JP2001316473A - Dendrimer-structure-container polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel dendrimer-structure-containing polymer obtained by hydrosilylating an organosilicon compound having an acrylic or methacrylic group and a specified dendrimer structure with a silicon-bonded-hydrogen- containing polymer. SOLUTION: There is provided is a dendrimer-structure-containing polymer obtained by reacting an organosilicon compound represented by the general formula: (wherein R1 is a 1-10C alkyl or an aryl; R2 is a divalent organic group; c is 2 or 3; X1 is a specified silylalkyl; and Y is an organic group containing an acrylic or methacrylic group) with a silicon-bonded-hydrogen-containing polymer in the presence of a transition metal hydrosilylation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer having a dendrimer structure. More specifically, the present invention relates to a novel polymer having a dendrimer structure obtained by subjecting an organosilicon compound having an acrylic group or a methacrylic group and a specific dendrimer structure to a polymer containing a silicon-bonded hydrogen atom, by a hydrosilylation reaction.

[0002]

2. Description of the Related Art A polybranched siloxane / silalkylene copolymer containing one radically polymerizable group in one molecule and having two or more branch points in the molecule, that is, a radical polymerization reaction Functional carbosiloxane dendrimers are known, and it is also known that various graft copolymers having a dendrimer structure in a side chain can be obtained by reacting them with other radically polymerizable monomers (Japanese Patent Application Laid-open No. Japanese Patent Application Laid-Open No. 11-1485 and Japanese Unexamined Patent Application Publication No.
No. 1530). Furthermore, the present inventors have proposed a carbosiloxane dendrimer exhibiting high radical polymerization reactivity by using a linking structure between the multibranched structure and the radical polymerizable group as an organic group other than an alkylene group (Japanese Patent Application No. 11-110). 216468). However, a hydrosilylation reaction between such a radical polymerization reactive carbosiloxane dendrimer and a compound containing a silicon-bonded hydrogen atom has not been known. In particular, acrylic and methacrylic groups have lower hydrosilylation reactivity than alkenyl groups.In addition, the hydrosilylation reaction between an acrylic or methacrylic group and a silicon-bonded hydrogen atom generally involves only a carbon-carbon double bond. In addition, it proceeds at both ends of the carbon-oxygen double bond or the conjugated carbon-carbon bond and carbon-oxygen double bond, so that only the reaction between the silicon-bonded hydrogen atom and the carbon-carbon double bond proceeds selectively. This was because it was considered difficult. From these, a hydrosilylation reaction product of a carbosiloxane dendrimer having an acryl group or a methacryl group and a compound having a silicon-bonded hydrogen atom has not been known.

On the other hand, as a method for producing a silicon-containing dendrimer, a divergence method and a convergence method are known. While the divergence method is a method of radially assembling a branched structure from the nucleus of a dendrimer molecule, the convergence method first creates a plurality of intermediates having a branched structure, and then uses them as a structure that becomes the core of the dendrimer molecule. This is a method of bonding to units. However, conventionally, in the convergent method, due to the convenience of the synthesis method, the intermediate can have only one functional group required for dendrimer formation, and the available intermediate is limited to those having a molecular weight of 1,000 or less. Had been. For this reason, it was not possible to increase the number of silicon-containing dendrimers by two or more by the convergence method.

[0004]

The inventors of the present invention have made intensive studies to solve the above problems, and as a result, have reached the present invention.
That is, an object of the present invention is to provide a novel dendrimer structure-containing polymer obtained by subjecting an organosilicon compound having an acrylic group or a methacryl group and a specific dendrimer structure to a polymer containing a silicon-bonded hydrogen atom to undergo a hydrosilylation reaction. Is to provide.

[0005]

SUMMARY OF THE INVENTION The present invention provides a compound represented by the general formula:

Embedded image In the formula, R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, R ² is a divalent organic group, and c is 2 to 3
And X ¹ is a silylalkyl group represented by the following formula when i = 1.

Embedded image (Wherein, R ¹ is the same as described above, and R ³ has 2 to 1 carbon atoms.
0 is an alkylene group, R ⁴ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a substituted or unsubstituted 1 to 30 carbon atom containing no silylalkyl group or aliphatic unsaturated bond. It is a substituted monovalent hydrocarbon group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group ^;
It is 0~3, b ⁱ is 0-1. ) Y is a general formula:

Embedded image Or

Embedded image (In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom or an alkyl group or an aryl group having 1 to 10 carbon atoms.) The present invention relates to a polymer having a dendrimer structure obtained by reacting an organosilicon compound represented by｝ with a polymer having a silicon-bonded hydrogen atom in the presence of a catalyst for a transition metal hydrosilylation reaction.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an organosilicon compound as a raw material of the polymer having a dendrimer structure of the present invention will be described. The organosilicon compound used in the present invention is a carbosiloxane dendrimer having one acryl group or methacryl group in one molecule, and has a general formula:

Embedded image Indicated by In the above formula, R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, and as the alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group, A cyclohexyl group is exemplified, and a phenyl group and a naphthyl group are exemplified as the aryl group. Among these, a methyl group is preferred. R ² is a divalent organic group, but is preferably a group composed of a plurality of elements selected from a carbon atom, a silicon atom, a hydrogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom. Specifically, R ² is represented by the formula:

Embedded image An alkylene group as shown by the formula:

Embedded image An arylene group or an aralkylene group represented by the formula:

Embedded image An ether bond-containing hydrocarbon group or an ether bond-containing hydroxyl-substituted hydrocarbon group represented by the formula:

Embedded image A carboxyloxy group as shown by the formula:

Embedded image And a group represented by the following formula, in addition to a siloxy group represented by

Embedded image Y is a general formula:

Embedded image Or

Embedded image And an organic group containing an acryl group or a methacryl group. R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom or an alkyl group or an aryl group having 1 to 10 carbon atoms. As the alkyl group or the aryl group having 1 to 10 carbon atoms, the same groups as in R ¹ are exemplified. Examples of such YR ² — in which R ² and Y are bonded include a group represented by the following formula.

Embedded image c is 2-3. X ¹ is a silylalkyl group represented by the following formula when i = 1.

Embedded image In the above formula, R ³ 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 include a branched alkylene group such as a len group and a 1,4-dimethylbutylene group. Among them, an ethylene group, a methylmethylene group, a hexylene group, a 1-methylpentylene group, and a 1,4-dimethylbutylene group are preferred. R ⁴ 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, an isopropyl group, an isobutyl group,
Examples thereof include a cyclopentyl group and a cyclohexyl group. Among these, a methyl group is preferred. R ¹ is the same as described above. X ^{i + 1} is a silylalkyl group or a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms which does not contain an aliphatic unsaturated bond. Examples of the substituted hydrocarbon group having 1 to 30 carbon atoms not containing an aliphatic unsaturated bond include an alcoholic hydroxyl group, a phenolic hydroxyl group, an amino group, a carboxyl group, a nitrile group, a halogen atom, a cyclic or acyclic ether, and a carboxylic acid. Hydrocarbon groups containing one or more groups, atoms or structures selected from acid esters are preferred. Specifically, 3-hydroxypropyl group, hydroxymethyl group, hydroxyethoxypropyl group is exemplified as the alcoholic hydroxyl group-containing hydrocarbon group, and hydroxyphenyl group, hydroxyphenylpropyl group is exemplified as the phenolic hydroxyl group-containing hydrocarbon group. An aminopropyl group as an amino group-containing hydrocarbon group,
Examples include aminomethyl group, N-butylaminopropyl group, N-cyclohexylaminopropyl group, N, N-dibutylaminopropyl group, N, N-dibutylaminomethyl group, and 3-carboxypropyl as a carboxyl group-containing hydrocarbon group. And a 10-carboxydecyl group; a 2-cyanoethyl group and a 3-cyanopropyl group as a nitrile group-containing hydrocarbon group; a 3-chloropropyl group, a chloromethyl group and a 3,3 as a halogen atom-containing hydrocarbon group;
Examples thereof include 3,3-trifluoropropyl, p-chloromethylphenethyl and nonafluorohexyl, and glycidoxypropyl, 5,6-oxiranylbutyl, and tetrahydrofuryloxy as cyclic ether-containing hydrocarbon groups. Propyl group, and methoxyethoxypropyl, polyoxyethylenylpropyl, and polyoxypropylenylpropyl groups as non-cyclic ether-containing hydrocarbon groups, and acetoxypropyl group and ethoxy as carboxylic acid ester-containing hydrocarbon groups. An example is a carbonylpropyl group. Examples of the unsubstituted hydrocarbon group containing no aliphatic unsaturated bond include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group and a cyclohexyl group; And aryl groups such as naphthyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group and phenethyl group. a ⁱ is 0 to 3 and b ⁱ is 0 to 1, but (a ⁱ + b ⁱ ) needs to be 3 or less. i is an integer of 1 to 10, which indicates the number of levels of the silylalkyl group, that is, the number of repetitions of the silylalkyl group. Accordingly, an organosilicon compound having one rank has the general formula:

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁴ , Y and c are the same as described above, and R ⁷ has 1 to 3 carbon atoms not containing an aliphatic unsaturated bond.)
0 is a substituted or unsubstituted monovalent hydrocarbon group. a ¹ is a 0~3, b ¹ is 0-1. ). If the number of layers is 2, the general formula:

Embedded image (Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁷ , Y and c are the same as above, a ¹ and a ² are 0 to 3, b ¹ and b ² are 0 to ¹
And (a ¹ + b ¹ ) is less than 3. ). If the number of layers is three, the general formula:

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁷ , Y and c are the same as above, a ¹ , a ² and a ³ are 0 to 3, b ¹ , b ² and b
³ is 0 to ¹ , and (a ¹ + b ¹ ) and (a ² + b ² ) are each less than 3. ).

Specific examples of such an organosilicon compound include an organosilicon compound represented by the following average molecular formula.

Embedded image

Embedded image

Embedded image

A polymer containing a silicon-bonded hydrogen atom, which is another raw material of the polymer having a dendrimer structure of the present invention, will be described. The polymer containing a silicon-bonded hydrogen atom used in the present invention contains two or more silicon-bonded hydrogen atoms in one molecule and forms a bond by a hydrosilylation reaction with the organosilicon compound. . Examples of such polymers include organopolysiloxane containing silicon-bonded hydrogen atoms, polyolefin containing silicon-bonded hydrogen atoms, polyalkylene oxide containing silicon-bonded hydrogen atoms, polyester containing silicon-bonded hydrogen atoms, and polyester containing silicon-bonded hydrogen atoms. Examples include polyamides, polyimides containing silicon-bonded hydrogen atoms, and dendrimers substituted with silicon-bonded hydrogen atoms. Among these, organopolysiloxanes containing silicon-bonded hydrogen atoms or dendrimers substituted with silicon-bonded hydrogen atoms are preferred.

Examples of the organopolysiloxane containing silicon-bonded hydrogen atoms include linear, branched and cyclic siloxanes. In this organopolysiloxane, an organic group bonded to a silicon atom other than a hydrogen atom includes an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a cyclopentyl group and a cyclohexyl group. An aryl group such as a phenyl group, a naphthyl group, a tolyl group, and a xylyl group; and a monovalent hydrocarbon group such as an aralkyl group such as a benzyl group and a phenethyl group. As such an organopolysiloxane, a siloxane represented by the following average molecular formula is exemplified.

Embedded image

[0010] The silicon-bonded hydrogen atom terminal-substituted dendrimer is a component constituting a core structure when the polymer containing a dendrimer structure of the present invention is synthesized by a convergent method. This dendrimer is a multi-branched compound having a silicon-bonded hydrogen atom at the branch end, that is, the outermost shell, and the core structure and the number of generations are not particularly limited. Bonding units constituting the dendrimer skeleton include siloxane, silalkylene,
Examples include amines, amides, esters, and ethers. Among these, a carbosiloxane dendrimer composed of a siloxane unit and a silalkylene unit is preferable. As such a dendrimer, a compound represented by the following formula is exemplified.

Embedded image

The polymer having a dendrimer structure of the present invention is
The above acrylic or methacrylic group in one molecule
It is produced by reacting one organosilicon compound and a polymer containing silicon-bonded hydrogen atoms in the presence of a catalyst for a transition metal hydrosilylation reaction. As described above, the hydrosilylation reaction between an acryl group or a methacryl group and a silicon-bonded hydrogen atom involves not only a carbon-carbon double bond but also a carbon-oxygen double bond or a conjugated carbon-carbon bond and a carbon-oxygen dibond. Although it has been conventionally difficult to achieve only the reaction for the carbon-carbon double bond because it proceeds at both ends of the heavy bond, the present invention surprisingly shows that the hydrosilylation reaction is carried out at the carbon-carbon double bond. Only found to progress. The reason for this is not clear, but it is considered that the steric bulkiness of the dendrimer structure has an effect. As the catalyst for the transition metal hydrosilylation reaction, a platinum-based transition metal catalyst is preferable, and examples thereof include chloroplatinic acid, alcohol-modified chloroplatinic acid, an olefin complex of platinum, and a diketonate complex of platinum. The molecular shape of the polymer having a dendrimer structure of the present invention is not specified, and a wide variety of shapes can be obtained by selecting the polymer having a silicon-bonded hydrogen atom. For example, assuming that the dendrimer portion is spherical, a linear polymer having spheres bonded to one or both ends, a linear polymer having several spheres bonded to its side chain, or a branched polymer And spheres bonded to an arbitrary portion of the sphere, and a large sphere formed as a whole by bonding a large number of spheres to a spherical nucleus. The number average molecular weight is preferably in the range of 1,000 to 100,000, and more preferably in the range of 2,000 to 50,000. Examples of such a polymer having a dendrimer structure of the present invention include a polymer represented by the following formula.

Embedded image

Embedded image

Embedded image

The polymer having a dendrimer structure of the present invention as described above has a characteristic that it maintains a low viscosity without gelling, despite having a highly branched structure partially or in the whole molecule. In particular, when the dendrimer structure has a reactive functional group on its surface, that is, when X ^{i + 1} is a group substituted with various reactive groups, their reactivity is very high, and various polymer materials are used. Is useful as a viscoelasticity improver or a crosslinking agent. Furthermore, the polymer having a dendrimer structure of the present invention can be produced in one step using a dendrimer structure having a molecular weight sufficient to exhibit the properties of a dendrimer. Therefore, according to this method, there is an advantage that a polymer having a new special structure having a dendrimer structure at an arbitrary site of a linear polymer or a new dendrimer having two or more generations expanded can be produced in one step. . In particular, the reaction to increase the generation of dendrimers in such a convergent method may be applicable to the case where a dendrimer structure is introduced into a specific site of various polymer compounds. Therefore, it is expected that various dendrimer structure-containing polymers are synthesized. Is done.

[0013]

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

[0014]

Example 1 A 200-ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with the following formula:

Embedded image Was charged and 7.5 mg of a divinylhexamethyldisiloxane solution of platinum divinyltetramethyldisiloxane complex (platinum concentration: 4% by weight) was heated to 140 ° C. while stirring.
This is then added to the average formula:

Embedded image Was added dropwise over 30 minutes.
After completion of the dropwise addition, the reaction solution was heated at 140 ° C. for 2 hours. After cooling, 57.3 g of a light brown transparent liquid was obtained. When this liquid was analyzed by nuclear magnetic resonance analysis, it was found that the obtained reaction product was a dimethylpolysiloxane having a dendrimer structure represented by the following average molecular formula. It was also confirmed that the dendrimer structure-containing dimethylpolysiloxane had a number average molecular weight in terms of polystyrene of 4330 as determined by gel permeation chromatography and a dispersity index of 1.46.

Embedded image

[0015]

Example 2 In a 100 ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, the formula:

Embedded image Was charged and 6.3 mg of a divinylhexamethyldisiloxane solution of a platinum divinyltetramethyldisiloxane complex (platinum concentration: 4% by weight) was heated to 140 ° C. with stirring. This is then added to the average formula:

Embedded image Was added dropwise over 30 minutes.
After completion of the dropwise addition, the reaction solution was heated at 140 ° C. for 2 hours. After cooling, 49.3 g of a light brown transparent liquid was obtained. When this liquid was analyzed by nuclear magnetic resonance analysis, it was found that the obtained reaction product was a dimethylpolysiloxane having a dendrimer structure represented by the following average molecular formula. In addition, it was confirmed that the dendrimer structure-containing dimethylpolysiloxane had a number average molecular weight in terms of polystyrene of 3925 as determined by gel permeation chromatography and a dispersity index of 1.44.

Embedded image

[0016]

Example 3 A 200-ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with the following formula:

Embedded image Was charged and 7.5 mg of a divinylhexamethyldisiloxane solution of a platinum divinyltetramethyldisiloxane complex (platinum concentration: 4% by weight) was heated to 140 ° C. while stirring.
This is then added to the average formula:

Embedded image 2.6 g of a silicon-bonded hydrogen atom-containing polydiorganosiloxane represented by the formula below was added dropwise over 10 minutes. After completion of the dropwise addition, the reaction solution was heated at 140 ° C. for 2 hours. After cooling,
22.8 g of a light brown transparent liquid were obtained. When this liquid was analyzed by nuclear magnetic resonance analysis, the obtained reaction product was found to be a siloxane having a dendrimer structure represented by the following average molecular formula. In addition, it was confirmed that the dendrimer structure-containing siloxane had a number average molecular weight in terms of polystyrene of 5312 by gel permeation chromatography and a dispersity index of 1.23.

Embedded image

[0017]

Example 4 A 200-ml four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with the formula:

Embedded image Was charged and 7.5 mg of a divinylhexamethyldisiloxane solution of a platinum divinyltetramethyldisiloxane complex (platinum concentration: 4% by weight) was heated to 140 ° C. while stirring.
This is then added to the average formula:

Embedded image Was added dropwise over 5 minutes over a period of 5 minutes. After completion of the dropwise addition, the reaction solution was heated at 140 ° C. for 2 hours. After cooling, 22.0 g of a light brown transparent liquid was obtained.
When this liquid was analyzed by nuclear magnetic resonance analysis, it was found that the obtained reaction product was a carbosiloxane dendrimer represented by the following average molecular formula. The carbosiloxane dendrimer has a number average molecular weight in terms of polystyrene of 92 by gel permeation chromatography.
30, and the dispersity index was confirmed to be 1.08.

Embedded image

[0018]

The polymer having a dendrimer structure of the present invention can be obtained by subjecting an organosilicon compound having an acrylic or methacrylic group and a specific dendrimer structure to a polymer containing a silicon-bonded hydrogen atom by a hydrosilylation reaction. It has the characteristic of being a novel polymer.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08G 73/10 C08G 73/10 4J100 (72) Inventor Satoshi Onodera 2-2 Chikusa Kaigan, Ichihara-shi, Chiba Dow Corning Toray F-term in Silicone Corporation R & D Headquarters (reference) HA35 HA61 HC80

Claims (3)

[Claims] 1. A compound of the general formula: In the formula, R ¹ is an alkyl group or an aryl group having 1 to 10 carbon atoms, R ² is a divalent organic group, and c is 2 to 3
And X ¹ is a silylalkyl group represented by the following formula when i = 1. Embedded image (Wherein, R ¹ is the same as described above, and R ³ has 2 to 1 carbon atoms.
0 is an alkylene group, R ⁴ is an alkyl group having 1 to 10 carbon atoms, and X ^{i + 1} is a substituted or unsubstituted 1 to 30 carbon atom containing no silylalkyl group or aliphatic unsaturated bond. It is a substituted monovalent hydrocarbon group. i is an integer of 1 to 10 indicating the hierarchy of the silylalkyl group ^;
It is 0~3, b ⁱ is 0-1. ) Y is a general formula: Or (In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom or an alkyl group or an aryl group having 1 to 10 carbon atoms.) A dendrimer structure-containing polymer obtained by reacting the organosilicon compound represented by｝ with a silicon-bonded hydrogen atom-containing polymer in the presence of a transition metal hydrosilylation reaction catalyst. 2. A polymer containing a silicon atom-bonded hydrogen atom,
Organopolysiloxane containing silicon-bonded hydrogen atoms,
Silicon atom-bonded hydrogen atom terminal substituted dendrimer, Silicon atom-bonded hydrogen atom-containing polyolefin, Silicon atom-bonded hydrogen atom-containing polyalkylene oxide, Silicon atom-bonded hydrogen atom-containing polyester, Silicon atom-bonded hydrogen atom-containing polyamide and Silicon atom-bonded hydrogen atom-containing polyimide 2. A polymer selected from the group consisting of:
4. The polymer having a dendrimer structure according to 1.). 3. A polymer containing a silicon atom-bonded hydrogen atom,
The dendrimer structure-containing polymer according to claim 1, which is a silicon-bonded hydrogen atom-containing organopolysiloxane or a silicon-bonded hydrogen atom terminal-substituted dendrimer.