JP3468665B2 - Carborane group-containing silicon-based polymer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates are those which relate to the heat resistance, useful novel carborane-containing silicon-based polymer as an excellent functional material in flame retardancy and heat distortion resistance and a manufacturing how.

[0002]

2. Description of the Related Art Conventionally, silicon-based polymers having excellent heat resistance and flame retardancy have been developed. Further, it has been attempted to improve the molecular weight and mechanical strength by a method of crosslinking a polymer by a polymer reaction (Organometallics, 15, 75 (1996)), but the heat resistance,
The flame retardancy was not always sufficient.

On the other hand, some carborane-containing silicon polymers are known, for example, J. Macromol. S.
ci.-Rev. Macromol. Chem., C17 (2), 173-208 (1979)
Reports on poly (dodecacarborane-siloxane). In addition, Japanese Patent Publication No. 8-505649 discloses an organic boron polymer, and it is reported that the thermal stability of a siloxane polymer is improved by introducing carborane.

However, the above-mentioned organoboron polymer is obtained from the reaction of an acetylene group-containing dilithio salt and a carborane siloxane containing both terminal chloro groups, and it takes several steps to synthesize a monomeric carborane-containing silicon-based compound, so that it is convenient. It wasn't the right way. In addition to the above-mentioned conventional organic boron polymers, almost no carborane-containing silicon polymer is known, and development of a novel carborane-containing silicon polymer having excellent heat resistance is expected.

[0005]

An object of the present invention is to provide a to provide a heat resistance, novel carborane-containing silicon-based polymer is excellent in flame retardancy and heat distortion resistance and a manufacturing how.

[0006]

In view of the above drawbacks, the present invention has attempted to complex a silicon-based polymer having a reactive double bond group in its side chain with a silyl-substituted carborane derivative. The reaction between the double bond group and the silyl group is very efficient, and it can be expected that carborane is easily introduced into the polymer. Further, since a reactive double bond exists in the side chain of the polymer, more carborane can be introduced efficiently, and further improvement in heat resistance and flame retardancy of the polymer can be expected.

The invention according to claim 1 of the present invention (hereinafter referred to as the first
The carborane-containing silicon polymer according to the invention)
Homopolymers of carborane-containing unit represented by the general formula (1), a homopolymer of carborane-containing unit represented by the general formula (2), or carborane-containing represented by the general formula (1) and (2) units of the copolymer or Rannahli, weight average molecular weight is characterized in that 500 or more.

The invention according to claim 2 of the present invention (hereinafter referred to as the second
The carborane-containing silicon polymer according to the invention)
It consists of a carborane-containing unit represented by the general formula (1) and / or (2), the general formula (4) to a hydrocarbon group consisting of one or more units represented by (7), the weight average
It has a molecular weight of 500 or more .

The invention according to claim 3 of the present invention (hereinafter, referred to as the third
The method for producing a carborane-containing silicon polymer according to the invention is the method for producing a carborane-containing silicon polymer according to the first or second invention, which is represented by the general formula (8).
A silicon-based polymer composed of a knit or a silicon-based polymer composed of a combination of hydrocarbon groups composed of one or more units represented by the general formula (8) and the general formulas (4) to (7); 9) or a silyl-substituted carborane derivative represented by the general formula (10) is reacted.

The carborane-containing silicon polymer of the first invention will be described below. The carborane-containing silicon-based polymer of the first invention is a homopolymer of a carborane-containing unit represented by the general formula (1); a homopolymer of a carborane-containing unit represented by the general formula (2); ),
It may be any of the copolymers of the carborane-containing unit represented by (2).

[0011]

[Chemical 13]

[0012]

[Chemical 14]

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

In the formula, R ² is a carbon bonded to a silicon atom.
C1-C20 alkylene group or C6-C30 aryl
It represents a len group, and l is 0 or 1 .

In the formula, R ³ is 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). Represent CBxHx'C represents carborane which is a divalent cage boron compound, and x and x'are 3-1.
Represents an integer of 6.

[0016]

[Chemical 15]

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

In the above formulas (1) to (3), when the number of carbon atoms of the hydrocarbon group represented by R ^{1 to} R ⁴ is aliphatic, the bond is easily broken and the heat resistance is lowered, When the amount of aromatics increases, the solubility in solvents decreases, so
It is limited to the above range.

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

The aryl group represented by R ¹ is
Examples thereof include a phenyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group and an anthracenyl group.

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

Examples of the arylene group represented by R ² include a phenylene group, a tolylene group, a xylylene group, a biphenylene group, a naphthalenylene group, and an anthracenylene group.

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

The hydrocarbon group represented by R ^{1 to} R ⁴ is
The following also represents the same hydrocarbon group, and the carborane represents the same component in the following.

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

Next, the second invention will be described. The carborane-containing silicon polymer of the second invention comprises a carborane-containing unit represented by the general formula (1) and / or (2) and one or more units represented by the general formulas (4) to (7). comprising comprising a hydrocarbon radical.

[0027]

[Chemical 16]

[0028]

[Chemical 17]

In the formula, R ¹ is a hydrogen atom bonded to a silicon atom, an alkyl group having 1 to 20 carbon atoms or 6 to 30 carbon atoms.
Represents an aryl group and may be the same or different. In the formula, R ² is a carbon bonded to a silicon atom.
C1-C20 alkylene group or C6-C30 aryl
It represents a len group, and l is 0 or 1 . In the formula, R ³ is a hydrogen atom bonded to a carbon atom of carborane, having 1 to 2 carbon atoms.
It represents an alkyl group of 0, an aryl group of 6 to 30 carbon atoms or a silicon compound represented by the general formula (3). CBxHx '
C represents carborane which is a divalent cage boron compound, and x and x ′ represent an integer of 3 to 16.

[0030]

[Chemical 18]

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

[0032]

[Chemical 19]

In the formula, 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 they may be the same or different. R ⁶ represents an arylene group having 6 to 30 carbon atoms .

Examples of the hydrocarbon group composed of one or more units represented by the above general formulas (4) to (7) include:
Examples thereof include an alkylene group consisting of only general formulas (4) to (7), an arylene group, or a hydrocarbon group having the following structure consisting of a combination of general formulas (4) to (7).
It should be noted that these are merely examples of combinations, and the present invention is not limited to these combinations.

[0035]

[Chemical 20]

Specific examples of R ⁵ include a hydrogen atom and an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Group, undecyl group,
Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, and the like; aryl groups include phenyl group, tolyl group, xylyl group, biphenyl group, naphthyl group, anthracenyl group. Groups and the like.

Specific examples of R ⁶ include a phenylene group, a tolylene group, a xylylene group, a biphenylene group, a naphthalenylene group and an anthracenylene group.

As the hydrocarbon group represented by R ⁵ and R ⁶ , the following groups are the same.

Examples of the hydrocarbon group composed of one or more units represented by the above general formulas (4) to (7) include, for example,
Methylene, ethylene, propylene, methylmethylene, methylethylene, dimethylmethylene, dimethylethylene,
Vinylene, butylene-1, 3 - diene, ethynylene, Jiechiniren, phenylene, biphenylene, naphthalenylene, propylene-1-ene, butylene-2-ene, pentylene-1,4-diene, propylene-1-yne, butylene-2 In, pentylene-1,4-diyne, methylenephenylene, 1,4-dimethylenebenzene, diphenylenemethane, vinylenephenylene, 1,4-divinylenebenzene, 1,2-diphenylenevinylene, ethynylenephenylene, 1, 4-diethynylene benzene, diphenylene acetylene, etc. are mentioned.

As the hydrocarbon group consisting of one or more of the units represented by the above general formulas (4) to (7), the following groups are the same.

Weight average molecule of the silicon-based polymer of the second invention
If the amount becomes small, sufficient heat resistance and moldability will not be obtained.
Therefore, it is limited to 500 or more. Weight average molecular weight
Upper limit is not particularly limited, when too large dissolved in
Since the degradability decreases and it becomes difficult to obtain a molded product, 5
It is preferably 1 million or less.

Next, the third invention will be described. A third invention is a method for producing a carborane-containing silicon polymer according to the first or second invention, which is a unit represented by the general formula (8).
Or a silicon-based polymer of the formula (8) and a combination of a hydrocarbon group consisting of one or more units represented by the general formulas (4) to (7). The heavy bond is reacted with the silyl-substituted carborane derivative represented by the general formula (9) or (10).

[0043]

[Chemical 21]

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, and they may be the same or different. In the formula, 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. l is 0 or 1.

When the number of carbon atoms of the hydrocarbon group represented by R ⁷ is aliphatic, the bond is easily broken and the heat resistance is lowered, and when it is aromatic, the solubility in the solvent is lowered. Therefore, it is limited to the above range.

[0046]

[Chemical formula 22]

In the formula, 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 they may be the same or different. R ⁶ represents an arylene group having 6 to 30 carbon atoms.

[0048]

[Chemical formula 23]

[0049]

[Chemical formula 24]

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. In the formula, R ³ is a hydrogen atom bonded to a carbon atom of carborane, an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms.
It represents a silicon compound represented by the aryl group of 30 or the general formula (3). CBxHx′C represents carborane which is a divalent cage boron compound, and x and x ′ are 3 to.
Represents an integer of 16.

Examples of the alkylene group represented by R ⁷ include methylene group, ethylene group, propylene group,
Butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, nonadecylene group, eicosylene group Etc.

Examples of the arylene group represented by R ⁷ include a phenylene group, a tolylene group, a xylylene group, a biphenylene group, a naphthalenylene group and an anthracenylene group.

Silicon-based polymerization represented by the above general formula (8)
Examples of body constituent units include methyl vinyl chloride.Re
LesEthyl vinylLillePropyl vinyl chlorideLille
Butyl vinylLillePentyl vinylLilleThe
Hexyl vinylLillePhenyl vinyl esterLilleN, To
Ril vinylLilleXylyl vinylLilleN, methyl
ArylLilleAnd ethyl allylLilleN, propyl ant
LuciLilleButyl allylLillePentyl allyl
LilleHexyl allylLillePhenyl allylRe
LesAnd tolyl allylLilleXylyl allylLille
Methyl propenylLilleAnd ethyl propenylRe
LesPropyl propenylLilleButylpropenyl
ShiLillePentyl propenylLilleHexyl Pro
PenisLillePhenylpropenylLilleTrill
PropenylLilleXylylpropenylLilleThe
ChilbutenylLilleEthyl butenylLilleN, professional
PilbutenilciLilleButyl butenylLilleA pen
ChilbutenylLilleHexylbutenylLilleN, F
PhenylbutenylLilleTril butenylLilleN, ki
Cyril butenylLilleAnd the like.

As the silyl-substituted carborane derivative represented by the above general formula (9) or (10), examples of mono-substituted compounds include dimethylsilylcarborane, diethylsilylcarborane, dipropylsilylcarborane, dibutylsilylcarborane and dipentyl. Silylcarborane, dihexylsilylcarborane, diphenylsilylcarborane, ditolylsilylcarborane, dixylylsilylcarborane, dibiphenylsilylcarborane, dinaphthylsilylcarborane, dianthracenylsilylcarborane,
Examples thereof include methylphenylsilylcarborane, ethylphenylsilylcarborane, propylphenylsilylcarborane, butylphenylsilylcarborane, pentylphenylsilylcarborane, and hexylphenylsilylcarborane.

Examples of the 2-substituted product 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 (dixylylsilyl) carborane, m-
Bis (dibiphenylsilyl) carborane, m-bis (dinaphthylsilyl) carborane, m-bis (dianthracenylsilyl) carborane, m-bis (methylphenylsilyl) carborane, m-bis (ethylphenylsilyl)
Carborane, m-bis (propylphenylsilyl) carborane, m-bis (butylphenylsilyl) carborane, m-bis (pentylphenylsilyl) carborane,
Examples include m-bis (hexylphenylsilyl) carborane, and ortho-isomers and para-isomers thereof.

Examples of the catalyst used in the above reaction include chloroplatinic acid, hexarhodium hexadecacarbonyl [Rh ₆ (CO) ₁₆ ], and the like. The catalyst amount is
If the amount is too small, the reaction does not proceed sufficiently, and if the amount is too large, it tends to remain in the polymer after synthesis, and the heat resistance decreases.
0.001 to 20 m with respect to the constitutional unit of the silicon-based polymer
ol% is preferable, and more preferably 0.01 to 10 mo.
1%.

The molar ratio of the silicon-based polymer used in the above reaction to the silyl-substituted carborane derivative is such that if the amount of the introduced carborane is too small, the heat resistance and flame retardancy of the resulting polymer will not be improved so much. The silyl-substituted carborane derivative is preferably 0.01 to 10 moles, and more preferably 0.1 to 5 moles, relative to 1 mole of the polymer.

The solvent used in the above reaction may be 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 constituent unit of the silicon-based polymer.
0 mol / L is preferable, and more preferably 0.05 to 5
It is mol / L.

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

If the reaction time of the above reaction is too short, the carborane introduction reaction will not proceed sufficiently and the heat resistance will not be improved. On the contrary, if it is too long, the crosslinking reaction will proceed and it will not dissolve in the solvent, making handling difficult. Therefore, 1 to 24 hours are preferable. After the completion of the reaction, examples of the method for purifying the silicon-based polymer include reprecipitation method and fractionation by gel permeation chromatography (GPC).

The method of crosslinking the silicon-based polymer will be described below. The heating temperature in the case of thermally crosslinking the silicon-based polymer is 100 to 500 ° C. because if the temperature is low, the crosslinking reaction does not sufficiently occur and thus the curing is insufficient, and if it is high, the temperature is deteriorated before the silicon-based polymer is crosslinked. Preferably
More preferably, it is 250 to 400 ° C.

The above thermal crosslinking reaction proceeds in air, in an inert gas atmosphere or under reduced pressure. If the reaction time of this thermal crosslinking reaction becomes shorter, the crosslinking reaction will not proceed sufficiently and curing will be insufficient, and if it becomes longer, a deterioration reaction will occur.
It is preferably 1 minute to 10 hours, more preferably 30 minutes to 5 hours.

Photocrosslinking of the silicon-based polymer is carried out by irradiation with active rays such as ultraviolet rays and electron beams. When ultraviolet rays are irradiated, the crosslinking reaction does not proceed sufficiently and the curing becomes insufficient when the irradiation amount is small, and the decomposition reaction occurs when the irradiation amount is large, so that the integrated exposure amount at 365 nm is 50 to 5,0.
00 mJ / cm ² is preferable.

As the light source used for the irradiation of the ultraviolet rays, for example, a high pressure mercury lamp, a halogen lamp, a xenon lamp, a nitrogen laser, a He-Cd laser, an Ar laser or the like is used.

In the case where the above silicon-based polymer is subjected to electron beam cross-linking, when the irradiation dose of electron beam is small, the crosslinking reaction does not proceed sufficiently and curing is insufficient, and when it is large, a decomposition reaction occurs. ~ 100 Mrad is preferred.

The photocrosslinking reaction proceeds in either air or an inert gas atmosphere, but is preferably in an inert gas atmosphere such as nitrogen or argon.

[0067]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the present invention will be given below. (Example 1) poly 2-necked 100ml flask with a reflux tube was replaced with argon (m-diethynylbenzene-phenylvinyl Shi Li
Put Les emissions) 2.56g (10.0mmol), was dissolved in tetrahydrofuran 50 ml. The temperature of the reaction solution was raised to 55 ° C., and 0.024 g of catalyst (H ₂ PtCl ₆ · 6H ₂ O)
1 ml of an isopropanol solution (0.05 mmol) was added and stirred for 10 minutes. 15 ml of a tetrahydrofuran solution containing 1.30 g (5.0 mmol) of 1,7-bis (dimethylsilyl) dodecacarborane was added dropwise, the temperature of the oil bath was raised to 75 ° C., and the mixture was heated under reflux for 10 hours. After the reaction solution was distilled off under reduced pressure, it was put into 500 ml of methanol. The precipitate was filtered off to obtain 2.57 g of yellowish white powder.
The weight average molecular weight of this polymer was 7,400 in terms of polystyrene.

The ¹ H-NMR spectrum of the above polymer (measured by “DRX300” manufactured by Bruker) is shown in FIG.
The R spectra (measured by "FTS135 system" manufactured by Bio-Rad) are shown in FIG. 2, respectively. In FIG. 1, 0.
A peak of protons based on carborane is seen from 7 to 4 ppm. Further, a proton peak of a methyl group and a methylene group bonded to a silicon atom was confirmed at 0.07 to 0.6 ppm, and a proton peak of a phenyl group was confirmed at 7 to 8 ppm. 2155 cm in FIG.
^-1 ethynylene group, absorption due to carborane the 2594Cm ^-1 was observed, respectively. From these, it was confirmed that Example 1 was a carborane-containing silicon-based polymer having the structure of the general formula (11).

[0069]

[Chemical 25]

[0070] (Example 2) Poly 2-necked 100ml flask with a reflux tube was replaced with argon (m-diethynylbenzene-phenyl allyl Shi Li
Put Les emissions) 1.08g (4.0mmol), was dissolved in tetrahydrofuran 50 ml. The temperature of the reaction solution was raised to 55 ° C., and 0.011 g of catalyst (H ₂ PtCl ₆ .6H ₂ O)
1 ml of an isopropanol solution of (0.02 mmol) was added and stirred for 10 minutes. After dropping 15 ml of a tetrahydrofuran solution containing 0.52 g (2.0 mmol) of 1,7-bis (dimethylsilyl) dodecacarborane, the temperature of the oil bath was set to 75 ° C., and the mixture was heated under reflux for 10 hours. After the reaction solution was distilled off under reduced pressure, it was put into 500 ml of methanol. The precipitate was filtered off to obtain 0.98 g of yellowish white powder. The weight average molecular weight of this polymer is 4, in terms of polystyrene.
It was 100.

The ¹ H-NMR spectrum of the above polymer (measured by "DRX300" manufactured by Bruker) is shown in FIG.
The R spectrum (measured by "FTS135 system" manufactured by Bio-Rad) is shown in FIG. In FIG. 3, 0.7-4 pp
A proton peak based on carborane is observed over m. Further, the proton peaks of the methyl group and the methylene group bonded to the silicon atom at 0.07 to 0.6 ppm are 7
A proton peak of a phenyl group was confirmed at ˜8 ppm. Further, ethynylene group, absorption attributable to carborane to 2593cm ^-1 were observed respectively 2155Cm ^-1 in FIG. From these, it was confirmed that Example 2 was a carborane-containing silicon-based polymer having the structure of the general formula (12).

[0072]

[Chemical formula 26]

(Example 3) 12.62 g of 1,4-diethynylbenzene was placed in a 200 ml three-necked flask equipped with a reflux tube and a funnel replaced with argon.
(100.0 mmol), and tetrahydrofuran 4
It was dissolved in 50 ml. The reaction solution was cooled in a dry ice / methanol bath, 125 ml of a n-butyllithium hexane solution (1.6 mol / L) was added dropwise over 30 minutes, and the mixture was stirred for 1 hour. Next, 80 ml of a tetrahydrofuran solution containing 20.34 g (100.1 mmol) of phenylvinyldichlorosilane was added dropwise over 30 minutes, and the mixture was stirred at room temperature for 24 hours. The obtained reaction solution was put into 400 ml of a saturated aqueous solution of ammonium chloride, and the mixture was stirred for several minutes, and then the tetrahydrofuran layer was separated. The aqueous layer was extracted 3 times with diethyl ether, and the organic layers were combined and dried over anhydrous magnesium sulfate. Next, the organic solvent was concentrated and poured into 1 L of methanol, and then the precipitate was filtered off to obtain 5.68 g of a yellowish brown powdery polymer.

100 ml of 2 with a reflux tube replaced with argon
One mouth flask poly (1,4-diethynylbenzene-phenylvinyl Shi relay emissions) 1.05 g (4.1 mmol)
Was added and dissolved in 20 ml of toluene. Reaction liquid at 55 ° C
The temperature was raised to 0.01 and the catalyst (H ₂ PtCl ₆ · 6H ₂ O) 0.01
1 ml of isopropanol solution containing g (0.02 mmol)
Was charged and stirred for 10 minutes. Then, 0.57 g of 1,7-bis (dimethylsilyl) dodecacarborane (2.0 m
15 ml of a toluene solution of (mol) was added dropwise, the temperature of the oil bath was set to 120 ° C., and the mixture was heated under reflux for 10 hours. Further, after distilling off the reaction solution under reduced pressure, 500 ml of methanol
After throwing in, the precipitate was filtered off to obtain 1.3 g of yellowish white powder. The weight average molecular weight of this polymer was 35,100 in terms of polystyrene.

The ¹ H-NMR spectrum of the above polymer (measured by "DRX300" manufactured by Bruker) is shown in FIG.
The R spectrum (measured by "FTS135 system" manufactured by Bio-Rad) is shown in FIG. In FIG. 5, 0.7-4 pp
A proton peak based on carborane is observed over m. Further, the proton peaks of the methyl group and the methylene group bonded to the silicon atom at 0.07 to 0.6 ppm are 7
A proton peak of a phenyl group was confirmed at ˜8 ppm. Further, in FIG. 6, absorption due to carborane was observed at 2594 cm ⁻¹ . From these, it was confirmed that Example 3 was a carborane-containing silicon-based polymer having the structure of the following general formula (13).

[0076]

[Chemical formula 27]

[0077] (Comparative Example 1) poly 2-necked 100ml flask with a reflux tube was replaced with argon (m-diethynylbenzene-phenylvinyl Shi Li
Put Les emissions) 0.51g (2.0mmol), was dissolved in tetrahydrofuran 10 ml. The temperature of the reaction solution was raised to 55 ° C., and 0.005 g of catalyst (H ₂ PtCl ₆ · 6H ₂ O)
1 ml of an isopropanol solution of (0.01 mmol) was added and stirred for 10 minutes. After adding dropwise 5 ml of a tetrahydrofuran solution containing 0.19 g (1.0 mmol) of 1,4-bis (dimethylsilyl) benzene, the temperature of the oil bath was set to 7
The mixture was brought to 5 ° C. and heated under reflux for 10 hours. The reaction solution was cooled to room temperature and put into 500 ml of methanol. The precipitate was filtered off to obtain a polymer represented by the general formula (14) (yellowish white powder 0.478 g). The weight average molecular weight of this polymer was 14,500 in terms of polystyrene.

[0078]

[Chemical 28]

The following performance evaluations were performed on the polymers obtained in the above Examples and Comparative Examples. (1) The heat resistance of the heat resistance Evaluation of Examples and obtained in Comparative Example polymer, Se
Using the "SSC5200 system" manufactured by Iko Denshi
It was evaluated by a thermal decomposition curve. 5% by weight of under air atmosphere
Decomposition temperature (Td ₅ ), weight residual ratio at 800 ° C (W
₈₀₀ ) is shown in Table 1 . FIG. 7 shows the measurement results of the thermal decomposition curves of Example 1 (upper side) and Comparative Example 1 (lower side) under the air atmosphere, and FIG. 8 shows Example 2 (upper side) and Comparative Example 1 (lower side).
9 shows the measurement results of the thermal decomposition curves of Example 3 (upper side) and Comparative Example 1 (lower side).
Shown respectively.

(2) Flame retardance evaluation The polymers obtained in Examples and Comparative Example 1 were treated with aluminum.
In a mold and melt-mold at 240 ° C for 2 hours to obtain a molded body.
It was The obtained molded product was evaluated for flame retardancy by a combustion test in an atmosphere with an oxygen concentration of 50%, and the evaluation results are shown in Table 1.

[0081]

[Table 1]

As is clear from Table 1, the carborane-containing silicon-based polymers of Examples are materials having very excellent heat resistance, and also because they are extinguished immediately after ignition, they are materials having excellent flame retardancy. It can be said that there is.

The carborane-containing silicon-based polymer of Example 1 was melt-molded at 240 ° C. for 2 hours, and the molded product was heated at 330 ° C. for 2 hours in an air atmosphere to obtain a carborane-containing silicon-based resin cured product. This molded article and its cured resin I
The R spectra are shown in FIG. 10 , respectively. As is clear from FIG. 10 , in the resin cured product (lower curve), the absorption due to acetylene at 2155 cm ⁻¹ is reduced as compared with the molded body (upper curve), and the crosslinking curing reaction occurs by heating. I understand that.

The thermal decomposition curve of the carborane-containing silicon polymer ( unheated ) of Example 1 and its resin cured product was measured in the same manner as above under the atmosphere of air and nitrogen, and the measurement result of the thermal decomposition curve was shown. Tables 2 and 3 show the 5 wt% decomposition temperature (Td ₅ ) and the weight residual rate (W ₈₀₀ ) at 800 ° C. in air atmospheres 11 and 12 , respectively.

[0085]

[Table 2]

The heat distortion temperature of the molded product of Example 1 and the resin cured product thereof was measured using "SSC120 system" manufactured by Seiko Denshi KK. Measurement is 250
While applying a constant load of g, the temperature was raised from room temperature to 400 ° C. at a temperature rising rate of 10 ° C./min, and the change in thickness of the cured resin sample with respect to temperature was evaluated. That is, the temperature T ₁ (° C.) at which the molded body and the resin cured product sample having a thickness of 10 mm are deformed (shrinked) by 0.2 mm and the temperature T ₂ (° C.) when the maximum shrinkage amount D (mm) is shown. Compared. The measurement results of the heat distortion temperature are shown in Table 3 and FIG.

[0087]

[Table 3]

From Table 2, the cured resin is not cured (polymer).
It can be seen that the heat resistance is improved compared to. In addition, it can be seen from Table 3 that the cured resin has improved thermal deformation resistance as compared with that before curing (molded body) . That is, the cured product of the silicon-based resin is a material having excellent heat resistance and heat distortion resistance, and it is considered that the result is the effect of the cross-linking curing reaction of the acetylene group.

[0089]

The silicon-based polymer of the present invention and the case of the present invention
As described above, the silicon-based resin cured product obtained by curing the iodine-based polymer is excellent in heat resistance, flame retardancy and heat deformation resistance,
It is suitable for use in space / aviation materials and building materials.

[Brief description of drawings]

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

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

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.

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

6 is an IR spectrum of the silicon-based polymer of Example 3. FIG.

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

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

9 is a thermal decomposition curve of the silicon-based polymer of Example 3 and the polymer of Comparative Example 1. FIG.

10 is an IR spectrum of the molded product of Example 1 and a cured product thereof.

11 is a thermal decomposition curve (under air atmosphere) of the silicon-based polymer of Example 1 and a cured product thereof. FIG.

FIG. 12 is a thermal decomposition curve (under nitrogen atmosphere) of the silicon-based polymer of Example 1 and a cured product thereof.

13 is a thermal deformation curve of the molded product of Example 1 and its cured product. FIG.

Continuation of the front page (56) Reference JP-A-50-44299 (JP, A) JP-A-5-262878 (JP, A) JP-A-6-49430 (JP, A) JP-A-6-172712 (JP , A) JP 10-168197 (JP, A) JP-B 44-2240 (JP, B1) JP-A 8-505649 (JP, A) JP-A 8-507795 (JP, A) US Patent 3388090 (US, A) US Patent 3388091 (US, A) US Patent 5552505 (US, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 77/00-77/62 C08G 79/00- 79/14 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A homopolymer of a carborane-containing unit represented by the general formula (1), a homopolymer of a carborane-containing unit represented by the general formula (2), or a homopolymer of the carborane-containing unit represented by the general formula (1) or (2). carborane-containing silicon-based polymer copolymers or <br/> Rannahli carborane-containing unit represented a weight average molecular weight is equal to or less than 500. [Chemical 1] [Chemical 2] [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, and may be the same or different. R ² is an alkyl group having 1 to 20 carbon atoms bonded to a silicon atom.
Represents a alkylene group or an arylene group having 6 to 30 carbon atoms,
l is 0 or 1 . 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 boron compound, and x and x ′ are 3 to.
Represents an integer of 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, and may be the same or different.] 2. A general formula (1) and / or (2) carborane-containing units of the general formula (4) represented by - (7) consists of one or more units represented by a hydrocarbon group Tona
And has a weight average molecular weight of 500 or more.
Carborane-containing silicon-based polymer that. [Chemical 4] [Chemical 5] [Chemical 6] [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, and may be the same or different. R ² is an alkyl group having 1 to 20 carbon atoms bonded to a silicon atom.
Represents a alkylene group or an arylene group having 6 to 30 carbon atoms,
l is 0 or 1 . 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 boron compound, and x and x ′ are 3 to.
Represents an integer of 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] [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, and may be the same or different.] 3. A unit represented by the general formula (8).
Silicon-based polymer, or general formula (8) and general formula (4)
To react a silicon-based polymer composed of a combination of hydrocarbon groups composed of one or more units represented by (7) to a silyl-substituted carborane derivative represented by the general formula (9) or (10). The method for producing a carborane-containing silicon-based polymer according to claim 1 or 2, wherein [Chemical 8] [Chemical 9] [Chemical 10] [Chemical 11] [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, and 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). R ⁵ is a hydrogen atom bonded to a carbon atom, having 1 to 1 carbon atoms.
It represents an alkyl group having 20 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. R ⁷ represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 30 carbon atoms, which is bonded to a silicon atom, and l is 0 or 1. CBxHx′C represents carborane, which is a divalent cage boron compound, and x and x ′ represent an integer 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, and may be the same or different.]