JP2001181398A - Silicon-containing polymer and manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide novel silicon-containing polymers whose major skeleton is constituted of a siloxane bond, a silicon atom-nitrogen atom bond, and a silalkylene bond, and a method of manufacturing the same. SOLUTION: The silicon-containing polymers have a number average molecular weight of 500-100,000 and a major skeleton constituted of a siloxane bond, a silicon atom-nitrogen atom bond, and a silalkylene bond, and are obtained by polymerizing (a) an organic silicon compound having aliphatic unsaturated bond-containing groups at both molecular chain terminals and (b) a siloxane compound selected from an organopolysiloxane or silalkylenesiloxane which contains one or two hydrogen atoms bonded to the silicon atom per molecule by hydrosilylation reaction. The method of manufacturing the same is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon-containing polymer and a method for producing the same, and more particularly, to a silicon-containing polymer whose main skeleton is composed of a siloxane bond, a silicon atom-nitrogen atom bond, and a silalkylene bond. It relates to a manufacturing method.

[0002]

2. Description of the Related Art A main skeleton is composed of a siloxane bond and a silicon atom.
Examples of the silicon-containing polymer composed of a nitrogen atom bond and a silalkylene bond include, for example, JP-A-2-497
The compounds described in JP-A-93-93 and JP-A-10-182828 are known. The former JP-A-2-49
No. 793 discloses a dehydrocondensation reaction between an aliphatic unsaturated bond-containing amine compound and one of silicon-bonded hydrogen atoms in a siloxane compound having silicon-bonded hydrogen atoms at both molecular chain terminals using a platinum-based catalyst. To prepare a siloxane compound in which one end of the molecular chain is blocked with a silicon-bonded hydrogen atom and the other end is blocked with an aliphatic unsaturated bond-containing amino group, and then the siloxane compound is used as a catalyst for a hydrosilylation reaction. A method of producing a silicon-containing polymer by addition polymerization in the presence is described. However, this production method is dangerous because hydrogen gas is generated, and as a side reaction, a dehydrocondensation reaction between the silicon-bonded hydrogen atoms at both ends of the raw material siloxane compound and the amine compound occurs, so that the target silicon-containing compound is produced. There was a problem that the yield of the polymer was low. On the other hand, the latter JP-A-10-182828 discloses that a siloxane compound having a silicon-bonded hydrogen atom at one end and a halogenosilyl group at the other end and an amine compound containing an aliphatic unsaturated bond are dehydrohalogenated. A condensation reaction is performed to synthesize an organosiloxane compound in which one terminal of the molecular chain is blocked with a silicon-bonded hydrogen atom and the other terminal is blocked with an aliphatic unsaturated bond-containing amino group, and then the siloxane compound is subjected to a hydrosilylation reaction. It describes a silicon-containing polymer obtained by addition polymerization using a catalyst. However, the siloxane compound having a silicon-bonded hydrogen atom at one terminal and a halogenosilyl group at the other terminal used in this method has difficulty in synthesizing a high polymer. There is a disadvantage that it is difficult to increase the ratio of siloxane units in the skeleton.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have intensively studied 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 silicon-containing polymer whose main skeleton is composed of a siloxane bond, a silicon atom-nitrogen atom bond, and a silalkylene bond, which can increase the content of the siloxane unit, and a method for producing the same. To provide.

[0004]

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

Embedded image [Wherein A is the same or different aliphatic unsaturated bond-containing monovalent hydrocarbon group or formula:

Embedded image (In the formula, R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ⁵ is a divalent hydrocarbon group having no aliphatic unsaturated bond or an alkyleneoxyalkylene group. )), R ¹ is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ² is a monovalent hydrocarbon group having no aliphatic unsaturated bond. A is a valent hydrocarbon group or a hydrogen atom, and a is an integer of 0 or more. An organosilicon compound represented by the formula:
(B) General formula:

Embedded image [Wherein, R ¹ is the same as described above, R ³ is a divalent hydrocarbon group having no aliphatic unsaturated bond, 1 and m are 1 or 2, and n is an integer of 0 or more. , (L + n) is 3 or more. And a siloxane compound selected from an organopolysiloxane or a silalkylenesiloxane represented by the following formula (c):

Embedded image (Wherein, A, R ¹ and R ⁵ are the same as described above). The main skeleton is formed by polymerization of an organic compound selected from the compounds represented by the following formulas by a hydrosilylation reaction. The present invention relates to a silicon-containing polymer having a number average molecular weight of 500 to 100,000 and comprising a nitrogen atom bond and a silalkylene bond, and a method for producing the same.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The general formula of the component (a) used in the present invention:

Embedded image Is a component that forms a silicon atom-nitrogen atom bond in the silicon-containing polymer of the present invention. In the above formula, A is an aliphatic unsaturated bond-containing monovalent hydrocarbon group, or a compound represented by the formula:

Embedded image (In the formula, R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ⁵ is a divalent hydrocarbon group having no aliphatic unsaturated bond or an alkyleneoxyalkylene group. ), Specifically, an alkenyl group such as a vinyl group, an allyl group, a butenyl group, and a hexenyl group; an acryloxypropyl group, a methacryloxypropyl group, and a methacryloxyethyloxy group. An example is a propyl group. Among them, A is preferably an alkenyl group from the viewpoint of high addition reactivity. In addition, A in the same molecule may be the same or different. R ¹ is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aryl group such as a phenyl group, a tolyl group, and a xylyl group. Groups; aralkyl groups such as benzyl and phenethyl; Among these,
R ¹ is preferably an alkyl group or a phenyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group. R ² is a monovalent hydrocarbon group having no aliphatic unsaturated bond or a hydrogen atom. As the monovalent hydrocarbon group, those having 1 to 20 carbon atoms are preferable, and an ethyl group, a butyl group, and a t-butyl group are preferred. And an aryl group such as a phenyl group and a tolyl group. This R ² is preferably an alkyl group or a hydrogen atom,
It is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. a is an integer of 0 or more, preferably in the range of 0 to 200, and more preferably in the range of 0 to 100.

Examples of the organosilicon compound of the component (a) include compounds represented by the following formula.

Embedded image

The organosilicon compound of the component (a) is, for example, (d) a general formula:

Embedded image (Wherein X is a halogen atom, and R ¹ , A and a are the same as described above), and (e) a general formula:

Embedded image (Wherein, A and R ² are the same as those described above).

As the halogen atom of X in the component (d), a chlorine atom or a bromine atom is exemplified, but a chlorine atom is preferred. As such a halogenosilyl group-containing organosilicon compound, the following compounds are exemplified.

Embedded image

The method of preparing the organosilyl group-containing organosilicon compound is not limited. For example, when the siloxane unit is an organosiloxane having 3 or more,
General formula:

Embedded image (In the formula, R ¹ is the same as described above. B is an integer of 3 or more, preferably in the range of 3 to 10, more preferably in the range of 3 to 6.) And the general formula:

Embedded image (Wherein R ¹ , A and X are the same as those described above). As the cyclic siloxane compound used here, hexamethylcyclotrisiloxane,
Octamethylcyclotetrasiloxane is exemplified. Among them, hexamethylcyclotrisiloxane is preferable because of high ring opening reactivity. Examples of the silane compound represented by the above general formula include dimethylvinylchlorosilane,
Methylphenylvinylchlorosilane is exemplified, in particular,
Dimethylvinylchlorosilane is preferred because of its reactivity and availability.

The amine compound of the above component (e) is (a)
It is a raw material for introducing an aliphatic unsaturated bond-containing amino group into an organosilicon compound as a component. The component (e) includes a general formula:

Embedded image The amine compound represented by is preferred. In the above formula, R ³ is a divalent hydrocarbon group having no aliphatic unsaturated bond, and preferably has 1 to 20 carbon atoms, specifically, methylene, ethylene, propylene, and butylene. And an alkylene group such as a group; and an arylene group such as a phenylene group, a tolylene group, and a xylylene group. Among them, R ³ is preferably an alkylene group, more preferably an alkylene group having 1 to 4 carbon atoms. Examples of the amine compound as the component (e) include the following compounds.

Embedded image

In the dehydrohalogenation condensation reaction between the organosilyl group-containing organosilicon compound (d) and the amine compound (e), the amine compound (e) is equimolar to the organosilicon compound (d). It is preferable to use the above. At this time, it is preferable to add a hydrogen halide scavenger in order to trap the by-produced hydrogen halide. As the hydrogen halide scavenger used,
Examples include triethylamine, pyridine, diethylamine, ethylamine, N, N-dimethylaminopyridine. The use of an organic solvent in this condensation reaction is optional, but it is preferable to use a solvent in order to facilitate stirring and mixing. The organic solvent that can be used is not limited as long as it is non-reactive with the above-mentioned raw materials. However, a solvent having low solubility of the generated salt is desirable.
Preferred are n-heptane, toluene, xylene and the like. The temperature conditions during the condensation reaction are not limited, but are preferably in the range of 0 ° C to 60 ° C.

The siloxane compound of the component (b) used in the present invention is selected from compounds represented by the following general formula, and contains one or two silicon-bonded hydrogen atoms per molecule. It is a polysiloxane or a silalkylenesiloxane, and is a component for introducing a siloxane unit into the silicon-containing polymer of the present invention.

Embedded image In the above formula, R ¹ and R ³ are the same as described above. l and m
Is 1 or 2. n is an integer of 0 or more;
000 is preferred. Further, (l + n) is an integer of 3 or more, and preferably in the range of 3 to 20.

Examples of the siloxane compound as the component (b) include the following compounds.

Embedded image

Further, in the present invention, as the component (c), addition polymerization is carried out in the presence of an organic compound having one or two aliphatic unsaturated bond-containing groups in one molecule and which does not inhibit addition polymerization. Can be. This organic compound is selected from compounds represented by the following general formula.

Embedded image In the above formula, A, R ¹ and R ⁵ are the same as described above. Examples of such organic compounds include the following compounds.

Embedded image

The hydrosilylation reaction catalyst used in the present invention includes a platinum metal catalyst, a rhodium catalyst, and a palladium catalyst. Among these, platinum metal catalysts are particularly preferable because of their good reactivity. Specifically, chloroplatinic acid, an alcohol solution of chloroplatinic acid, an olefin complex of platinum, an alkenylsiloxane complex of platinum, An example is a carbonyl complex of platinum. The addition amount of the hydrosilylation reaction catalyst may be an amount sufficient to promote addition polymerization. For example, when a platinum metal-based catalyst is used, the components (a) and (b), or It is preferable that the amount of platinum metal is in the range of 2 to 100 parts by weight with respect to 1,000,000 parts by weight of the total of components (a) to (c). This is because if the amount is less than 2 parts by weight, the addition polymerization tends not to proceed sufficiently, while if it exceeds 100 parts by weight, side reactions tend to occur.

The above components (a) and (b), or
The reaction temperature conditions in the addition polymerization of the components (a) to (c) are not limited, but are preferably in the range of 50 to 220 ° C, and more preferably in the range of 80 to 180 ° C. This addition polymerization may be performed in an organic solvent. The organic solvent that can be used is not limited as long as it does not inhibit the addition polymerization reaction.
aliphatic hydrocarbons such as n-heptane; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as methyl ethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate;
Ethers such as dioxane and diethyl ether are exemplified. One of these solvents may be used alone,
Two or more types may be used in combination. The solvent used is preferably dried in advance. The number average molecular weight of the silicon-containing polymer of the present invention obtained by such addition polymerization is usually in the range of 500 to 100,000,
Preferably within the range of 500-50,000, 1,000-2
More preferably, it is within the range of 0,000.

The silicon-containing polymer of the present invention as described above is
Since the main skeleton is a polymer compound composed of a siloxane bond, a silicon atom-nitrogen atom bond, and a silalkylene bond, for example, it has excellent compatibility with an organic resin and is useful as a physical property modifier of the organic resin. .

[0018]

The present invention will be described below in detail with reference to examples. In the examples, the viscosity is a value measured at 25 ° C. The number average molecular weight of the obtained silicon-containing polymer was a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene. The silicon-bonded hydrogen atom content of the siloxane compound as the raw material and the vinyl group content of the organosilicon compound were quantified by nuclear magnetic resonance (NMR) analysis.

[0019]

REFERENCE EXAMPLE 1 Under a nitrogen atmosphere, 45.5 g (0.45 mol) of triethylamine, 18 g (0.32 mol) of allylamine and 70 ml of hexane were charged into a 300 ml four-necked flask equipped with a stirrer, a dropping funnel and a thermometer. Then dimethylvinylchlorosilane 3
A mixed solution of 6.2 g (0.3 mol) and 30 ml of hexane was dropped over 20 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours, and the produced salt was filtered using a glass filter. This filtrate was subjected to atmospheric distillation to obtain 112
As a fraction at ~ 119 ° C, the formula:

Embedded image 14.2 g of an organosilicon compound represented by the formula was prepared. The vinyl group content of this organosilicon compound is 37.1% by weight.
Met.

[0020]

REFERENCE EXAMPLE 2 Under a nitrogen atmosphere, 20 g (277 mmol) of 3-buten-1-ol, 0.1 g (0.82 mmol) of 4-dimethylaminopyridine, and 200 g of a 4-neck flask equipped with a stirrer and a thermometer were placed in a 200-ml four-necked flask. Pyridine 5
After stirring for 30 minutes, 18.8 g (92 m) of terephthalic acid chloride was added.
mol) was added. After stirring for an additional hour, the reaction solution was poured into a saturated aqueous solution of potassium sulfate to stop the reaction,
Then it was extracted with toluene. The obtained organic layer was washed with water, dried over magnesium sulfate, and dried under reduced pressure for 60 to 7 days.
By distilling off the solvent at 0 ° C., the formula:

Embedded image 16.3 g of the compound represented by were obtained. The vinyl group content of this compound was 19.7% by weight.

[0021]

Example 1 Under a nitrogen atmosphere, a 200 ml four-necked flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer was charged with 80 ml of toluene, 80 g of a polydimethylsiloxane having a viscosity of 18 mm ² / S and capped at both ends with dimethylsiloxy groups ( Silicon atom-bonded hydrogen atom content: 0.12% by weight) and 5.01 g of the organosilicon compound prepared in Reference Example 1, and then a complex of platinum and divinyltetramethyldisiloxane was added to the polydimethylsiloxane. Platinum metal is 0.0 with respect to 100 parts by weight of the total amount of the organosilicon compound.
It was added in an amount of 02 parts by weight. Next, this was heated and stirred at 105 ° C. for 2 hours, 3.5 g of 1-hexene was added, and the mixture was further heated and stirred at 95 ° C. for 1 hour. The low-boiling substances were distilled off from the reaction mixture thus obtained to obtain 85.2 g of a reaction product. When this was analyzed by NMR,
It was found that the obtained reaction product was a silicon-containing polymer represented by the following average composition formula. The number average molecular weight of this silicon-containing polymer was 2,900, and the degree of dispersion was 1.6.

Embedded image

[0022]

Example 2 Under a nitrogen atmosphere, 80 g of toluene, 80 g of a polydimethylsiloxane capped with dimethylsiloxy groups at both ends having a viscosity of 18 mm ² / S were placed in a 200 ml four-necked flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer. Silicon-bonded hydrogen atom content: 0.12% by weight), 3.42 g of the organosilicon compound prepared in Reference Example 1 and 6.43 g of the organic compound prepared in Reference Example 2 were added, and then platinum and divinyltetramethyl were added. A complex with disiloxane was added in such an amount that platinum metal was 0.002 parts by weight based on 100 parts by weight of the total of polydimethylsiloxane, organosilicon compound and organic compound. Then, add 10
After heating and stirring at 5 ° C for 2 hours, 1.0 g of 1-hexene was added.
In addition, the mixture was further heated and stirred at 95 ° C. for 1 hour. The low-boiling substances were distilled off from the reaction mixture thus obtained to obtain 90.2 g of a reaction product. NMR analysis revealed that the obtained reaction product was a silicon-containing polymer represented by the following average composition formula. This silicon-containing polymer had a number average molecular weight of 4,000 and a dispersity of 2.
It was 2.

Embedded image

[0023]

Example 3 Under a nitrogen atmosphere, in a 200 ml four-necked flask equipped with a stirrer, a dropping funnel, a condenser and a thermometer, 80 ml of toluene and one end having a viscosity of 60 mm ² / S were blocked with a dimethylsiloxy group. Polydimethylsiloxane 8 having one end blocked with a trimethylsiloxy group 8
0 g (silicon-bonded hydrogen atom content: 0.027% by weight) and 1.6 of the organosilicon compound prepared in Reference Example 1.
4 g was added, and then a complex of platinum and divinyltetramethyldisiloxane was added in such an amount that platinum metal was 0.002 parts by weight based on 100 parts by weight of the total amount of the dimethylsiloxane and the organosilicon compound. Then, add 10
The mixture was heated and stirred at 5 ° C. for 2 hours. From the reaction mixture thus obtained, low-boiling substances were distilled off to obtain a reaction product 81.2.
g was obtained. NMR analysis revealed that the obtained reaction product was a silicon-containing polymer represented by the following average composition formula. The number average molecular weight of this silicon-containing polymer was 11,400, and the degree of dispersion was 1.3.

Embedded image

[0024]

The silicon-containing polymer of the present invention is a novel polymer compound whose main skeleton is composed of a siloxane bond, a silicon-nitrogen atom bond and a silalkylene bond,
Further, the production method of the present invention is characterized in that the siloxane bond in the main skeleton of such a silicon-containing polymer can be adjusted to an arbitrary length.

[Brief description of the drawings]

FIG. 1 is a chart of a ²⁹ Si-NMR spectrum of the silicon-containing polymer prepared in Example 1.

FIG. 2 is a chart of a ²⁹ Si-NMR spectrum of the silicon-containing polymer prepared in Example 2.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J035 BA01 CA02U CA021 CA10U CA13U CA131 CA14U CA141 CA18M CA18U CA181 GA01 GA05 GB03 GB05 GB08 LB20

Claims (5)

[Claims] (A) a general formula: Wherein A represents the same or different aliphatic unsaturated bond-containing monovalent hydrocarbon group or a compound represented by the formula: (In the formula, R ⁴ is a hydrogen atom or a monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ⁵ is a divalent hydrocarbon group having no aliphatic unsaturated bond or an alkyleneoxyalkylene group. )), R ¹ is the same or different monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ² is a monovalent hydrocarbon group having no aliphatic unsaturated bond. A is a valent hydrocarbon group or a hydrogen atom, and a is an integer of 0 or more. An organosilicon compound represented by the formula:
(B) General formula: [Wherein, R ¹ is the same as described above, R ³ is a divalent hydrocarbon group having no aliphatic unsaturated bond, 1 and m are 1 or 2, and n is an integer of 0 or more. , (L + n) is 3 or more. And a siloxane compound selected from an organopolysiloxane or a silalkylenesiloxane represented by the following formula:
A number average molecular weight of 5, wherein the main skeleton is composed of a siloxane bond, a silicon atom-nitrogen atom bond and a silalkylene bond
100 to 100,000 silicon-containing polymers. (A) a general formula: (In the formula, A, R ¹ , R ² and a are the same as described above.)
And an organosilicon compound represented by the formula: (b) a general formula: (Wherein R ¹ , R ³ , l, m and n are the same as described above), and a siloxane compound selected from an organopolysiloxane or a silalkylenesiloxane, and (c) a general formula: 6] (Wherein, A, R ¹ and R ⁵ are the same as described above). The main skeleton is formed by polymerization of an organic compound selected from the compounds represented by the following formulas by a hydrosilylation reaction. A silicon-containing polymer having a number average molecular weight of 500 to 100,000 and comprising a nitrogen atom bond and a silalkylene bond. (3) The component (a) has a general formula: (Wherein R ¹ , R ² , R ³ and a are the same as above). The silicon-containing polymer according to claim 1 or 2, which is an organosilicon compound represented by the formula: (4) (a) a general formula: (In the formula, A, R ¹ , R ² and a are the same as described above.)
And an organosilicon compound represented by the general formula (b): (Wherein R ¹ , R ³ , l, m and n are the same as those described above) and a siloxane compound selected from organopolysiloxanes or silalkylenesiloxanes using a hydrosilylation reaction catalyst. 2. The method for producing a silicon-containing polymer according to claim 1, wherein the addition polymerization is carried out. (5) (a) a general formula: (In the formula, A, R ¹ , R ² and a are the same as described above.)
An organosilicon compound represented by the general formula (b): (Wherein R ¹ , R ³ , l, m and n are the same as described above), and a siloxane compound selected from an organopolysiloxane or a silalkylenesiloxane, and (c) a general formula: 12] Wherein A, R ¹ and R ⁵ are as defined above, and an organic compound selected from the compounds represented by the following formulas, using a hydrosilylation reaction catalyst: A method for producing the silicon-containing polymer according to claim 2.