JP2002155144A - Borazine-containing silicon-based copolymer and method for producing thin film thereof - Google Patents

Abstract

[PROBLEMS] To provide a novel ternary borazine-containing silicon-based copolymer and a method for producing a thin film of the copolymer. SOLUTION: General formula (1) (Wherein, R ¹ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom, and R ² represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom). Trialquinyl borazines and a compound represented by the general formula (2) (R ⁷ C≡C) _m R ⁸ (2) (wherein R ⁷ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁸ represents 2 A divalent or trivalent group) and a compound represented by the general formula (3) (Wherein, R ³ and R ⁴ represent an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁵ is a divalent group) in the presence of a platinum-containing catalyst. By applying the solution, a thin film of a ternary borazine-containing silicon-based copolymer is obtained by an addition reaction of a hydrosilyl group to an alkynyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel borazine-containing silicon-based copolymer useful as a coating film having, for example, flame resistance and heat resistance, and a method for producing a thin film of the borazine-containing silicon-based copolymer.

[0002]

2. Description of the Related Art Borazine-containing silicon-based polymers exhibit excellent thermal stability even in air, and are expected to be applied to combustion-resistant and heat-resistant coating materials. Had not been. Further, there has been no known tertiary borazine-containing silicon-based copolymer containing a normal diyne or triin compound as a monomer component and capable of suppressing the amount of borazine monomer used.

[0003]

Accordingly, the present invention provides a novel tertiary borazine-containing silicon-based copolymer containing a conventional diyne or triin compound as a monomer component and capable of suppressing the amount of borazine monomer used. It is another object of the present invention to provide a method for efficiently producing a thin film of the copolymer having excellent flame resistance and heat resistance.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the combination of B, B ', B "-trialkynylborazines with a diyne or triin compound has shown A novel tertiary borazine-containing silicon-based copolymer is obtained by mixing a silicon compound having at least two hydrosilyl groups with a platinum-containing catalyst and applying the resulting solution to add a hydrosilyl group to an alkynyl group. The present inventors have found a novel fact that a polymer thin film can be easily obtained, and have completed the present invention.

That is, the present invention has the following configuration. 1. General formula (1)

[0006]

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Wherein R ¹ is an alkyl group, an aryl group,
An aralkyl group or a hydrogen atom, and R ² represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom)
And B, B ', B "-trialkynyl borazine represented by the following general formula (2) (R ⁷ C≡C) _m R ⁸ (2) (where R ⁷ is an alkyl group, an aryl group, an aralkyl R ⁸ represents an aromatic or aliphatic divalent or trivalent group which may have a substituent,
m by using both the diyne or avian compound represented by R ⁸ is a divalent In group 2, R ⁸ is a trivalent group is 3), they general formula (3)

[0008]

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(Wherein R ³ and R ⁴ are the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group and a hydrogen atom, and R ⁵ has a substituent. A borazine-containing silicon-based copolymer obtained by reacting with a silicon compound having at least two or more hydrosilyl groups represented by an aromatic divalent group). 2. The following general formula (4)

[0010]

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Or the general formula (5)

[0012]

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(Wherein R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁷ and R ⁸ are the same as those in the general formulas (1), (2) and (3), and c, d, e, f,
g, h and i are integers equal to or greater than 0, and c + d
≧ 1 and e ≧ 1, and in Formula (5), f + g ≧ 1 and h + i ≧ 1). 3. 3. The borazine-containing silicon-based copolymer according to 1 or 2, wherein the 5% weight loss temperature in air is 200 ° C. or more. 4. General formula (1)

[0014]

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(Wherein R ¹ is an alkyl group, an aryl group,
An aralkyl group or a hydrogen atom, and R ² represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom)
And B, B ', B "-trialkynyl borazine represented by the following general formula (2) (R ⁷ C≡C) _m R ⁸ (2) (where R ⁷ is an alkyl group, an aryl group, an aralkyl R ⁸ represents an aromatic or aliphatic divalent or trivalent group which may have a substituent,
m by using both the diyne or avian compound represented by R ⁸ is a divalent In group 2, R ⁸ is a trivalent group is 3), they general formula (3)

[0016]

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(Wherein R ³ and R ⁴ are the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁵ is a substituent. A borazine-containing silicon-based copolymer, which is mixed with a silicon compound having two hydrosilyl groups represented by a good aromatic divalent group) in the presence of a platinum catalyst, and applying the solution. Method of manufacturing thin film.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ²
Represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. The alkyl group has 1 to 24, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. The aralkyl group has 7 to 2 carbon atoms
4, preferably 7-12. To illustrate the R ^2, a methyl group, an ethyl group, an isopropyl group, t- butyl group, and an octyl group, a phenyl group, a naphthyl group, an aryl group such as a biphenyl group, a benzyl group, aralkyl groups such as phenethyl groups , A hydrogen atom and the like.

Specific examples of the B, B ', B "-trialkynylborazine compound having these substituents and represented by the general formula (1) include B, B', B" -triethynylborazine, B, B ', B "-triethynyl-N, N', N"
-Trimethylborazine, B, B ', B "-tri (1-propynyl) borazine, B, B', B" -tri (phenylethynyl) borazine, B, B ', B "-tri (phenylethynyl) -N , N ', N "-trimethylborazine,
B, B ', B "-triethynyl-N, N', N" -triphenylborazine, B, B ', B "-tri (phenylethynyl) -N, N', N" -triphenylborazine,
B, B ', B "-ethynyl-N, N', N" -tribenzylborazine and the like, but are not limited thereto. Further, one kind of B, B ′, B ″ -trialkynylborazine compound can be used alone.
Use of a combination of more than one type of B, B ', B "-trialkynylborazine compound is also included in an advantageous embodiment of the present invention.

[0020] In the present invention, B, B ', B " - with tri alkynyl borazine compound, diyne or avian compound is reacted with a silicon compound having two or more hydrosilyl groups of the general formula (2) (R ⁷ C≡ C) _m R ⁸ (2), wherein R ⁷ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, wherein the alkyl group has 1 to 24, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20, preferably 6 to 14. The aralkyl group has 7 to 24, preferably 7 to 16 carbon atoms.

Examples of the above R ¹ include alkyl groups such as methyl group, ethyl group, isopropyl group, t-butyl group and octyl group, aryl groups such as phenyl group, naphthyl group and biphenyl group, benzyl group, phenethyl group and the like. Aralkyl group, hydrogen atom and the like. R ⁸ represents an aromatic or aliphatic divalent or trivalent group which may have a substituent. m, in ^{R 8} is a divalent group in 2, ^{R 8} is a trivalent group is three. The aromatic divalent or trivalent group has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. The aliphatic divalent or trivalent group has 2 to 20 carbon atoms, preferably 3 to 16 carbon atoms. Examples of R ⁸ include a phenylene group, a benzenetriyl group, a naphthylene group, a naphthalenetriyl group, an anthrylene group, a biphenylene group, a terphenylene group, an ethylene group, a trimethylene group, a pentamethylene group, an octamethylene group, and a dodecamethylene group. And a hexadecamethylene group.

Examples of these diyne or triyne compounds include p- and m-diethynylbenzene,
3,5- and 1,2,4-triethynylbenzene, p
-And m-di (1-propynyl) benzene, 1,3,
5- and 1,2,4-tri (1-propynyl) benzene, p- and m-di (phenylethynyl) benzene,
p- and m-di (3-phenyl-1-propynyl) benzene, 1,3,5- and 1,2,4-tri (phenylethynyl) benzene, 1,4- and 1,5-diethynylnaphthalene, 9,10-diethynylanthracene,
4,4′-diethynylbiphenyl, 1,5-hexadiyne, 1,6-heptadiyne, 1,8-nonadiyne, 1,
11-dodecadine, 1,15-hexadecadine,
Examples thereof include 1,19-eicosadiyne, but are not limited thereto. One type of diyne or triin compound can be used alone, but the use of two or more types in combination is also included in an advantageous embodiment of the present invention.

As the silicon compound having two or more hydrosilyl groups used in the present invention, those represented by the general formula (3) are used.

[0024]

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In the formula, R ³ and R ⁴ are the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group and a hydrogen atom. The alkyl group has 1 to 24, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms. The aralkyl group has 7 to 24 carbon atoms, preferably 7 to 12 carbon atoms. Examples of the above R ³ and R ⁴ include alkyl groups such as methyl group, ethyl group, isopropyl group, t-butyl group and octyl group, aryl groups such as phenyl group, naphthyl group and biphenyl group, benzyl group, phenethyl group and the like. Aralkyl group, hydrogen atom and the like.

In the general formula (3), R ⁵ represents an aromatic divalent group which may have a substituent. The aromatic divalent group has 6 to 24 carbon atoms, preferably 6-1.
2. Examples of the aromatic divalent group include a divalent aromatic hydrocarbon group (such as an arylene group), an arylene group containing a hetero atom such as oxygen as a linking group, and the like. Examples of the substituent that may be bonded to the aromatic divalent group include an alkyl group, an aryl group, and an aralkyl group. Examples of such an aromatic divalent group include an arylene group such as a phenylene group, a naphthylene group, and a biphenylene group, and a substituted arylene group such as a diphenyl ether group.

The bis (hydrosilane) compounds having these substituents and represented by the general formula (3) include bis (monohydrosilane) s, bis (dihydrosilane) s and bis (trihydrosilane) s. . Specific examples of these bis (hydrosilane) compounds include m-bis (dimethylsilyl) benzene, p-bis (dimethylsilyl) benzene,
1,4-bis (dimethylsilyl) naphthalene, 1,5-
Bis (dimethylsilyl) naphthalene, m-bis (methylethylsilyl) benzene, m-bis (methylphenylsilyl) benzene, p-bis (methyloctylsilyl) benzene, 4,4′-bis (methylbenzylsilyl) biphenyl, Examples include, but are not limited to, 4,4'-bis (methylphenethylsilyl) diphenyl ether, m-bis (methylsilyl) benzene, and m-disilylbenzene.

The quantity relationship of the starting compounds in the reaction of the present invention is such that the molar ratio of the B, B ', B "-trialkynylborazine compound of the general formula (1) to the diyne or the diyne of the general formula (2) in an arbitrary molar ratio is determined. Triin compounds can be used,
Generally, the molar ratio is from 0.01 to 200, preferably from 0.03 to 150, more preferably from 0.05 to 10
It is in the range of 0. Ratio of the molar amount of the silicon compound having two hydrosilyl groups of the general formula (3) to the total molar amount of the B, B ', B "-trialkynylborazine compound (1) and the diyne or triyne compound (2). Is generally in the range of 0.1 to 10, preferably 0.2 to 5.

In the present invention, by reacting these monomers usually in the presence of a platinum-containing catalyst, the following:
General formula (4)

[0030]

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Or the general formula (5)

[0032]

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(Wherein R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁷ and R ⁸ are the same as those in the general formulas (1), (2) and (3), and c, d, e, f,
g, h and i are integers equal to or greater than 0, and in the formula (4), c + d
≧ 1 and e ≧ 1, and in Formula (5), f + g ≧ 1 and h + i ≧ 1).
A novel ternary borazine-containing silicon-based copolymer can be obtained. In the formula, Z ²¹ , Z ³¹ , and Z ⁴¹ are monovalent organic groups derived from the raw material compounds, such as a vinyl group which may have a substituent, a hydrogen atom, and the like. The terminal group in these polymers is a hydrosilyl group or an ethynyl group.

The portion represented by the following formula (6) in the above general formula (4) or (5) means that there are four bonding states shown by the following formula (7).

[0035]

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[0036]

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As the platinum-containing catalyst used in the present invention, those conventionally used for hydrosilylation can be used. For example, platinum divinyltetramethyldisiloxane, platinum cyclic divinylmethylsiloxane, chloroplatinic acid, dichloroplatinum, platinum carbon, tris (dibenzylideneacetone) diplatinum, bis (ethylene) tetrachlorodiplatinum, cyclooctadienedichloro Platinum, bis (cyclooctadiene) platinum, cyclooctadienedimethylplatinum, bis (triphenylphosphine) dichloroplatinum,
Examples include, but are not limited to, tetrakis (triphenylphosphine) platinum.

These platinum-containing catalysts are B, B ', B "-
0.000001 to 0.5 in terms of the molar ratio of the metal atom to the raw material having a smaller molar amount among the trial quinyl borazine compound (1) and the diyne or triin compound (2) or the bis (hydrosilane) compound (3). Used in range. In the production of the polymer of the present invention, since the reaction proceeds almost quantitatively, the target polymer can be easily obtained by a method such as removing the solvent under reduced pressure or normal pressure. In addition, fractionation can also be performed by a method such as reprecipitation or gel permeation chromatography.

The present invention can be carried out irrespective of the presence or absence of a solvent. When a solvent is used, various solvents other than those which react with the raw materials can be used. Examples of such solvents include aromatic hydrocarbons, saturated hydrocarbons, aliphatic ethers, and aromatic ethers, and more specifically, toluene, benzene, xylene, hexane, tetrahydrofuran, diphenyl ether, and the like. Is mentioned.

In the present invention, by reacting these solvents with a platinum-containing catalyst and applying the resulting solution to a substrate or the like, a borazine-containing silicon-based compound having excellent combustion resistance and heat resistance can be obtained. A thin film of the polymer can be obtained. When forming a thin film of the borazine-containing silicon-based copolymer of the present invention, the method of applying the solution on the substrate is not particularly limited, and any method such as application by a brush, spray application, or spin coating is used. You can also. The temperature for preparing the solution to be applied in the present invention may be generally room temperature, but depending on the structure of the raw material, it may be cooled or heated in the range of −20 ° C. to 200 ° C. to achieve a preferable rate. . The preferred temperature is 0 to 150 ° C, more preferably 0 to 100 ° C.

After applying the solution, a thin film of a borazine-containing silicon-based copolymer can be obtained by drying in air, under an inert atmosphere, or in vacuum. In the present invention, a thin film of a borazine-containing silicon-based copolymer is not particularly limited in its thickness,
It is not a resin such as a lump, but a resin formed into a film. In particular, the method of the present invention is characterized in that a film can be formed in a range from a thin film in μm unit to a relatively thick film in mm order, and there is no particular upper limit of the film thickness.

[0042]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. (Example 1) B, B ', B "-triethynyl-N,
N ', N "-trimethylborazine (0.125 mmol
l), m-diethynylbenzene (0.125 mmol
l), p-bis (dimethylsilyl) benzene (0.25
was dissolved in toluene (5 ml), a 2% solution of platinum divinyltetramethyldisiloxane in platinum (0.00025 mmol platinum) was added, and the mixture was stirred at room temperature under nitrogen for 4 days. 0.1 ml of this solution was applied on a glass substrate and dried in air to obtain a colorless and transparent thin film. The thickness of the thin film measured using the tally step was 2 μm. As a result of measuring the thermal stability of the polymer of this film by thermogravimetric analysis, the 5% weight loss temperature was 320 ° C.
(Under nitrogen) and 360 ° C. (in air). ¹ H-NMR (C ₆ D ₆ , δ, ppm) 8.1-7.9 (m, 0.7H), 7.8-7.6
(m, 3.4H), 7.5-7.1 (m, 0.7H), 6.9-6.7 (m, 0.9H), 6.
6-6.4 (m, 0.8H), 6.2-5.7 (m, 1.5H), 3.5-2.5 (m, 5H)
, 0.6-0.2 (br s, 12H) .IR (KBr disk, cm ^-1 ) 2072 (w), 1578, 1446, 1396, 12
49, 1133, 1104, 1019,839, 774.

Example 2 B, B ', B "-triethynyl-N, N', N" -trimethylborazine (0.125
mmol), 1,3,5-triethynylbenzene (0.
125 mmol) and p-bis (dimethylsilyl) benzene (0.25 mmol) were dissolved in toluene (5 ml), and platinum 2% of platinum divinyltetramethyldisiloxane was dissolved.
Add a xylene solution (0.00025 mmol platinum),
Stirred at room temperature under nitrogen for 4 days. 0.1 ml of this solution was applied on a glass substrate and dried in air to obtain a colorless and transparent thin film. The thickness of the thin film measured using the tally step was 3 μm. As a result of measuring the thermal stability of the polymer of this film by thermogravimetric analysis, the 5% weight loss temperature was 320 ° C. (under nitrogen) and 380 ° C. (in air). IR (KBr disk, cm ^-1 ) 2120, 2074, 1578, 1448, 1381,
1251, 1135, 988, 880,820.

Example 3 B, B ', B "-triethynyl-N, N', N" -trimethylborazine (0.125
mmol), m-diethynylbenzene (0.125 mm
ol), p-bis (dimethylsilyl) benzene (0.2
5 mmol) was dissolved in toluene (0.5 ml), a platinum 2% xylene solution of platinum divinyltetramethyldisiloxane (0.00025 mmol platinum) was added, and the mixture was stirred at room temperature under nitrogen for 5 days. Obtained. The reaction solution was heated and concentrated under reduced pressure to obtain a powdery borazine-containing silicon-based copolymer (4a) in almost quantitative yield. This polymer has the same structure as the polymer of Example 1. Thermogravimetric analysis (nitrogen) _Td 5 (5% weight loss temperature) 321 ° C. 63% residual (985 ° C.) thermogravimetric analysis (in air) _Td 5 (5% weight loss temperature) 362 ° C. 59% residual (985 ° C.)

Example 4 B, B ', B "-triethynyl-N, N', N" -trimethylborazine (0.125
mmol), 1,3,5-triethynylbenzene (0.
125 mmol) and p-bis (dimethylsilyl) benzene (0.25 mmol) were dissolved in toluene (0.5 ml), and a 2% solution of platinum divinyltetramethyldisiloxane in xylene (0.00025 mmol platinum) was added. Under stirring at room temperature for 6 days, a gel-like solution was obtained. The reaction solution was concentrated by heating under reduced pressure to obtain a powdery borazine-containing silicon-based copolymer (5a) in almost quantitative yield. This polymer has the same structure as the polymer of Example 2. Thermogravimetric analysis (in nitrogen) Td ₅ (5% weight loss) 322 ° C. 75% residue (985 ° C.) Thermogravimetric analysis (in air) Td ₅ (5% weight loss temperature) 382 ° C. 66% residue (985
℃)

[0046]

According to the present invention, the B, B ', B "-trialkynylborazine compound (1) and the ordinary diyne or triyne compound (2) can be converted into a silicon compound (3) having at least two hydrosilyl groups. ) To produce a novel tertiary borazine-containing silicon-based copolymer that reduces the amount of expensive borazine monomer used, and a thin film having excellent flame resistance and heat resistance of the copolymer.
It can be manufactured simply and safely. Therefore, the industrial significance of the present invention is great.

Claims (4)

[Claims] 1. A compound of the general formula (1) (Wherein, R ¹ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom, and R ² represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom). Trialquinyl borazines and a compound represented by the general formula (2) (R ⁷ C≡C) _m R ⁸ (2) (wherein R ⁷ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁸ is An aromatic or aliphatic divalent or trivalent group which may have a group,
m by using both the diyne or avian compound represented by the R ⁸ is a divalent group in 2, R ⁸ is a trivalent group is 3), they general formula (3) ## STR2 ## (Wherein, R ³ and R ⁴ are the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁵ is an aromatic group which may have a substituent. A borazine-containing silicon-based copolymer obtained by reacting with a silicon compound having at least two hydrosilyl groups represented by the following formula: 2. The following general formula (4): Or the general formula (5): (In these formulas, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁷ and R ⁸ are the same as those in the general formulas (1), (2) and (3), and c , D, e, f, g, h and i
Is an integer greater than or equal to 0, and in formula (4), c + d ≧ 1 and e ≧
The borazine-containing silicon-based copolymer according to claim 1, further comprising a repeating unit represented by Formula (5), wherein f + g ≧ 1 and h + i ≧ 1 in Formula (5). 3. The 5% weight loss temperature in air is 200 ° C.
The borazine-containing silicon-based copolymer according to claim 1 or 2, wherein: 4. A compound of the general formula (1) (Wherein, R ¹ represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom, and R ² represents an alkyl group, an aryl group, an aralkyl group, or a hydrogen atom). Trialquinyl borazines and a compound represented by the general formula (2) (R ⁷ C≡C) _m R ⁸ (2) (wherein R ⁷ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁸ is An aromatic or aliphatic divalent or trivalent group which may have a group,
m by using both the diyne or avian compound represented by the R ⁸ is a divalent group in 2, R ⁸ is a trivalent group is 3), they general formula (3) embedded image (Wherein, R ³ and R ⁴ are the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁵ is an aromatic group which may have a substituent. A borazine-containing silicon-based copolymer thin film, which is mixed with a silicon compound having two hydrosilyl groups represented by the following formula: Production method.