JP3459985B2 - Method for producing thin film of borazine-containing silicon polymer and borazine-containing silicon polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Borazine-containing silicon-based polymers show excellent thermal stability even in air and are expected to be applied to flammability-resistant and heat-resistant coating materials, etc., but simple examples of thin film production are still unknown. It wasn't done. In addition, a borazine-containing silicon-based polymer having a linear or cyclic polysiloxane structure industrially usable has not been produced.

[0003]

DISCLOSURE OF THE INVENTION The present invention has an efficient method for producing a thin film of a borazine-containing silicon polymer having excellent combustion resistance and heat resistance, and a novel linear or cyclic polysiloxane structure. An object is to provide a borazine-containing silicon-based polymer.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that B, B ', B "-trialquinylborazines and silicon having two or more hydrosilyl groups. The novel fact that a thin film of a borazine-containing silicon-based polymer formed by the addition reaction of a hydrosilyl group to an alkynyl group can be easily obtained by mixing a compound with a platinum-containing catalyst and coating the solution. In addition to the discovery, a new borazine-containing silicon-based polymer having a linear or cyclic polysiloxane structure was discovered, and the present invention was completed based on these findings.

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

[0006]

[Chemical 8]

(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)
The B, B ′, B ″ -trialquinylborazine compound represented by the formula (1) and a silicon compound having at least two hydrosilyl groups are mixed in the presence of a platinum catalyst, and the solution is applied. Method for producing thin film of borazine-containing silicon-based polymer 2. Silicon compound having at least two hydrosilyl groups is represented by the general formula (2):

[0008]

[Chemical 9]

(In the formula, R ³ and R ⁴ represent the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁵ has a substituent. Is a bis (hydrosilane) compound represented by an aromatic divalent group, an oxygen atom, or an oxypoly (dimethylsiloxy) group. 3.2 A silicon compound having two or more hydrosilyl groups has the general formula (3)

[0010]

[Chemical 10]

(In the formula, R ⁶ is an alkyl group, an aryl group,
Or represents an aralkyl group, and n represents an integer of 3 or more)
2. The production method according to 1, which is a poly (hydrosilane) compound represented by: 4. General formula (1)

[Chemical 11]

(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)
A B, B ′, B ″ -trialquinylborazine compound represented by the following general formula (3)

[0013]

[Chemical 12]

(Wherein R ⁶ is an alkyl group, an aryl group,
Or represents an aralkyl group, and n represents an integer of 3 or more)
Or general formula (4)

[0015]

[Chemical 13]

(Wherein R ⁹ and R ¹⁰ are alkyl groups,
Silicon having at least two or more hydrosilyl groups represented by aryl groups, aralkyl groups or monovalent groups selected from hydrogen atoms, which are the same or different, and R ¹¹ represents an oxypoly (dimethylsiloxy) group. A borazine-containing silicon-based polymer obtained by reacting with a compound. 5. General formula (5)

[0017]

[Chemical 14]

(Wherein R ¹ , R ² , R ⁹ , R ¹⁰ and R
¹¹ and R ⁶ are the same as those in the general formulas (1), (3) and (4), and a and b are integers of 0 or more and a + b ≧ 1). 4. The borazine-containing silicon-based polymer described in 4 above.
6. The borazine-containing silicon-based polymer as described in 4 or 5, wherein the 5% weight loss temperature in air is 200 ° C. or higher.

[0019]

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 carbon atoms, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20, preferably 6 to 10 carbon atoms. Aralkyl group has 7 to 2 carbon atoms
4, preferably 7-12. Examples of R ² 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, aralkyl groups such as benzyl group and phenethyl group. , Hydrogen atom and the like.

Specific examples of the B, B ', B "-trialquinylborazine 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,
Examples thereof include, but are not limited to, B, B ', B "-ethynyl-N, N', N" -tribenzylborazine and the like. Further, one kind of B, B ′, B ″ -trialquinylborazine compound can be used alone, but 2
The combined use of more than one type of B, B ′, B ″ -trialquinylborazine compound is also included in an advantageous aspect of the present invention.

Examples of the bis (hydrosilane) compound among the silicon compounds having two or more hydrosilyl groups used in the present invention include those represented by the general formula (2).

[0022]

[Chemical 15]

In the formula, R ³ and R ⁴ represent 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 carbon atoms, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20, preferably 6 to 10 carbon atoms. The carbon number of the aralkyl group is 7 to 24, preferably 7 to 12. Examples of 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 (2), R ⁵ represents an aromatic divalent group which may have a substituent, an oxygen atom or an oxypoly (dimethylsiloxy) group. The aromatic divalent group has 6 to 24 carbon atoms, preferably 6 to 12 carbon atoms. Examples of the aromatic divalent group include a divalent aromatic hydrocarbon group (arylene group and the like) as well as an arylene group containing a hetero atom such as oxygen as a linking group. Further, examples of the substituent that may be bonded to the aromatic divalent group include an alkyl group, an aryl group, an aralkyl group and the like. Exemplifying the case where R ⁵ is an aromatic divalent group,
Examples thereof 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.

Bis (hydrosilane) compounds having these substituents and represented by the general formula (2) 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, 4,4′-bis (methylphenethylsilyl) diphenyl ether, m-bis (methylsilyl) benzene, m-disilylbenzene, 1,1,3,3-tetramethyl-1,3-disiloxane, hydrodimethylsiloxypoly (dimethyl) Examples thereof include siloxy) dimethylsilane, but are not limited thereto.

The poly (hydrosilane) compound among the silicon compounds having two or more hydrosilyl groups includes, for example, those represented by the following general formula (3).

[0027]

[Chemical 16]

In the formula, R ⁶ represents an alkyl group, an aryl group or an aralkyl group, and n represents an integer of 3 or more. The alkyl group has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms. The aryl group has 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms.
It is 0. The carbon number of the aralkyl group is 7 to 24, preferably 7 to 12. Examples of R ⁶ include a methyl group,
Examples thereof include an alkyl group such as an ethyl group, an isopropyl group, a t-butyl group and an octyl group, an aryl group such as a phenyl group, a naphthyl group and a biphenyl group, and an aralkyl group such as a benzyl group and a phenethyl group. In addition, n is an integer of 3 or more,
It is preferably 3 to 10, more preferably 3 to 6.

Examples of these poly (hydrosilane) compounds are 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, 1,3,5,7. -Tetraethylcyclotetrasiloxane, 1,3,5-triphenylcyclotrisiloxane, 1,3,5,7-tetraphenylcyclotetrasiloxane, 1,3,5,7-tetrabenzylcyclotetrasiloxane and the like. However, the present invention is not limited to these. Further, the silicon compound having two or more hydrosilyl groups can be used alone or in combination of two or more, which is also included in an advantageous aspect of the present invention.

The reaction of the compound represented by the general formula (1) of the present invention with a silicon compound having at least two or more hydrosilyl groups is shown, for example, in the following schemes 1 and 2.

[0031]

[Chemical 17]

The amount relationship of the starting compounds in the reaction of the present invention is such that the molar ratio of the silicon compound having at least two hydrosilyl groups to the B, B ', B "-trialquinylborazine compound is in the range of 0.1 to 10. Carried out, preferably in the range of 0.2-5.

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

These platinum-containing catalysts are B, B ', B "-
The triquinylborazine compound or the bis (hydrosilane) compound is used in a range of 0.000001 to 0.5 in terms of the molar ratio of metal atom to the raw material having a small molar amount.

The present invention can be carried out with or without a solvent. When a solvent is used, various solvents other than those which react with the raw materials can be used. Examples of these solvents include aromatic hydrocarbon-based, saturated hydrocarbon-based, aliphatic ether-based, aromatic ether-based solvents, and more specifically, toluene, benzene, xylene, hexane, tetrahydrofuran, diphenyl ether, etc. Is mentioned.

When forming the thin film of the borazine-containing silicon polymer of the present invention, the method of applying the solution onto the substrate is not particularly limited, and any method such as brush application, spray application or spin coating method may be used. It can also be taken. 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. in order to reach a preferable rate. . The preferred temperature is 0 ° C to 150 ° C, more preferably 0 ° C to 100 ° C.

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

According to the present invention, the general formula (1)

[Chemical 18]

(In the formula, 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)
A B, B ′, B ″ -trialquinylborazine compound represented by the following general formula (3)

[0040]

[Chemical 19]

(In the formula, R ⁶ is an alkyl group, an aryl group,
Or represents an aralkyl group, and n represents an integer of 3 or more)
Or general formula (4)

[0042]

[Chemical 20]

(Wherein R ⁹ and R ¹⁰ are alkyl groups,
Silicon having at least two or more hydrosilyl groups represented by aryl groups, aralkyl groups or monovalent groups selected from hydrogen atoms, which are the same or different, and R ¹¹ represents an oxypoly (dimethylsiloxy) group. By reacting the compound with a compound of the general formula (5)

[0044]

[Chemical 21]

(Wherein R ¹ , R ² , R ⁹ , R ¹⁰ and R
¹¹ and R ⁶ are the same as those in the general formulas (1), (3) and (4), and a and b are integers of 0 or more and a + b ≧ 1). A novel borazine-containing silicon-based polymer is provided.

In these formulas, specific examples of R ¹ , R ² and R ⁵ include those shown in the above description. Further, specific examples of R ⁹ and R ¹⁰ include the above R
³ and R ⁴ may be mentioned. R ¹¹
Is an oxypoly (dimethylsiloxy) group. On the other hand, a
And b are integers of 0 or more, and a + b is 1 or more, preferably 1 to 50000, and more preferably 1 to 2000.
It is an integer of 0. Z is a monovalent organic group derived from the raw material compound, and is, for example, a vinyl group which may have a substituent or a hydrogen atom. The terminal group in these polymers is, for example, a hydrosilyl group or an ethynyl group.

Further, the portion represented by the following formula (6) in the general formula (5) is meant to include four kinds of bonding states shown in the following formula (7).

[0048]

[Chemical formula 22]

[0049]

[Chemical formula 23]

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.
It can also be separated by a method such as reprecipitation or gel permeation chromatography.

[0051]

The present invention will now 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 (0.25 mmol), p-bis (dimethylsilyl) benzene (0.25 mmol) and toluene were added. (5 ml), platinum 2% xylene solution of platinum divinyl tetramethyl disiloxane (0.00025mm
ol platinum) was added, and the mixture was stirred under nitrogen at room temperature for 4 days. 0.1 ml of this solution was applied onto a glass substrate and dried in air to obtain a colorless transparent thin film. The film thickness of the thin film measured using the Taristep was 2 μm.
This thin film is heat resistant, and the thermal stability of the polymer of this film was measured by thermogravimetric analysis to find that the 5% weight loss temperature was 49%.
0 ° C (under nitrogen) and 430 ° C (in air). ¹ H-NMR (C ₆ D ₆ , δ, ppm) 7.9-7.4 (m, 4H), 7.2-6.9
(m, 0.5H), 6.9-6.7 (m, 0.5H), 6.6-6.4 (m, 0.5H),
6.2-5.6 (m, 2.5H), 3.5-2.5 (m,, 10H), 0.6-0.2 (br
s, 12H) .IR (KBr disk, cm ^-1 ) 2072, 1580 (w), 1500-1350 (pea
k top, 1448, 1396), 1247, 1133, 1085 (w), 1004
(w), 951, 841, 772 (w), 648 (w). Elemental analysis C ₁₉ H ₃₀ N ₃ B ₃ Si ₂ : Theoretical value C, 58.66; H, 7.77;
N, 10.80. Found C, 57.50; H, 7.82; N, 9.83.

(Example 2) B, B ', B "-triethynyl-N, N', N" -trimethylborazine (0.25 mmol), 1,3,5,7
-Tetramethylcyclotetrasiloxane (0.25 mm
is dissolved in toluene (5 ml), and a platinum 2% xylene solution of platinum divinyltetramethyldisiloxane (0.
(000225 mmol platinum) was added, and the mixture was stirred under nitrogen at room temperature for 2 days. 0.1 ml of this solution was applied onto a glass substrate and dried in air to obtain a colorless transparent thin film. The thickness of the thin film measured using the Taristep is 4μ.
It was m. This thin film showed excellent heat resistance as in Example 1. IR (KBr disk, cm ^-1 ) 2164, 1230, 1021, 90
9, 731.

Example 3 B, B ', B "-triethynyl-N, N', N" -trimethylborazine (0.25 mmol), hydrodimethylsiloxypoly (dimethylsiloxy) dimethylsilane (H
Me ₂ SiO (SiMe ₂ O) _r SiMe ₂ H, Mn =
6000; 0.25 mmol) and toluene (0.5 m
1), a 2% platinum xylene solution of platinum divinyltetramethyldisiloxane (0.00025 mmol platinum) was added, and the mixture was stirred at room temperature under nitrogen for 1 hour. As a result, a gel solution was obtained. The reaction solution was heated and concentrated under reduced pressure to obtain a powdery borazine-containing silicon-based polymer (5a) in a substantially quantitative yield.

IR (KBr disk, cm ^-1 ) 2056, 1945, 1593,
1470-1350, 1320-1220, 1200-900. Elemental analysis C ₂₀₁ H ₄₈₆ N ₃ O ₈₁ B ₃ Si ₈₁ : Theoretical value C, 33.12; H,
8.09. Measured value C, 32.91; H, 8.24. Thermogravimetric analysis (in nitrogen) Td ₅ (5% weight loss temperature) 329 ° C 26% remaining (985 ° C) Thermogravimetric analysis (in air) Td ₅ (5% weight) Decreased temperature) 333 ℃ 36% remaining (985 ℃)

Example 4 B, B ′, B ″ -triethynyl-N, N ′, N ″ -trimethylborazine (0.25 mmol), 1,3,5,7
-Tetramethylcyclotetrasiloxane (0.25 mm
ol) was dissolved in toluene (0.5 ml), platinum 2% platinum divinyltetramethyldisiloxane in xylene solution (0.00025 mmol platinum) was added, and the mixture was stirred at room temperature for 2 hours under nitrogen. Was obtained. The reaction solution was heated and concentrated under reduced pressure to obtain a powdery borazine-containing silicon-based polymer (5b) in a substantially quantitative yield. This polymer has the same structure as the polymer of Example 2.

Thermogravimetric analysis (in nitrogen) Td ₅ (5% weight loss temperature) 204 ° C. 81% residue (985 ° C.) Thermogravimetric analysis (in air) Td ₅ (5% weight loss temperature) 200 ° C. 83% residue ( (985 ° C)

[0058]

INDUSTRIAL APPLICABILITY According to the present invention, a B, B ', B "-trialquinylborazine compound and a silicon compound having at least two hydrosilyl groups are used to contain a borazine which functions as a flame-resistant and heat-resistant coating film. A thin film of a silicon-based polymer can be simply and safely produced, and a novel industrially applicable borazine-containing silicon-based polymer can be obtained, so that the industrial significance of the present invention is great. .

─────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-5-331293 (JP, A) JP-A-7-196374 (JP, A) JP-A-2000-256466 (JP, A) JP-A-2002-155144 ( (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 77/00-77/62

Claims (6)

(57) [Claims] 1. A compound represented by the general formula (1): (In the formula, 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), B, B ′, B ″ — A method for producing a thin film of a borazine-containing silicon-based polymer, which comprises mixing a trialkynylborazine compound and a silicon compound having at least two hydrosilyl groups in the presence of a platinum catalyst and applying the solution. 2. A silicon compound having two or more hydrosilyl groups has the general formula (2): (In the formula, R ³ and R ⁴ represent the same or different monovalent groups selected from an alkyl group, an aryl group, an aralkyl group or a hydrogen atom, and R ⁵ represents an aromatic group which may have a substituent. 2. A method for producing a thin film according to claim 1, which is a bis (hydrosilane) compound represented by a divalent group of the group, an oxygen atom, or an oxypoly (dimethylsiloxy) group. 3. A silicon compound having two or more hydrosilyl groups has the general formula (3): (In the formula, R ⁶ represents an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 3 or more), which is a poly (hydrosilane) compound. Thin film manufacturing method. 4. A compound represented by the general formula (1): (In the formula, 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), B, B ′, B ″ — A trialquinylborazine compound and a compound represented by the general formula (3): (In the formula, R ⁶ represents an alkyl group, an aryl group, or an aralkyl group, and n represents an integer of 3 or more) or the general formula (4): (In the formula, R ⁹ and R ¹⁰ are an alkyl group, an aryl group,
An aralkyl group or a hydrogen atom, the same or different monovalent groups, and R ¹¹ represents an oxypoly (dimethylsiloxy) group) and a silicon compound having at least two hydrosilyl groups. A borazine-containing silicon-based polymer obtained by the reaction. 5. A compound represented by the general formula (5): (Wherein, R ¹ , R ² , R ⁹ , R ¹⁰ , R ¹¹ and R ⁶
Are the same as those in the general formulas (1), (3) and (4), and a and b are integers of 0 or more and a + b ≧ 1). The borazine-containing silicon-based polymer according to claim 4. 6. The 5% weight loss temperature in air is 200 ° C.
The above is the borazine-containing silicon-based polymer according to claim 4 or 5.