solution was washed twice with 100 ml of water and once with 100 ml of a saturated aqueous solution of sodium hydrogen carbonate, and dried over anhydrous sodium sulfate. The solid content was separated by filtration, and the obtained solution was concentrated under reduced pressure to obtain 273 g of a colorless transparent liquid. This was designated as Intermediate N. Finally, 200 ml 4 equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was added.
In a one-necked flask, vinyl tris (trimethylsiloxy)
105 g of silane and 0.07 g of a 3% solution of chloroplatinic acid in isopropanol were added, and these were heated to 100 ° C. with stirring. This was then added to the intermediate N35.0 obtained above.
g was slowly added dropwise using a dropping funnel so that the reaction temperature was maintained at 100 ° C. After completion of the dropwise addition, the reaction solution is
Heated at 0 ° C. for 1 hour. After cooling, the reaction solution was concentrated under reduced pressure to obtain 80.3 g of a slightly brown liquid. The reaction product was analyzed by ²⁹ Si-nuclear magnetic resonance analysis and found to be a carbosiloxane dendrimer represented by the following average molecular formula. The carbosiloxane dendrimer was found to have a polystyrene reduced number average molecular weight of 6,586 as determined by gel permeation chromatography and a dispersity index of 1.14.

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[0019]

The carbosiloxane dendrimer of the present invention has a highly branched structure in which a siloxane bond and a silalkylene bond are alternately arranged with a polysiloxane structure as a nucleus, is capable of increasing the molecular weight, and has a molecular weight distribution. It has the characteristic of being narrow. Further, the carbosiloxane dendrimer of the present invention has such a characteristic that despite having such a highly branched structure, the viscosity is low, the glass transition temperature is as low as that of the linear polysiloxane, and crystallization hardly occurs. Have.

[Brief description of the drawings]

FIG. 1 is a ²⁹ Si-nuclear magnetic resonance spectrum of the carbosiloxane dendrimer obtained in Example 1.

FIG. 2 is a ²⁹ Si-nuclear magnetic resonance spectrum of the carbosiloxane dendrimer obtained in Example 2.

FIG. 3 is a ²⁹ Si-nuclear magnetic resonance spectrum of the carbosiloxane dendrimer obtained in Example 3.

FIG. 4 is a ²⁹ Si-nuclear magnetic resonance spectrum of the carbosiloxane dendrimer obtained in Example 4.

FIG. 5 is a ²⁹ Si-nuclear magnetic resonance spectrum of the carbosiloxane dendrimer obtained in Example 5.

FIG. 6 is a ²⁹ Si-nuclear magnetic resonance spectrum of the carbosiloxane dendrimer obtained in Example 6.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H049 VN01 VP10 VQ02 VQ79 VR21 VR23 VR41 VR43 VR44 VW02 4J035 CA01N HA01 HB10

Claims (2)

[Claims] 1. A general formula: X ¹ R ¹ _a SiO _{(3-a) / 2 wherein} R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, and a is an integer of 0 to 2. And X ¹ is a silylalkyl group represented by the following formula when i = 1. Embedded image (Wherein, R ¹ is an alkyl group having 1 to 10 carbon atoms or an aryl group, R ² is an alkylene group having 2 to 10 carbon atoms, and R ³ is an alkyl group having 1 to 10 carbon atoms. X ^{i + 1} is the above silylalkyl group or 1 to 1 carbon atoms
30 hydrocarbon groups. i is an integer from 1 to 10, which shows the hierarchy of the silylalkyl group, b ⁱ is an integer of 0 to 3. ) Having a polysiloxane structure having two or more silicon atoms containing a siloxane unit represented by に as a nucleus;
Formula: Wherein R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, and R ⁴ is a hydrocarbon group having 1 to 30 carbon atoms. Siloxane dendrimer. 2. The carbosiloxane dendrimer according to claim 1, which has a polystyrene equivalent molecular weight polydispersity index of 2 or less.