JPH08231727A - Copolymer containing silicon and its production - Google Patents

Abstract

PURPOSE: To obtain a silicon-containing copolymer, excellent in heat resistance, flexibility and mechanical characteristics, useful for heat-resistant coating, films, etc., for heat-resistant electric wires and capable of contributing to reduction in weight and cost and higher efficiency. CONSTITUTION: This copolymer has 500-100,000 number-average molecular weight and randomly contains a structure of at least formulas I to III [R<1> , R<2> and R<4> to R<7> are each an alkyl(amino) or an alkenyl; R<3> and R<8> are each a bivalent aromatic group; (p), (q) and (r) are each (p)/(q) is 0.01-99; (p)/(r) is 0.01-99 91/47/28}. The copolymer is obtained by reacting a mixture containing an organodihalosilane of formula IV (X is a halogen) and a disilyl compound of formula V with a diamine of the formula, NH2 -R<3> -NH2 and ammonia.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicon-containing copolymer and a method for producing the same, which copolymer can be widely used in heat-resistant coatings, coatings for heat-resistant electric wires and the like where heat resistance is required. is there.

[0002]

2. Description of the Related Art Regarding heat-resistant polymers, aromatic / heterocyclic polymers such as fluorine-based materials, polyimide bendazole, aromatic polyamide, and polyimide have been studied since silicone was synthesized by Rocho et al. . Furthermore, in recent years, the demand for heat resistance has increased along with the development of the space and aviation fields, and the progress of research on aromatic / heterocyclic polymers has been observed, and the improvement of aromatic polyimides has been promoted. In addition to this, organometallic polymers such as polyborosiloxane and polytitanosiloxane whose main chains are composed of metal elements such as Si, Ti, and B and O, N, and the like have been studied.

In recent years, improvement of heat resistance is desired in various heat resistant / insulating material fields. For example, the most typical applications are in the field of rotating machines such as generators, high-voltage AC motors, industrial DC motors, and train motors, and those belonging to these high-voltage rotating machines tend to have larger capacities and higher pressures. Yes, downsizing and high heat resistance are required. Moreover, the required heat resistance in some of these fields exceeds 400 ° C. in the atmosphere. Furthermore, in addition to this, heat resistance as well as insulation, flexibility, mechanical properties, etc. are required. However, regarding the organic polymers among the current heat-resistant polymers, the heat-resistant temperature that has been put into practical use is 300 ° C. or lower.

On the other hand, organometallic polymers such as silicone resin and polyborosiloxane resin have high heat stability of the polymer, and thus have high heat resistance of 500 ° C. or more.
However, while the organic polymer has a linear structure with little branching, the organic metal polymer has a network structure with many branches, which results in a huge reaction due to dehydrogenative condensation reaction or oxidation reaction between OH groups. A three-dimensional mesh structure is formed,
As a result, it was poor in flexibility and could not be used in the field of rotating machines.

[0005]

Therefore, in order to solve the drawbacks of the organometallic polymer, it has been attempted to combine an organic resin and an inorganic material, for example, an inorganic polysilazane portion and an organic polysilazane portion. A block copolymer silazane consisting of
175726). However, such a composite polymer has not yet been satisfactory because, for example, mechanical properties are insufficient.

Therefore, an object of the present invention is to solve the above-mentioned problems, that is, to provide an organometallic polymer having heat resistance of 400 ° C. or higher and excellent in mechanical strength and flexibility, and a method for producing the same. To do.

[0007]

As a result of intensive studies, the present inventor has attempted to introduce a C═C bond, a bifunctional group and an Si bond into a polymer, resulting in an increase in bond energy. And the progress of linearization of the polymer and the improvement of oxidative stability were achieved, and the present invention was reached.

That is, according to the present invention, firstly, it is characterized by having a number average molecular weight of 500 to 100,000 and containing at least structural units represented by the following general formulas (I) to (III). Silicon-containing copolymers are provided.

Embedded image

Embedded image

[Chemical 3] [In the above formula, R¹, R², R^Four, R^Five, R⁶And R⁷Is that
Independently, alkyl group, alkenyl group, cycloalkyl
Group, aryl group, aralkyl group, alkylamino group or
Alkylsilyl group, R³And R⁸Each independently
It is a divalent aromatic group. In addition, structural units (I) to (II
I) is random and the respective molar ratios p, q and r
Has the following relationship. p / q = 0.01 to 99 p / r = 0.01 to 99] Second, the divalent aromatic group is an aralkylene group or naphthyl group.
A len group or a group represented by the following general formula (A)
The first silicon-containing copolymer is provided
It

[Chemical 4] [In the formula, R ¹⁰ is a halogen atom or a lower alkyl group, a is an integer of 0 to 4, and Z is a direct bond or a group represented by the following general formula (B).

Embedded image (In the formula, R ¹¹ is a halogen atom or a lower alkyl group, b is an integer of 0 to 4, and Y is a direct bond or a divalent group.) Thirdly, optionally, the following general formula There is provided the above-mentioned first silicon-containing copolymer characterized by comprising a structural unit represented by the formula (IV) or (V).

[Chemical 6]

[Chemical 7] [In the above formula, R ⁹ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkylsilyl group, and R ³ is the same as defined above. The structural units (I) to (V) are random, and the respective molar ratios p, q, r, m and n have the following relationship. (M + n) / (p + q) = 0.01 to 99 (m + p) / (n + q) = 0.01 to 99 r / (m + n + p + q) = 0.01 to 99]

According to the present invention, fourthly, a mixture containing an organodihalosilane represented by the following general formula (VI) and a disilyl compound represented by the following general formula (VII); There is provided a method for producing the above-mentioned first silicon-containing copolymer, which comprises reacting a diamine represented by VIII) with ammonia (the diamine and the ammonia may be in any order).

[Chemical 8] (In the formula, R¹, R²Is the same as above, X is a halogen element
It )

[Chemical 9] (In the formula, R^Four, R^Five, R⁶, R⁷And R⁸Is the same as above
Is a halogen element. )

Embedded image NH ₂ —R ³ —NH ₂ (VIII) (wherein R ³ is the same as defined above) Fifth, the mixture is further treated with an organohydrodihalogenate represented by the following general formula (IX). A fourth method of manufacture is provided, comprising silane, and thus forming the third silicon-containing copolymer.

[Chemical 11] (In the formula, R ⁹ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylamino group or an alkylsilyl group.) Sixth, in the first step of the reaction, the following general formula (VI ) Represented by the following general formula (VII
The diamine represented by I) is reacted with ammonia (the diamine and the ammonia may be in any order) to obtain an oligomer, and in the second step of the reaction, the above oligomer and the disilyl compound represented by the following general formula (VII) are combined. There is provided a method for producing the first silicon-containing copolymer, which comprises reacting.

[Chemical 8] (In the formula, R¹, R²Is the same as above, X is a halogen element
It )

[Chemical 9] (In the formula, R^Four, R^Five, R⁶, R⁷And R⁸Is the same as above
Is a halogen element. )

Embedded image NH ₂ —R ³ —NH ₂ (VIII) (In the formula, R ³ is the same as above.) Seventh, the organohalosilane is further represented by the following general formula (I
The sixth production method is provided, which comprises the organohydrohalosilane represented by X), and thus forms the third silicon-containing copolymer.

[Chemical 11] (In the formula, R ⁹ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylamino group or an alkylsilyl group, and X is a halogen element.)

According to the present invention, the following polymers and methods for producing the polymers are provided as preferred embodiments. In the above general formulas (I) to (V), the silicon-containing copolymer as described above, wherein R ^{1 to} R ² and R ^{4 to} R ⁷ are methyl groups or phenyl groups. In the general formulas (VI), (VII) and (IX),
The method for producing a silicon-containing copolymer as described above, wherein R ^{1 to} R ² , R ^{4 to} R ⁷ and R ⁹ are methyl groups or phenyl groups. In the general formulas (II), (III) and (V), R ³
And the silicon-containing copolymer as described above, wherein R ⁸ is an arylene group. The method for producing a silicon-containing copolymer as described above, wherein R ³ and R ^{8 in the} general formulas (VII) and (VIII) are arylene groups. In the general formulas (VI), (VII) and (IX),
The method for producing a silicon-containing copolymer as described above, wherein X is a Cl atom. A molded product such as a film or a coating obtained from the above-mentioned silicon-containing copolymer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The silicon-containing copolymer of the present invention has the above general formulas (I) to (III), and optionally (I) to (V).
Having a structural unit represented by
It is characterized by being in the range of 100,000. That is,
The copolymer of the present invention is particularly preferably the above-mentioned general formula (II) and
Since it has a structural unit represented by (III) optionally further (V), C = C bond by bonding energy increases, and is a straight of the polymer by the introduction of difunctional (R ^3, R ⁸⁾ is Since it progresses and of course has high oxidative stability due to Si bond, it has heat resistance of 400 ° C. or higher, and also has flexibility and high mechanical strength.

Regarding the polymer obtained by reacting a halosilane and a bifunctional amine, Plast und Kautshuk 3
3. Jahrgng Heft 6/1986, but it is structurally different from the copolymer of the present invention in structure, and its heat resistance is not described. For heat resistant paints containing silazane bonds, see the Journal of Pai
nt Technology Vol. 42, No. 543, April 1970, it is structurally completely different from the copolymer of the present invention and has low heat resistance.

The silicon-containing copolymer of the present invention has the general formulas (I) to (III), and optionally (I) as described above.
To (V), particularly the above general formulas (II) and (III), and optionally further structural units represented by (V), and having a C = C bond. There are features. In addition, general formula (I)-(III) or (I)-(V)
The bonding order of each structural unit is random, and the ratio p, q, r or m, n, p, q, r of each structural element can take the following range. p / q = 0.01 to 99 p / r = 0.01 to 99 or (m + n) / (p + q) = 0.01 to 99 (m + p) / (n + q) = 0.01 to 99 r / (m + n + p + q ) = 0.01-99

Next, the method for producing the silicon-containing copolymer of the present invention will be described. One of the production methods of the present invention is represented by the general formula (VIII) in a mixture containing an organodihalosilane represented by the general formula (VI) and a disilyl compound represented by the general formula (VII). It is characterized in that the intended silicon-containing copolymer of the present invention is obtained by reacting diamine and ammonia (whichever may be first in the order of diamine and ammonia).

That is, in the present invention, a mixture of an organodihalosilane and a disilyl compound is used as a starting material. The organodihalosilane is represented by the following general formula (V
It is represented by I).

[Chemical 8] (In the formula, R¹And R²Are each independently an alkyl group,
Kenyl group, cycloalkyl group, aryl group, alkyl group
A mino group, an aralkyl group or an alkylsilyl group
It )

In the above general formula (VI), R ¹ and R ² usually have 1 to 7, preferably 1 to 5 and more preferably 1 to 2 carbon atoms, and more preferably 1 to ² carbon atoms, and 2 to 7 alkenyl groups. A cycloalkyl group or an aryl group of 5 to 7 is generally used, and X is usually a fluorine, chlorine, bromine or iodine atom, preferably a chlorine atom. As the aryl group, a phenyl group, a tolyl group, a xylyl group, a cumenyl group,
Benzyl group, phenethyl group, α-methylbenzyl group, benzhydryl group, trityl group, styryl group, cinnamyl group, biphenyl group, naphthyl group and the like can be used. As the alkylsilyl group (mono, di, tree substitution product), alkylamino group (mono, di substitution product), and alkoxy group, those having 1 to 7 carbon atoms are usually used. R ¹ and R ² may be the same or different. Further, X is preferably a Cl atom. In particular, diphenyldichlorosilane is preferable as the compound represented by the above general formula (VI).

One disilyl compound has the following general formula (VI
It is represented by I).

[Chemical 9] [In the above formula, R^Four~ R⁷Are each independently an alkyl group,
Kenyl group, cycloalkyl group, aryl group, alkyl group
Represents a mino group, an aralkyl group or an alkylsilyl group
X represents the same as in the case of the general formula (VI),
R⁸Each independently represents a divalent aromatic group. Note that R⁸Good luck
The aromatic group is an aralkylene group, a naphthylene group or the above general
It is preferably a group represented by formula (A)
Is an alkylene group, alkenylene group, cycloalkylene
Group, arylene group, alkylimino group or alkyl
A silylene group, and further R⁸At least one of
Is preferably an arylene group. ]

In the general formula (VII), R ⁸ is preferably an arylene group. As the arylene group, a phenylene group, a tolylene group, a xylylene group, a benzylidene group, a phenethylidene group, an α-methylbenzylidene group, a cinnamylidene group, a naphthylene group and the like can be used. Specific examples of the compound represented by the general formula (VII) include 1,4-bis (dimethylchlorosilyl)
Benzene and the like are preferred.

In the method of the present invention, a mixture of the above-mentioned organodihalosilanes and a disilyl compound is reacted with a diamine represented by the general formula (VIII) NH ₂ —R ³ —NH ₂ and ammonia. R ³ in the general formula (VIII)
Represents a divalent aromatic group similar to R ⁸ in the general formula (VII), preferably an alkylene group, an alkenylene group, a cycloalkylene group, an arylene group, an alkylimino group or an alkylsilylene group, and particularly Arylene groups are preferred. Specific examples of the diamine include those shown in Table 1. Among these, para-phenylenediamine (p-PDA), meta-phenylenediamine (m-PDA), and 4,4′-diphenyldiaminoether (oxydianiline, ODA) are particularly preferable.

[0020]

[Table 1]

As the reaction solvent, either a Lewis base and a non-reactive solvent may be used alone, or a mixture thereof may be used. In this case, examples of the Lewis base include tertiary amines (tolualkylamines such as trimethylamine, dimethylethylamine, diethylmethylamine, and triethylamine, pyridine, picoline, dimethylalinine, and their derivatives) and sterically hindering groups. Examples of secondary amines, phosphine, stipine, arsine and their derivatives (eg, trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, triethylphosphine, trimethylarsine, trimethylstipine, trimethylamine, triethylamine, etc.) be able to. Among them, a base having a low boiling point and a basicity lower than that of ammonia (for example, pyridine, picoline, trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, triethylphosphine).
Are preferred, and pyridine and picoline are particularly preferred from the viewpoint of handling and economy.

As the non-reactive solvent, a hydrocarbon solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon; a halogenated hydrocarbon such as a halogenated methane, a halogenated ethane or a halogenated benzene; Ethers such as aliphatic ether and alicyclic ether can be used. Of these, preferred are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane, halogenated hydrocarbons such as tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-
Ethers such as dioxyethane, dioxane, dimethyldioxane, tetrahydrofuran, tetrahydropyran, pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene,
Hydrocarbons such as xylene, ethylbenzene, N-methyl-2-pyrrolidone and diglyme. Among these solvents, dichloromethane, xylene and N-methyl-2-pyrrolidone are preferable from the viewpoint of safety.

In the method of the present invention, first, the above general formula (VI) is used.
The organodihalosilane represented by the formula (II) and the disilyl compound represented by the general formula (VII) are mixed in an organic solvent, and then the diamine represented by the general formula (VIII) is reacted therewith. The mixing ratio with the disilyl compound may be in the range of 1:99 to 99: 1 in terms of molar ratio, preferably 90:10 to 10:90, and more preferably 80:20 to 40:60. . The molar ratio of both dihalosilicon compounds and diamine may be in the range of 90:10 to 10:90, preferably 87.5: 12.5 to 25:75, and It is preferably 87.5: 12.5 to 40:60. The amount of amine modification is preferably 25 to 75 mol% of the theoretical reaction amount of both dihalosilicon compounds. The concentration of the dihalosilicon compound in the solvent can be arbitrarily selected, but it is preferably in the range of 5 to 25% by weight. The temperature is in the range where the reaction system becomes liquid (typically -4
Any from 0 to 300 ° C. may be used. The pressure is generally from normal pressure to under pressure, but nitrogen pressure is preferred.

After the reaction between the dihalosilicon compound and the diamine is carried out, ammonia is added to carry out an aminolysis reaction. (Of course, the order of the reaction with the diamine and the aminolysis reaction is arbitrary as described above.) The conditions such as the reaction solvent and the reaction temperature in this case are the same as those in the case of the preceding diamine. The amount of ammonia added is determined by the amount of diamine previously reacted. That is, assuming that the theoretical amount required for ammonolysis of the dihalosilicon compound is X mol and the amount of the added diamine is Y mol, (XY) mol is the necessary amount of ammonia. However, ammonia may be in excess. The pressure is generally from normal pressure to increased pressure, but nitrogen pressure is preferable. HCl in this reaction
Is produced, which can be separated from the target substance by forming a salt with a base such as triethylamine or ammonia. The copolymerized silazane thus produced and the by-product ammonium chloride are separated by filtration, and the solvent is removed from the filtrate under reduced pressure to obtain the copolymerized silazane.

Another one of the production methods of the present invention is to add the organohydrodihalosilane represented by the general formula (IX) and the organodihalosilane represented by the general formula (VI) in an organic solvent. A copolymerized silazane is obtained by reacting with a diamine represented by the general formula (VIII) and ammonia.
Further, the obtained copolymerized silazane is reacted with the disilyl compound represented by the general formula (VII) to obtain the intended silicon-containing copolymer of the present invention.

In the present production method, the organohydrodihalosilane represented by the general formula (IX) is an optional component and may be used without use. Further, in the above-mentioned production method using a mixture of an organodihalosilane and a disilyl compound as a starting material, there is no mention of the use of the above organohydrodihalosilane, but in the starting material mixture of the method, organohydrogen It is of course possible to add and use dihalosilane.

The organo (hydro) dihalosilane used as a starting material in the present invention has the following general formula (IX):
And (VII).

[Chemical 11]

[Chemical 8] (In the formula, R¹And R²Are each independently an alkyl group,
Kenyl group, cycloalkyl group, aryl group, alkyl group
A mino group, an aralkyl group or an alkylsilyl group
It )

In the above general formulas (IX) and (VI), R
¹ and R ² usually have 1 to 7 carbon atoms, and preferably 1
-5, more preferably 1-2 alkyl groups, 2-7 alkenyl groups, 5-7 cycloalkyl groups, aryl groups are common, and X is usually a fluorine, chlorine, bromine or iodine atom, preferably Is a chlorine atom. As the aryl group, use a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a benzyl group, a phenethyl group, an α-methylbenzyl group, a benzhydryl group, a trityl group, a styryl group, a cinnamyl group, a biphenyl group, a naphthyl group, etc. You can As the alkylsilyl group (mono, di, tree substitution product), alkylamino group (mono, di substitution product), and alkoxy group, those having 1 to 7 carbon atoms are usually used. R ¹ and R ² may be the same or different. Also, as X,
Cl atoms are preferred. In particular, methyldichlorosilane is preferable as the compound represented by the general formula (IX), and diphenyldichlorosilane is preferable as the compound represented by the general formula (VI).

In the method of the present invention, the above-mentioned organodihalosilanes are reacted with a diamine represented by the general formula (VIII) NH ₂ —R ³ —NH ₂ and ammonia. R ³ in the general formula (VIII) represents a divalent aromatic group, preferably an alkylene group, an alkenylene group, a cycloalkylene group, an alkylimino group or an alkylsilylene group, and particularly preferably an arylene group. Specific examples of the diamine include those shown in Table 1 above. Among these, particularly para-phenylenediamine (p-P
DA), meta-phenylenediamine (m-PDA),
4,4'-diphenyldiaminoether (oxydianiline, ODA) is preferred.

As the reaction solvent, either a Lewis base and a non-reactive solvent may be used alone, or a mixture thereof may be used. In this case, examples of the Lewis base include tertiary amines (tolualkylamines such as trimethylamine, dimethylethylamine, diethylmethylamine, and triethylamine, pyridine, picoline, dimethylalinine, and their derivatives) and sterically hindering groups. Examples of secondary amines, phosphine, stipine, arsine and their derivatives (eg, trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, triethylphosphine, trimethylarsine, trimethylstipine, trimethylamine, triethylamine, etc.) be able to. Among them, a base having a low boiling point and a basicity lower than that of ammonia (for example, pyridine, picoline, trimethylphosphine, dimethylethylphosphine, methyldiethylphosphine, triethylphosphine).
Are preferred, and pyridine and picoline are particularly preferred from the viewpoint of handling and economy.

As the non-reactive solvent, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons; halogenated hydrocarbons such as halogenated methane, halogenated ethane and halogenated benzene; Ethers such as aliphatic ether and alicyclic ether can be used. Of these, preferred are methylene chloride, chloroform, carbon tetrachloride, bromoform, ethylene chloride, ethylidene chloride, trichloroethane, halogenated hydrocarbons such as tetrachloroethane, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, 1,2-
Ethers such as dioxyethane, dioxane, dimethyldioxane, tetrahydrofuran, tetrahydropyran, pentane, hexane, isohexane, methylpentane, heptane, isoheptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, benzene, toluene,
Hydrocarbons such as xylene and ethylbenzene. Among these solvents, dichloromethane and pyridine are preferable from the viewpoint of safety and the like, and a pyridine / dichloromethane mixed solvent is particularly preferable.

In the present method, first, the organohydrodihalosilane represented by the general formula (IX) is reacted with the organodihalosilane represented by the general formula (VI) in an organic solvent, and then the above-mentioned general formula The diamine represented by the formula (VIII) is reacted, and the mixing ratio of the organohydrodihalosilane and the organodihalosilane is 0: 1 in a molar ratio.
It may be in the range of 00 to 99: 1, preferably 1
It is 0:90 to 90:10. Further, the use ratio of both the dihalosilane and the diamine is 1:99 to 9 in molar ratio.
It may be in the range of 9: 1, but preferably from 50:50.
It is 90:10. The amount of amine modification is preferably 10 to 50 mol% of the theoretical reaction amount of both dihalosilanes. The concentration of dihalosilane in the solvent can be arbitrarily selected, but it is preferably in the range of 1 to 20% by weight. The temperature is in the range where the reaction system becomes liquid (typically -4
Any of 0 to 160 ° C. may be used. The pressure is generally from normal pressure to under pressure, but nitrogen pressure is preferred.

After the reaction between the dihalosilane and the diamine is carried out, ammonia is added to carry out an aminolysis reaction. (Of course, the order of the reaction with the diamine and the aminolysis reaction is arbitrary.) In this case, the conditions such as the reaction solvent and the reaction temperature are the same as those in the case of the preceding diamine. The amount of ammonia added is determined by the amount of diamine previously reacted. That is, when the theoretical amount necessary for ammonolysis of dihalosilane is X mol and the amount of added diamine is Y mol, (XY) mol is the necessary amount of ammonia. However, ammonia may be in excess. The silazane oligomer (copolymerized silazane) thus produced and the by-product ammonium chloride are separated by filtration to obtain a silazane oligomer.

Next, the silazane oligomer obtained as described above and the following general formula (VII)

[Chemical 9]  A disilyl compound represented by
Target by reacting in a non-reactive solvent
A silicon-containing copolymer is obtained. General formula (VII)
In, X is a fluorine, base, bromine or iodine atom.
Generally, a chlorine atom is preferably used. R
^Four~ R⁷Are the same group or different
It may be a base. R^Four~ R⁷Is an alkyl group, alkenyl
Group, cycloalkyl group, aryl group, aralkyl group,
It is a alkylamino group or an alkylsilyl group. R⁸Two
Valent aromatic group such as aralkylene group and naphthylene group
Alternatively, it is preferably a group represented by the general formula (A).
Specifically, an alkylene group, an alkenylene group, a
A roalkylene group, an arylene group, an alkylimino group or
An alkylsilylene group is mentioned, and an aryl group is particularly preferable.
A len group is used. As an arylene group, phenyle
Group, tolylene group, xylylene group, benzylidene group, fluorine group
Ethylidene group, α-methylbenzylidene group, cinnami
Ridene group, naphthylene group and the like can be used. one
As the compound represented by the general formula (VII), specifically,
1,4-bis (dimethylchlorosilyl) benzene is preferred
Good.

The silazane oligomer and the general formula (VII)
In the reaction with the disilyl compound represented by, the reaction amount of the disilyl compound is in the range of 1:99 to 99: 1 by weight ratio with the silazane oligomer, and preferably 10: 9.
It is 0 to 90:10. The reaction temperature is 0 ° C to 300 ° C, preferably 20 ° C to 200 ° C.

According to the method of the present invention, the above-mentioned general formula (I) is used.
To (III), optionally a structural unit represented by (I) to (V), and having a number average molecular weight of 500 to 100,000.
A novel silicon-containing copolymer in the range of can be easily obtained. This polymer is soluble in general organic solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbon hydrocarbon solvents, halogenated hydrocarbons, ethers, alcohols, esters and ketones.

The copolymer obtained by the method of the present invention can be formed into a molded product having high heat resistance and excellent mechanical strength. For example, when the copolymer is applied to the surface of a metal wire and the temperature is 250 to 400 ° C. in air,
When fired for 2.0 hours, a film withstanding high temperatures and having excellent mechanical properties and flexibility is obtained. Furthermore, in an inert atmosphere of nitrogen, argon, etc., 400 to 550
By baking at 0.1 ° C. for 0.1 to 2 hours, a film having further improved heat resistance can be obtained.

[0038]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the technical scope of the present invention is not limited by these.

Example 1 After replacing the inside of a reaction vessel placed in a constant temperature bath with dry nitrogen, p-PDA (paraphenylenediamine) 7.5 gr (0.069 moles) was added to 200 ml of xylene, and the temperature inside the reaction vessel was changed. At 120 ° C. to dissolve p-PDA. Next, diphenyldichlorosilane (Ph ₂ SiC
1 ₂ ) 25.3 gr (0.1 moles), methyldichlorosilane (MeSiHCl ₂ ) 0.75 gr (0.0
065 moles), and 1,4-bis (dimethylchlorosilyl) benzene 6.6 gr (0.025 mole)
s) was dissolved in 100 ml of xylene to give 120
The mixture was added to a xylene solution of p-PDA kept at a constant temperature of ° C over 15 minutes for reaction. P-PDA with addition
It was confirmed that the hydrochloride salt was precipitated. Further, in order to destroy the hydrochloric acid and the hydrochloride formed in the reaction, 60m of triethylamine
1 was added. Then, the reaction tank was cooled, and when the temperature reached 30 ° C. or lower, 12 gr of ammonia was added to react unreacted halogenated silane. The addition of ammonia confirmed the formation of a white precipitate of ammonium chloride with increasing solution temperature. After completion of the reaction, dry nitrogen was blown into the reaction mixture to remove unreacted ammonia, followed by pressure filtration under a nitrogen atmosphere to obtain about 350 ml of a filtrate. The solvent was removed from the filtrate under reduced pressure to obtain 30 gr of a reddish brown solid polymer at room temperature.

The number average molecular weight of the obtained polymer is GP
It was 700 when measured by C. As a result of IR spectrum analysis, the wave number 3350 cm ~ ¹ based on the N-H absorption; based on 2170 cm ~ ¹ of Si-H absorption; 1
Absorption based on Si-Ph at 140 cm ~ ¹ ; 1020-8
The absorption based on the 810,780Cm ~ ¹ of the benzene ring C-H; 20cm ~ ¹ of Si-H and Si-N-Si based absorption; 3140,2980,2950,1270cm ~ based on ¹ C-H absorption It was confirmed to show. Furthermore, when the ¹ H-NMR (proton nuclear magnetic resonance absorption) spectrum of this polymer was analyzed, it was found to be δ7.2 ppm
(Br, C ₆ H ₆ ), δ 4.8 ppm (br, SiH),
δ1.4 ppm (br, NH), δ0.3 ppm (b
r, SiCH ₃ ) absorption was confirmed, and also 29SiNM
R NON-NOE BB-DC measurement result, -17pp
m and -20 ppm to -25 ppm (-Si-
NH-) l (peak caused by _{-Si-NH-C 6 H 5} -NH-) m is subjected to -25ppm~-35ppm (-
Si-NH-) n (-Si- NH-C 6 H 5 -NH-) o
Peak attributed to, but also is observed peaks due over a _{(-Si-C 6 H 5 -Si-} ) p in -2Ppm～8ppm, material was obtained with following structural units. _{- m-, (CH 3 SiH-} NH) - n-, (CH 3 SiH-NH-Ph-NH) - (SiPh 2 -NH) p-, - (SiPH 2 -NH-Ph-NH) q-, _{- {(CH 3) 2 Si} -Ph-Si (CH 3) 2} r- addition, a peak caused from measurement data 15NNMR DEPT 90 to -NH-C ₆ H ₅ -NH- in the polymer structure 50ppm~65ppm The peak due to the -NH- group derived from ammonia is 20 ppm to 40 pp.
It was observed over m. From the integrated intensity ratio of these peaks, the abundance ratio of each unit is estimated as follows. (L + m) / (n + o) = 0.09 (l + n) / (m + o) = 0.58 p / (l + m + n + o) = 0.40

Next, the physical properties of this product were investigated. This product was applied on an aluminum foil and heat-cured at 400 ° C. for 2 hours in the air, and then the aluminum foil was removed to form a film of 30 μm to 50 μm. This film has a tensile strength of 580 kg
It had f / cm ² and an elongation of 10%, and showed excellent physical properties at high temperatures. Further, the 5% weight loss temperature in air was 500 ° C. Further, this polymer was applied to a nickel-plated copper wire having a diameter of 2.4 mm to a thickness of 10 μm, and a heat deterioration test was conducted at 400 ° C. for 6 hours in the air. As a result, the coating film was observed 400 times under a microscope. It was totally sound. Furthermore, the coating film did not fall off even under the condition of 600 ° C. for 1 hour in severe atmosphere. The result is excellent heat resistance not found in existing organic resins (eg polyimide). Further, as shown by the elongation of the film, this polymer was applied to a copper wire and baked at 350 ° C. to harden the coating, and no crack was generated even if it was bent for 1d (self-diameter bending). It showed a flexibility not found in.

Examples 2 to 12 The same as Example 1 except that the raw material organodihalosilane type and mixing ratio, the type and addition amount of the diamine used, the reaction temperature, and the reaction solvent were changed to those shown in Table 2. Thus, a silicon-containing heat resistant polymer was obtained. Further, Table 3 shows the results of the physical property evaluation test of the obtained polymer in the same manner as in Example 1.

[0043]

[Table 2] P-PDA: paraphenylenediamine DDE: diaminodiphenyl ether NMP: N-methyl-2-pyrrolidone

[0044]

[Table 3] Flexibility: A film of a heat-resistant polymer was baked on a nickel-plated copper wire having a diameter of 2.4 mm to a thickness of 10 μm, and it was tested how many times the diameter of the wire bends without breaking. 1d: Equivalent to theoretical elongation of 50%

Example 13 After replacing the inside of a reaction vessel placed in a constant temperature bath having a temperature of -40 ° C. with dry nitrogen, dried methylene chloride (1,000 m)
1 and pyridine (80 ml) were added and the mixture was maintained until the temperature became constant. Then, while stirring, methyldichlorosilane (CH ₃ SiHCl ₂ ) 47.6 gr (0.413 mol
es), diphenyldichlorosilane (Ph ₂ SiCl ₂ ).
25.3 gr (0.10 moles) was added to each, and the mixture was stirred and held until the temperature in the reaction tank became constant. next,
DDE (diaminodiphenyl ether) 25 gr (0.
125 moles) in 100 gr of pyridine,
It was added into the reaction vessel at a slow speed of about 5.0 gr / min. After that, 20 gr of ammonia was further added and reacted.

After completion of the reaction, dry nitrogen was blown into the reaction mixture to remove ammonia from the reaction, and the mixture was pressure-filtered under a nitrogen atmosphere to obtain 1,150 ml of a filtrate. When 1,000 ml of dry m-xylene was added to this filtrate and the solvent was removed under reduced pressure,
45.0 gr of reddish brown viscous liquid was obtained.

The number average molecular weight of the obtained viscous liquid is GP
It was 850 when measured by C. As a result of IR spectrum analysis, the wave number 3350 cm ~ ¹ based on the N-H absorption; based on 2170 cm ~ ¹ of Si-H absorption; 1
Absorption based on Si-Ph at 140 cm ~ ¹ ; 1020-8
It was confirmed that the absorption based on Si-H and Si-N-Si at 20 cm ~ ¹ shows the absorption based on C-H at 3140, 2980, 2950, 1270 cm ~ ¹ . Furthermore, ¹ H-NMR (proton nuclear magnetic resonance absorption) of this polymer
When the spectrum was analyzed, δ7.2 ppm (br,
C ₆ H ₆ ), δ 4.8 ppm (br, SiH ₂ or Si
H), δ1.4 (br, NH), δ0.3 (br, Si
Absorption of CH ₃ ) was confirmed.

40 g of the viscous liquid was dissolved in m-xylene and charged into a reaction tank. The temperature was set to 150 ° C., and the mixture was stirred and held until the temperature became constant, and then m-xylene 3
A solution in which 40 gr of 1,4-bis (dimethylchlorosilyl) benzene was dissolved in 00 ml was gradually added to the reaction tank. Next, in order to trap the hydrochloric acid generated by the reaction when the temperature in the reaction tank falls below 90 ° C., 2
0 ml triethylamine was added. At this time, precipitation of triethylamine hydrochloride was confirmed. Further, when the temperature dropped to room temperature, 5.0 g of ammonia was added and reacted to crush unreacted 1,4-bis (dimethylchlorosilyl) benzene.

After completion of the reaction, dry nitrogen was blown to remove ammonia and then filtered to obtain 800 ml of a solution. When this filtrate was added and the solvent was removed under reduced pressure, 75 gr of a red viscous liquid was obtained.

The number average molecular weight of the obtained viscous liquid is GP
It was 2,000 as measured by C. Also, I
As a result of R spectrum analysis, 1,4-wavelengths of 820 cm- ¹
Par based on bis (dimethylchlorosilyl) benzene
It was confirmed that the absorption of benzene at the a position was large. Furthermore, from the ¹ H-NMR spectrum, δ7.2 pp
There was a relative increase in absorption based on the m bridged benzene rings. In addition, 29N NMR NON-NOE BB
-DC data and 29SiNMR DEPT90 data measurement results, -15 ppm to -25 ppm {-S
^{i (R 1) (H)} -NH-} l, {- Si (R 1) (H)
Peak caused by _{-NH-C 6 H 5 OC 6} H 5 -NH-} m is subjected to -30ppm~-35ppm {-Si (R
^{1) (R 2) -NH-}} n, {- Si (R 1) (R 2) -N
Peaks due to _{H-C 6 H 5 OC 6} H 5 -NH-} o is,
Also over the _{-2ppm~-5ppm (-Si-C 6} H 4
A peak due to -Si-) p was observed, and a substance having the following structural unit was obtained. _{- m-, (CH 3 SiH-} NH) - n-, (CH 3 SiH-NH-Ph-NH) - (SiPh 2 -NH) p-, - (SiPH 2 -NH-Ph-NH) q-, _{- {(CH 3) 2 Si} -Ph-Si (CH 3) 2} r- Moreover, peaks caused by the measurement data 15NNMR DEPT 90 to _{-NH-C 6 H 5 OC 6} H 5 -NH- in the polymer structure Is around 60 ppm, ammonia-derived -N
A peak due to H- was observed from 20 ppm to 40 ppm. From the integrated intensity ratio of these peaks, the abundance ratio of each unit is estimated as follows. (L + m) / (n + o) = 7.2 (l + n) / (m + o) = 5.1 p / (l + m + n + o) = 2.3

Next, the physical properties of this product were investigated. This product was applied on an aluminum foil, crosslinked and cured at 300 ° C. in the atmosphere, and then the aluminum foil was removed to form an independent film of 30 μm to 50 μm. This independent membrane has a pit tension of 450 kgf /
cm ² and elongation 8%, and the 5% weight loss temperature of this product was 450 ° C. Also, in nitrogen at 500 ° C, 2
The independent film obtained by firing for an hour is transparent and has a tensile strength of 600 kg.
f / cm ² , elongation was 12.0%, and 5% weight loss temperature in air was 500 ° C., showing excellent heat resistance. Further, this polymer was applied to a nickel-plated copper wire having a diameter of 2.4 mm and subjected to a heat deterioration test at 400 ° C. for 6 hours in the air. As a result, the coating film was quite sound.

Examples 14 to 23 Raw material organohydrodihalosilanes and organodihalosilanes and their mixing ratio, the type and amount of diamine used, the reaction temperature in the first step, the type of disilyl compound used,
And a silicon-containing copolymer was obtained in the same manner as in Example 13 except that the reaction temperature and the like in the second step were changed to the conditions shown in Table 4. Further, a physical property evaluation test for each of the obtained polymers was conducted in the same manner as in Example 13. The results are shown in Table 5.

[0053]

[Table 4]

[0054]

[Table 5]

[0055]

The silicon-containing copolymers according to claims 1 to 3 have the general formulas (I) to (III), and optionally (I).
To (V), particularly the structural units represented by (II), (III) and (V), the following excellent effects are exhibited. (A) Since it has excellent heat resistance, flexibility, and mechanical properties, it cannot be used with conventional organic resins.
It can be used in a high temperature environment above 0 ° C. For example,
It can be widely applied to areas where heat resistance is required, such as heat resistant coatings and coatings for heat resistant electric wires. (B) Since the resin can be used in a high temperature environment, the weight can be reduced, which contributes to cost reduction, high efficiency, and the like.

The method for producing a silicon-containing copolymer according to any one of claims 4 to 7 is directed to the organodihalosilane represented by the general formula (VI) [in some cases, the organohydrodihalosilane represented by the general formula (IX). And a disilyl compound represented by the general formula (VII) is reacted with a diamine represented by the general formula (VIII) and ammonia, or an organodihalogenated group represented by the general formula (VI). A silane (optionally containing an organohydrodihalosilane represented by the general formula (IX)) is reacted with a diamine represented by the general formula (VIII) and ammonia to obtain a copolymerized silazane, which is further obtained. According to this method, the copolymerized silazane is reacted with the disilyl compound represented by the general formula (VII). A high heat resistant polymer can be easily obtained.

Claims (7)

[Claims] 1. A number average molecular weight of 500 to 100,000.
And is represented by at least the following general formulas (I) to (III).
A silicon-containing compound characterized by containing a structural unit
Polymerized polymer. [Chemical 1] [Chemical 2] [Chemical 3] [In the above formula, R¹, R², R^Four, R^Five, R⁶And R⁷Is that
Independently, alkyl group, alkenyl group, cycloalkyl
Group, aryl group, aralkyl group, alkylamino group or
Alkylsilyl group, R³And R⁸Each independently
It is a divalent aromatic group. In addition, structural units (I) to (II
I) is random and the respective molar ratios p, q and r
Has the following relationship. p / q = 0.01 to 99 p / r = 0.01 to 99] 2. The divalent aromatic group is an aralkylene group,
The silicon-containing copolymer according to claim 1, which is a naphthylene group or a group represented by the following general formula (A). [Chemical 4] [In the formula, R ¹⁰ is a halogen atom or a lower alkyl group, a is an integer of 0 to 4, and Z is a direct bond or a group represented by the following general formula (B). Embedded image (In the formula, R ¹¹ is a halogen atom or a lower alkyl group, b is an integer of 0 to 4, and Y is a direct bond or a divalent group.) 3. The silicon-containing copolymer according to claim 1, which optionally further comprises a structural unit represented by the following general formula (IV) or (V). [Chemical 6] [Chemical 7] [In the above formula, R ⁹ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkylsilyl group, and R ³ is the same as defined above. The structural units (I) to (V) are random, and the respective molar ratios p, q, r, m and n have the following relationship. (M + n) / (p + q) = 0.01 to 99 (m + p) / (n + q) = 0.01 to 99 r / (m + n + p + q) = 0.01 to 99] 4. An organo represented by the following general formula (VI):
Dihalosilane and disilyl represented by the following general formula (VII)
Represented by the following general formula (VIII):
Reaction of diamine with ammonia (with diamine
Either order of ammonia may come first)
The method for producing the silicon-containing copolymer according to claim 1. [Chemical 8] (In the formula, R¹, R²Is the same as above, X is a halogen element
It ) [Chemical 9] (In the formula, R^Four, R^Five, R⁶, R⁷And R⁸Is the same as above
Is a halogen element. ) Embedded image NH₂-R³-NH₂(VIII) (In the formula, R³Is the same as above. ) 5. A process according to claim 4, characterized in that the mixture further comprises an organohydrodihalosilane of the general formula (IX) below, thus forming the silicon-containing copolymer of claim 3. Method. [Chemical 11] (In the formula, R ⁹ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylamino group or an alkylsilyl group.) 6. The following general formula in the first step of the reaction:
An organodihalosilane represented by (VI) and the following general
Diamine represented by formula (VIII) is reacted with ammonia.
Let's order (whichever comes first, diamine or ammonia)
A) oligomer and obtained in the second step of the reaction.
Rigomers and disilylation represented by the following general formula (VII)
The silicon-containing material according to claim 1, which comprises reacting with a compound.
Method for producing copolymer polymer. [Chemical 8] (In the formula, R¹, R²Is the same as above, X is a halogen element
It ) [Chemical 9] (In the formula, R^Four, R^Five, R⁶, R⁷And R⁸Is the same as above
Is a halogen element. ) Embedded image NH₂-R³-NH₂(VIII) (In the formula, R³Is the same as above. ) 7. The organohalohalosilane of claim 6 further comprising an organohydrohalosilane of general formula (IX) below, thus forming the silicon-containing copolymer of claim 3. Production method. [Chemical 11] (In the formula, R ⁹ is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkylamino group or an alkylsilyl group, and X is a halogen element.)