JPH11269270A - Carborane-containing silicon polymer and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a carborane-contg. silicon polymer excellent in heat resistance and flame retardance by forming a polymer or copolymer contg. carborane-contg. units in the molecule and having a specified wt. average mol.wt. SOLUTION: This silicone polymer is a polymer or copolymer having carborane-contg. units of formula I or II or is a mixture of such polymers or copolymers and has a wt. average mol.wt. of 500 or higher. In the formulas, R<1> is H, a 1-20C alkyl, or 6-30C aryl; R<2> a 1-2C alkylene or 6-30C arkylene; R<3> is H, a 1-20C alkyl, 6-30C aryl, or a silicon-contg. group of formula III (wherein R<4> is the same as R<1> ); CBxHx' C is a carborane unit (a divalent boron- contg. unit); and x and x' are each an integer of 3-16. This polymer is used for aerospace materials, building materials, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel carborane-containing silicon-based polymer useful as a functional material having excellent heat resistance and flame retardancy, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, silicon polymers having excellent heat resistance and flame retardancy have been developed. Further, attempts have been made to increase the molecular weight and improve the mechanical strength by a method of crosslinking a polymer by a polymer reaction [Organometallics, 15, 75 (1996)].
However, heat resistance and flame retardancy were not always sufficient. On the other hand, some carborane-containing silicon-based polymers are known, for example, J. Macromol. Sci. -Re
v. Macromol. Chem., C17 (2), 173-208 (1979)
It has been reported for poly (dodecacarborane-siloxane).

Further, Japanese Patent Publication No. Hei 8-505649 discloses an organic boron polymer, and reports that the thermal stability of a siloxane polymer is improved by introducing carborane. However, the above-mentioned organoboron polymer is obtained from the reaction between an acetylene group-containing dilithio salt and a chloro group-containing carborane siloxane at both ends, and requires several steps to synthesize a carborane-containing silicon-based compound from a monomer. It was not the way.

[0004] In addition to the above-mentioned conventional organic boron polymers, carborane-containing silicon-based polymers are scarcely known, and development of new carborane-containing silicon-based polymers having excellent heat resistance is expected.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel carborane-containing silicon-based polymer having excellent heat resistance and flame retardancy, and a method for producing the same.

[0006]

In the present invention, an attempt was made to complex a silyl-substituted carborane derivative with a silicon-based polymer having a reactive double bond group in the side chain. The reaction between the double bond and the silyl group is very efficient, and carborane can be easily introduced into the polymer. Further, since a reactive double bond is bonded to the side chain of the polymer, more carborane can be efficiently introduced, and further improvement in heat resistance and flame retardancy of the polymer can be expected.

The carborane-containing silicon-based polymer according to the first aspect of the present invention (hereinafter referred to as the first aspect of the present invention) has a general formula (1)
And / or a polymer or copolymer having in its structure a carborane-containing unit represented by the general formula (2),
The weight average molecular weight is 500 or more.

The carborane-containing silicon-based polymer of the invention described in claim 2 (hereinafter referred to as invention 2) is represented by the general formula (1):
And / or a carborane-containing unit represented by the general formula (2) and a hydrocarbon group comprising a combination of the units represented by the general formulas (4) to (7) in the structure, and having a weight average molecular weight of 500 or more.

The method for producing a carborane-containing silicon-based polymer according to the invention of claim 3 (hereinafter referred to as the present invention 3) is a method for producing a carborane-containing silicon-based polymer according to the invention 1 or 2, wherein In the silicon-based polymer having in its structure a hydrocarbon group comprising a combination of units represented by (4) to (7) and a silylene group represented by the general formula (8), A heavy bond and a compound represented by the general formula (9) or (1)
Characterized by reacting with a silyl-substituted carborane derivative represented by the formula (1).

Hereinafter, the present invention will be described in detail. The carborane-containing silicon-based polymer of the present invention 1 is a polymer having a carborane-containing unit represented by the general formula (1) or (2) in the structure, a general formula (1) or a general formula (2). Any of a copolymer having the carborane-containing unit represented in the structure, a mixture of these polymers and the copolymer may be used.

[0011]

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In the formulas (1) and (2), R ¹ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms. May also be different. R ² is an alkylene group having 1 to 20 carbon atoms for bonding silicon atoms or 6 to 6 carbon atoms.
Represents 30 arylene groups, which may be the same or different. R ³ represents a hydrogen atom bonded to a carbon atom of carborane, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a silicon compound represented by the general formula (3). CBxHx'C represents carborane which is a divalent cage-like boron compound, and x and x 'are 3 to 1
Represents an integer of 6.

[0013]

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In the formula (3), R ⁴ is a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or a carbon atom having 6 carbon atoms.
Represents up to 30 aryl groups, which may be the same or different.

When the number of carbon atoms in the hydrocarbon group represented by R ^{1 to} R ⁴ increases, the bond is apt to be broken when the number of aliphatic groups increases, and the heat resistance decreases. Since the solubility is reduced, each of the above ranges is limited.

The alkyl group represented by R ¹ , R ³ and R ⁴ includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl,
Examples include octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like.

The aryl groups represented by R ¹ , R ³ and R ⁴ include, for example, phenyl, tolyl, xylyl, biphenyl and naphthyl.

Examples of the alkylene group represented by R ² include a methylene group, an ethylene group, a propylene group,
Butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, trisilene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosylene group And the like.

The arylene group represented by R ² includes, for example, phenylene group, tolylene group, xylene group,
Examples include a biphenylene group, a naphthalenylene group, and an anthracenylene group.

Examples of the carborane represented by CBxHx'C include dodecacarborane, decacarborane, heptacarborane, hexacarborane, pentacarborane and the like.

The hydrocarbon group represented by R ^{1 to} R ⁴ and the carborane represented by CBxHx'C include the same components hereinafter.

The weight-average molecular weight of the silicon-based polymer of the present invention 1 is limited to 500 or more because sufficient heat resistance cannot be obtained if it is too small. The upper limit of the weight average molecular weight is not particularly limited, but if it is too large, the solubility is reduced and it becomes difficult to obtain a molded product.

Next, a second embodiment of the present invention will be described. The carborane-containing silicon-based polymer of the present invention 2 is a combination of a carborane-containing unit represented by the general formula (1) and / or the general formula (2) and a unit represented by the general formulas (4) to (7). And a combined hydrocarbon group in the structure.

[0024]

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[0025]

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In the formulas (1) and (2), R ¹ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms. May also be different. R ² is an alkylene group having 1 to 20 carbon atoms for bonding silicon atoms or 6 to 6 carbon atoms.
Represents 30 arylene groups, which may be the same or different. R ³ represents a hydrogen atom bonded to a carbon atom of carborane, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a silicon compound represented by the general formula (3). CBxHx'C represents carborane which is a divalent cage-like boron compound, and x and x 'are 3 to 1
Represents an integer of 6. In the formulas (4) and (5), R ⁵ represents a hydrogen atom bonded to a carbon atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms. You may. In the formula (7), R ⁶ represents an arylene group having 6 to 30 carbon atoms.

[0027]

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In the formula (3), R ⁴ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or a carbon atom having 6 carbon atoms.
Represents up to 30 aryl groups, which may be the same or different.

Examples of the hydrocarbon group comprising a combination of units represented by the above general formulas (4) to (7) include the following.

[0030]

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Examples of the alkyl group and aryl group represented by R ⁵ include the same alkyl groups and aryl groups as those described above for R ^1, and the same applies to the following. In addition, the above R
Examples of the arylene group represented by ⁶ include the same arylene groups as those described above for R ^2, and the same applies to the following.

Specific examples of the hydrocarbon group comprising the combination of the above (4) to (7) include, for example, a methylene group, an ethylene group, a propylene group, a methylmethylene group, a methylethylene group, a dimethylmethylene group, a dimethylethylene group. Group, vinylene group, 1-butylene group, 4-diene group, ethynylene group, diethynylene group, phenylene group, biphenylene group,
Naphthalenylene group, propylene-1-ene group, butylene-2-ene group, pentylene-1,4-diene group, propylene-1-yne group, butylene-2-yne group, pentylene-1,4-diyne group, methylene Phenylene group, 1,4-
Dimethylenebenzene group, diphenylenemethane group, vinylenephenylene group, 1,4-divinylenebenzene group, 1,
Examples thereof include a 2-diphenylenevinylene group, an ethynylenephenylene group, a 1,4-diethylenebenzene group, and a diphenyleneacetylene group.

The weight average molecular weight of the carborane-containing silicon-based polymer of the present invention 2 is 50 for the same reason as that of the present invention 1.
It is limited to 0 or more, and preferably 5,000,000 or less.

Next, the present invention 3 will be described. In the method for producing a carborane-containing silicon-based polymer according to the third aspect of the present invention, the hydrocarbon group composed of a combination of units represented by the general formulas (4) to (7) and the silylene group represented by the general formula (8) are used. General formula (8) for a silicon-based polymer having in the structure
By reacting the double bond therein with the silyl-substituted carborane derivative represented by the general formula (9) or (10), the carborane-containing silicon-based polymer of the present invention 1 or 2 is obtained.

[0035]

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[0036]

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[0037]

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[0038]

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In the formula, R ¹ is a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or a carbon atom having 6 to 30 carbon atoms.
Which may be the same or different. R ³ is a hydrogen atom bonded to a carbon atom of carborane, an alkyl group having 1 to 20 carbon atoms,
0 represents an aryl group or a silicon compound represented by the general formula (3). CBxHx'C represents carborane which is a bivalent cage-like boron compound, and x and x 'represent integers of 3 to 16. R ⁵ represents a hydrogen atom bonded to a carbon atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different. R ⁶ represents an arylene group having 6 to 30 carbon atoms. R
⁷ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms bonded to a silicon atom, but this is not always necessary, and in the case where no, a double bond group is directly bonded to the silicon atom.

[0040]

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In the formula, R ⁴ is a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms, or a C 6 to 30 carbon atom.
Which may be the same or different.

Specific examples of the hydrocarbon group comprising the combination of the above (4) to (7) include those similar to those of the present invention 2.

Examples of the silylene group represented by the general formula (8) include methylvinylsilylene, ethylvinylsilylene, propylvinylsilylene, butylvinylsilylene, pentylvinylsilylene, hexylvinylsilylene, phenylvinylsilylene, and tolylvinyl. Silylene,
Xylylvinylsilylene, methylallylsilylene, ethylallylsilylene, propylallylsilylene, butylallylsilylene, pentylallylsilylene, hexylallylsilylene, phenylallylsilylene, tolylallylsilylene, xylylallylsilylene, methylpropenylsilylene, ethylpropenylsilylene, Propylpropenylsilylene, butylpropenylsilylene, pentylpropenylsilylene, hexylpropenylsilylene, phenylpropenylsilylene, tolylpropenylsilylene, xylylpropenylsilylene, methylbutenylsilylene,
Ethylbutenylsilylene, propylbutenylsilylene,
Butylbutenylsilylene, pentylbutenylsilylene,
Hexylbutenylsilylene, phenylbutenylsilylene, tolylbutenylsilylene, xylylbutenylsilylene and the like can be mentioned.

Examples of the silyl-substituted carborane derivative represented by the general formula (9) include, for example, dimethylsilylcarborane, diethylsilylcarborane, dipropylsilylcarborane, dibutylsilylcarborane, dipentylsilylcarborane, dihexylsilylcarborane, diphenylsilylcarborane. , Ditolylsilylcarborane, dixylsilylcarborane, dibiphenylsilylcarborane, dinaphthylsilylcarborane, dianthracenylsilylcarborane, methylethylsilylcarborane, methylpropylsilylcarborane, methylbutylsilylcarborane, methylpentylsilylcarborane, methylhexylsilyl Carborane, ethylpropylsilylcarborane, ethylbutylsilylcarborane, ethylpentylsilylcarborane Ethylhexyl silyl carborane,
Propylbutylsilylcarborane, propylpentylsilylcarborane, propylhexylsilylcarborane,
Butylpentylsilylcarborane, butylhexylsilylcarborane, pentylhexylsilylcarborane, methylphenylsilylcarborane, ethylphenylsilylcarborane, propylphenylsilylcarborane, butylphenylsilylcarborane, pentylphenylsilylcarborane, hexylphenylsilylcarborane and the like.

Examples of the silyl-substituted carborane derivative represented by the above formula (10) include m-bis (dimethylsilyl) carborane, m-bis (diethylsilyl) carborane, m-bis (dipropylsilyl) carborane, m
-Bis (dibutylsilyl) carborane, m-bis (dipentylsilyl) carborane, m-bis (dihexylsilyl) carborane, m-bis (diphenylsilyl) carborane, m-bis (ditolylsilyl) carborane, m-bis (dixylsilyl) carborane , M-bis (dibiphenylsilyl) carborane, m-bis (dinaphthylsilyl) carborane, m-bis (dianthracenylsilyl)
Carborane, m-bis (methylethylsilyl) carborane, m-bis (methylpropylsilyl) carborane, m
-Bis (methylbutylsilyl) carborane, m-bis (methylpentylsilyl) carborane, m-bis (methylhexylsilyl) carborane, m-bis (ethylpropylsilyl) carborane, m-bis (ethylbutylsilyl) carborane, m -Bis (ethylpentylsilyl) carborane, m-bis (ethylhexylsilyl) carborane, m-bis (propylbutylsilyl) carborane, m
-Bis (propylpentylsilyl) carborane, m-bis (propylhexylsilyl) carborane, m-bis (pentylhexylsilyl) carborane, m-bis (methylphenylsilyl) carborane, m-bis (ethylphenylsilyl) carborane, m -Bis (propylphenylsilyl) carborane, m-bis (butylphenylsilyl) carborane, m-bis (pentylphenylsilyl)
Carborane, m-bis (hexylphenylsilyl) carborane, and their o- and p-isomers.

The catalyst used in the reaction in the production method of the present invention 3 includes, for example, chloroplatinic acid, hexarhodium hexadecacarbonyl, bis (divinyltetramethyldisiloxane) platinum, etc., but is not limited thereto. Not something. If the amount of the catalyst is too small, the reaction does not proceed sufficiently, and if the amount is too large, the catalyst tends to remain in the polymer after synthesis, and the heat resistance decreases due to the remaining. Therefore, the general formulas (8) and (4) ) To (7), preferably 0.001 to 20 mol%, more preferably 0.01 to 10 mol%, based on the structural units of the silicon-based polymer represented by (7).

The molar ratio of the silicon-based polymer to the silyl-substituted carborane derivative used in the above reaction is such that when the amount of carborane introduced is small, the heat resistance and flame retardancy of the obtained polymer are not significantly improved. Coalescence: The silyl-substituted carborane derivative is preferably 1: 0.01 to 20, more preferably 1: 0.1 to 10.

The solvent used in the above reaction may be either polar or non-polar, but is preferably an aprotic solvent such as toluene or tetrahydrofuran. The amount of the solvent used is 0.01 to 5 in terms of the concentration of the structural unit of the silicon-based polymer.
0 mol / L is preferable, and more preferably 0.05 to 5
mol / L.

The above reaction is preferably carried out between room temperature and the boiling point of the solvent. This reaction can be carried out either in air or under an inert gas atmosphere, but preferably under an argon gas or nitrogen gas atmosphere.

If the reaction time of the above reaction is short, the introduction reaction of carborane does not proceed sufficiently, and the heat resistance of the obtained polymer does not improve. Conversely, if the reaction time is long, a side reaction such as cross-linking proceeds, and It will not melt, making it difficult to handle,
Since heat resistance falls, 1 to 72 hours are preferable. After completion of the reaction, the silicon-based polymer may be purified by a reprecipitation method or gel permeation chromatography (GP).
C) and the like.

[0051]

Embodiments of the present invention will be described below.

(Example 1) A 1-liter three-necked flask equipped with a reflux tube purged with argon and a dropping funnel was charged with
25.23 g of 4-diethynylbenzene (200.0 mm
ol) and dissolved in 900 mL of tetrahydrofuran. After cooling the flask in a dry ice / methanol bath, a hexane solution of n-butyl lithium (1.6 mol) was used.
/ L) 250 mL was added dropwise over 30 minutes and stirred for 1 hour. Then, phenylvinyldichlorosilane 40.64
g (200.0 mmol) in tetrahydrofuran solution 1
00 mL was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 24 hours. The obtained reaction solution was treated with a saturated aqueous solution of ammonium chloride 1.
After pouring into 4 L and stirring for several minutes, the tetrahydrofuran layer was separated. After the aqueous layer was extracted three times with diethyl ether, the organic layers were combined and dried over anhydrous magnesium sulfate. The organic solvent was concentrated, poured into 4 L of methanol, and the precipitate was separated by filtration to obtain 37.60 g of poly (1,4-diethynylbenzene / phenylvinylsilylene) as a tan powder (polymer). .

500 mL of 4 with a reflux tube purged with argon
7.69 g (30.0 m) of the above poly (1,4-diethynylbenzene / phenylvinylsilylene) was placed in a one-necked flask.
mol) and dissolved in 150 ml of toluene.
° C, and 0.15 mmol of catalyst [bis (divinyltetramethyldisiloxane) platinum] ｛Pt [CH ₂ ＣC
_{HSi (CH 3) 2 OSi (} CH 3) 2 CH = CH 2] placed a toluene solution of _2}, and stirred for 10 minutes. Then, 1,
40 m of a toluene solution of 5.78 g (15.0 mmol) of 7-bis (phenylmethylsilyl) dodecacarborane
After the dropwise addition, the temperature of the oil bath was raised to 125 ° C.
The mixture was refluxed for 0 hours. Further, the reaction solution was distilled off under reduced pressure, and then poured into 1.7 L of isopropanol. The resulting precipitate was separated by filtration to obtain 9.9 g of a yellow-white powder (polymer). The weight average molecular weight of this polymer was 55,900 in terms of polystyrene.

(Example 2) 15.14 g (120.0 mmol) of 1,4-diethynylbenzene was placed in a 1 L four-necked flask equipped with a reflux tube and a dropping funnel reflux tube replaced with argon.
Was dissolved in 500 mL of tetrahydrofuran. After cooling the flask with a dry ice / methanol bath, n
-Butyllithium hexane solution (1.6 mol / L)
150 mL was added dropwise over 45 minutes, and the mixture was stirred for 1 hour. Next, 12.19 g of phenylvinyldichlorosilane (6
0.0mmol) in 120 mL of tetrahydrofuran solution
Was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 24 hours. The obtained reaction solution was put into 500 mL of a saturated aqueous solution of ammonium chloride, and after stirring for several minutes, a tetrahydrofuran layer was separated. After the aqueous layer was extracted three times with diethyl ether, the organic layers were combined and dried over anhydrous magnesium sulfate. After concentrating the organic solvent and pouring the mixture into 1.8 L of methanol, the precipitate is separated by filtration to obtain poly (1,4-diethynylbenzene / phenylvinylsilylene / methylphenylsilylene) as a yellowish white powder (polymer). 21.75 g were obtained.

Argon-replaced 500 mL 3 with a reflux tube
The above-mentioned poly (1,4-diethynylbenzene)
Phenylvinylsilylene / methylphenylsilylene
Add 10.02 g (20.0 mmol) and add toluene
After dissolving in 300 ml, the temperature was raised to 50 ° C.
mol of catalyst [bis (divinyltetramethyldisiloxa)
N) Platinum] @Pt [CH_Two= CHSi (CH_Three)_TwoOSi
 (CH_Three)_TwoCH = CH_Two] _TwoAdd the toluene solution of｝ and add 1
Stirred for 0 minutes. Then, 1,7-bis (dimethylsilicone
Le) 2.61 g (10.2 mmol) of dodecacarborane
After dropping 25 ml of toluene solution of
The temperature was raised to 120 ° C., and the mixture was refluxed for 10 hours. In addition,
After the reaction solution was distilled off under reduced pressure, it was poured into 2 L of methanol.
The obtained precipitate was separated by filtration, and yellowish white powder (polymer) 1
1.2 g were obtained. The weight average molecular weight of this polymer is
It was 41,200 in terms of styrene.

The ¹ H-NMR spectrum (“D” manufactured by Bruker) measured for the yellowish white powder of Example 1 above
RX300) and FIG. 2 show IR spectra (measured by Biorad “FTS135 System”), respectively. FIG. 3 shows a ¹ H-NMR spectrum (measured by Bruker “DRX300”) and an IR spectrum (measured by Bio-Rad “FTS135 System”) of the yellowish white powder of Example 2. 4 are shown.

In FIGS. 1 and 3, peaks of protons based on carborane are observed from 0.7 to 4 ppm. Further, the peak of the methyl group or methylene group proton bonded to the silicon atom at 0.07 to 0.6 ppm is 7 to 8 pp.
In m, a peak of a phenyl group proton was confirmed. 2 and 4, absorption due to carborane was observed at 2594 cm ⁻¹ , and these results indicate that Example 1 was used.
Is a carborane-containing silicon-based polymer represented by the formula (11), and the polymer obtained in Example 2 is a carborane-containing silicon-based polymer represented by the formula (12) Was confirmed.

[0058]

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[0059]

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COMPARATIVE EXAMPLE 1 Argon-substituted reflux tube 1
In a 00 ml two-necked flask, 0.51 g of poly (1,3-diethynylbenzene / phenylvinylsilane) (2.0
mmol) and dissolved in 10 ml of tetrahydrofuran. Then, the reaction solution was heated to 55 ° C., and a catalyst (H ₂ PtCl ₂ ) was added.
Put isopropanol solution 1mL of _{6 · 6H 2 O) 0.005g (} 0.01mmol), and stirred for 10 minutes.
Then, 1,4-bis (dimethylsilyl) benzene 0.1.
19 g (1.0 mmol) of tetrahydrofuran solution 5
After dropping mL, the temperature of the oil bath was raised to 75 ° C.
The mixture was refluxed for 0 hours. Next, the reaction solution was cooled to room temperature and poured into 500 ml of methanol. The resulting precipitate was separated by filtration to obtain 0.478 g of a yellow-white powder (polymer).

The obtained polymer was subjected to the same ¹ H-NMR spectrum measurement and IR spectrum measurement as in Example 1 to confirm that it was a silicon-based polymer represented by the formula (13).

[0062]

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The thermogravimetric analysis of the polymers obtained in Examples 1 and 2 and Comparative Example 1 was performed by using “SSC520” manufactured by Seiko Instruments Inc.
The measurement results were shown in FIG. In addition, a 5% by weight decomposition temperature (T
Table 5 shows d ₅ ) and the residual weight at 800 ° C. (W ₈₀₀ ).

[0064]

[Table 1]

Table 1 shows that the carborane-containing silicon-based polymers of Examples 1 and 2 are very excellent in heat resistance.

[0066]

As described above, the silicon-based polymer of the present invention is excellent in heat resistance and is suitably used for space / aviation materials, building materials and the like.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of a silicon-based polymer of Example 1.

FIG. 2 is an IR spectrum of the silicon-based polymer of Example 1.

FIG. 3 is a ¹ H-NMR spectrum of the silicon-based polymer of Example 2.

FIG. 4 is an IR spectrum of the silicon-based polymer of Example 2.

FIG. 5 is a thermal decomposition curve of the silicon-based polymer of Examples 1 and 2 and Comparative Example 1.

Claims (3)

[Claims] 1. A polymer or copolymer having in its structure a carborane-containing unit represented by the general formula (1) and / or the general formula (2), and having a weight average molecular weight of 50
A carborane-containing silicon-based polymer, which is 0 or more. Embedded image [In the formula, R ¹ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different. R ² has 1 to 20 carbon atoms for bonding silicon atoms.
And an arylene group having 6 to 30 carbon atoms, which may be the same or different. R ³
Represents a hydrogen atom bonded to a carbon atom of carborane, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a silicon compound represented by the general formula (3). CBx
Hx'C represents carborane which is a divalent cage-like boron compound, and x and x 'represent integers of 3 to 16.] (In the formula, R ⁴ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may be the same or different.) 2. A hydrocarbon group comprising a combination of a carborane-containing unit represented by the general formula (1) and / or the general formula (2) and a unit represented by the general formulas (4) to (7). Having a weight average molecular weight of 500
A carborane-containing silicon-based polymer as described above. Embedded image Embedded image [In the formula, R ¹ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different. R ² has 1 to 20 carbon atoms for bonding silicon atoms.
And an arylene group having 6 to 30 carbon atoms, which may be the same or different. R ³
Represents a hydrogen atom bonded to a carbon atom of carborane, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a silicon compound represented by the general formula (3). CBx
Hx'C represents carborane which is a divalent cage-like boron compound, and x and x 'represent integers of 3 to 16. R
⁵ represents a hydrogen atom bonded to a carbon atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different. R ⁶ represents an arylene group having 6 to 30 carbon atoms. (In the formula, R ⁴ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may be the same or different.) 3. A silicon-based polymer having a hydrocarbon group comprising a combination of units represented by formulas (4) to (7) and a silylene group represented by formula (8) in the structure. 3. The carborane-containing silicon-based polymer according to claim 1, wherein the double bond in the formula (8) is reacted with the silyl-substituted carborane derivative represented by the formula (9) or (10). Manufacturing method. Embedded image Embedded image Embedded image Embedded image [In the formula, R ¹ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, which may be the same or different. R ³ represents a hydrogen atom bonded to a carbon atom of carborane, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a silicon compound represented by the general formula (3). CBxHx'C represents carborane which is a bivalent cage-like boron compound, and x and x 'represent integers of 3 to 16. R ⁵ is a hydrogen atom bonded to a carbon atom, and has 1 to 1 carbon atoms.
Represents an alkyl group having 20 or an aryl group having 6 to 30 carbon atoms, and may be the same or different. R ⁶
Represents an arylene group having 6 to 30 carbon atoms. R ⁷ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms bonded to the silicon atom, but is not always necessary. In the case where there is no R ⁷ , a double bond group is directly bonded to the silicon atom. Embedded image (In the formula, R ⁴ represents a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may be the same or different.)