JP2000248069A - Silicon-containing composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silicon-containing composite material excellent in heat resistance and oxidation resistance by blending a specific silicon-containing polymer with a specific silicon-containing alkoxy compound in a specific content ratio, followed by gelation. SOLUTION: The objective composite material is obtained by blending (A) 100 pts.wt. silicon-containing polymer having a repeating unit of the formula [wherein R1 and R2 are each H, a 1-30C alkyl or alkenyl or the like; R3 is a 1-30C alkylene or alkenylene or the like; (m) is 0 or 1] with (B) 0.01-10,000 pts.wt. (preferably 0.1-1,000 pts.wt.) silicon-containing alkoxy compound of the formula R4nSi(OR5)4-n [wherein R4 is H, a 1-30C alkyl or alkenyl or the like; R5 is a 1-30C alkyl or alkenyl or the like; (n) is 0 or 1-3], if needed, in the presence of a solvent, followed by gelation preferably at 0-200 deg.C for 1-100 h. A silicon-containing inorganic material consisting of Si, C and O is obtained by burning the composite material under a reduced pressure or in an inert gas at 700-3,500 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a silicon-containing composite material and a silicon-containing inorganic material having excellent heat resistance and oxidation resistance.

[0002]

2. Description of the Related Art Many engineering plastics have been developed as heat-resistant and oxidation-resistant materials which are lightweight and have excellent mechanical properties and can be processed. However, at present, polyimide has the highest heat- and oxidation-resistance. A heat deformation temperature of 360 ° C., an oxygen index of 53), and further improvement in heat resistance and oxidation resistance would greatly reduce the workability of plastic. The present inventors have previously found that a silicon-containing polymer compound having a Si—H bond and a C≡C bond in the molecule is excellent in heat resistance and oxidation resistance,
It has been proposed that the ceramic yield is very high (for example, JP-A-7-102609, JP-A-8-27276, etc.).
Although this silicon-containing polymer compound is lightweight and excellent in workability, further improvement in heat resistance and oxidation resistance is desired. The present inventors have also proposed that the silicon-containing polymer compound
It has been proposed that a carbon material in which fine particles of silicon carbide are dispersed can be obtained by firing at a high temperature of 00 to 3500 ° C (Japanese Patent Laid-Open No. 8-151206).

[0003]

DISCLOSURE OF THE INVENTION The present inventors aimed at further improving the heat resistance and oxidation resistance of a silicon-containing polymer compound having a Si-H bond and a C に C bond in the molecule described in the preceding section. We worked diligently to solve the issues. As a result, they found that a specific silicon-containing composite material and a silicon-containing inorganic material synthesized using silica had extremely excellent heat resistance and oxidation resistance, and reached the present invention.

[0004]

According to the present invention, there is provided a compound represented by the general formula (1):
[Formula 2]

[0005]

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(Wherein R ¹ and R ² independently represent a hydrogen atom, an aromatic group selected from an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group. The group may include a substituent selected from a halogen atom, a hydroxyl group, an amino group, and a carboxyl group, and R ³ is selected from an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group, a phenylene group and a naphthylene group. The divalent aromatic group or aromatic group is a group linked to an alkylene group, alkenylene group, alkynylene group or aromatic group having 1 to 30 carbon atoms directly or by a crosslinking member, and these groups are halogen. May contain a substituent selected from an atom, a hydroxyl group, an amino group, and a carboxyl group, and m is 0 or 1.) 100 parts by weight of
⁴ _n Si (OR ⁵ ) _4-n (wherein R ⁴ and R ⁵ have 1 to 3 carbon atoms)
0 is an aromatic group selected from an alkyl group, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group, and may be the same. R ⁴ may be a hydrogen atom. n
Is 0, 1, 2 or 3. ) Is mixed with 0.01 to 10000 parts by weight of the silicon-containing alkoxy compound represented by the formula (1) in the presence or absence of a solvent, and then gelled to obtain a silicon-containing composite material. Also,
The present invention is a silicon-containing inorganic material comprising silicon, carbon, and oxygen, which is obtained by firing the above-described silicon-containing composite material under a reduced pressure or in an inert gas at a temperature of 700 to 3500 ° C.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The silicon-containing polymer of the present invention has a Si—H bond and a C≡C bond in the molecule, and specifically has a repeating unit of silyleneethynylene, methylsilylene, phenylsilylene, or silylene. Ethinylene-1,3-phenyleneethynylene (chemical formula (2))

[0008]

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Silyleneethynylene-1,4-phenyleneethynylene, silyleneethynylene-1,2-phenyleneethynylene, methylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (3))

[0010]

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[0011] Methylsilyleneethynylene-1,4-phenyleneethynylene, methylsilyleneethynylene-1,
2-phenyleneethynylene, dimethylsilyleneethynylene-1,3-phenyleneethynylene, dimethylsilyleneethynylene-1,4-phenyleneethynylene, dimethylsilyleneethynylene-1,2-phenyleneethynylene,
Diethylsilyleneethynylene-1,3-phenyleneethynylene, phenylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (4))

[0012]

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Phenylsilyleneethynylene-1,4-
Phenyleneethynylene, phenylsilyleneethynylene-
1,2-phenyleneethynylene, diphenylsilyleneethynylene-1,3-phenyleneethynylene, hexylsilyleneethynylene-1,3-phenyleneethynylene, vinylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (5 )) [Chemical formula 6]

[0014]

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Ethynylsilyleneethynylene-1,3-
Phenyleneethynylene, 2-propenylsilyleneethynylene-1,3-phenyleneethynylene, 2-propynylsilyleneethynylene-1,3-phenyleneethynylene,
Trifluoromethylsilylethynylene-1,3-phenyleneethynylene, 3,3,3-trifluoropropylsilyleneethynylene-1,3-phenyleneethynylene, 4
-Methylphenylsilyleneethynylene-1,3-phenyleneethynylene, 4-vinylphenylsilyleneethynylene-1,3-phenyleneethynylene, silyleneethynylene (5-methyl-1,3-phenylene) ethynylene, phenylsilyleneethylene Nylene (5-methyl-1,3-phenylene) ethynylene, phenylsilyleneethynylene (5
-Silyl-1,3-phenylene) ethynylene, phenylsilyleneethynylene (5-hydroxy-1,3-phenylene) ethynylene, phenylsilyleneethynylene-2,
7-naphthyleneethynylene, silyleneethynylene-5,
10-anthracene diethynylene, phenylsilyleneethynylene-4,4'-biphenyleneethynylene (chemical formula (6))

[0016]

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Phenylsilyleneethynylene-1,4-
Phenylenemethylene-1 ', 4'-phenyleneethynylene, phenylsilyleneethynylene-1,4-phenylene-2,2-propylidene-1', 4'-phenyleneethynylene, phenylsilyleneethynylene-1,4-phenylene -2,2- (1,1,1,3,3,3-hexafluoropropylidene) -1 ′, 4′-phenyleneethynylene, (chemical formula (7))

[0018]

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Phenylsilyleneethynylene-1,4-
Phenyleneoxy-1 ′, 4′-phenyleneethynylene (chemical formula (8))

[0020]

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Phenylsilyleneethynylene-2,5-
Pyridinedylethynylene, phenylsilyleneethynylene-2,5-thiophenedirylethynylene, methylsilyleneethynylenemethyleneethynylene, phenylsilylene-1,4-phenylene (phenylsilylene) ethynylene-1 ′, 3′- Phenyleneethynylene (chemical formula (9)
[Formula 10]

[0022]

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Phenylsilyleneoxy (phenylsilylene) ethynylene-1 ′, 3′-phenyleneethynylene (chemical formula (10))

[0024]

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Phenylsilyleneoxy (phenylsilylene) ethynylene-1 ′, 4′-phenyleneethynylene,
Phenylsilyleneimino (phenylsilylene) ethynylene-1 ′, 3′-phenyleneethynylene (chemical formula (1
1)) [Chemical formula 12]

[0026]

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Phenylsilyleneimino (phenylsilylene) ethynylene-1 ′, 4′-phenyleneethynylene,
Chemical formula (12)

[0028]

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Chemical formula (13):

[0030]

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Chemical formula (14) [Formula 15]

[0032]

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Chemical formula (15) [Formula 16]

[0034]

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Chemical formula (16) [Formula 17]

[0036]

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Chemical formula (17)

[0038]

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Chemical formula (18)

[0040]

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Silylene-1,3-phenyleneethynylene (chemical formula (19))

[0042]

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Silylene-1,4-phenyleneethynylene, silylene-1,2-phenyleneethynylene, phenylsilylene-1,3-phenyleneethynylene (chemical formula (20))

[0044]

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Phenylsilylene-1,4-phenyleneethynylene, phenylsilylene-1,2-phenyleneethynylene, diphenylsilylene-1,3-phenyleneethynylene, methylsilylene-1,3-phenyleneethynylene (chemical formula ( 21)) [Formula 22]

[0046]

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And methylsilylene-1,4-phenyleneethynylene, methylsilylene-1,2-phenyleneethynylene, dimethylsilylene-1,3-phenyleneethynylene, diethylsilylene-1,3-phenyleneethynylene and the like. Can be There is no particular limitation on the weight average molecular weight,
Preferably it is 500 to 500,000. The form of these silicon-containing polymers is solid or liquid at room temperature,
They may be used alone or in combination of two or more.

As a method for producing the silicon-containing polymer represented by the general formula (1), a method in which a deethynyl compound and a silane compound are dehydrogenated and copolymerized using a basic oxide, a metal hydride or a metal compound as a catalyst. (JP-A-7-90085,
(Japanese Patent Application Nos. 9-92424 and 9-318003),
A method of performing dehydrogenation polymerization of an ethynylsilane compound using a basic oxide as a catalyst (JP-A-9-143271), a method of reacting an organomagnesium reagent with dichlorosilanes (JP-A-7-102609), Dehydrogenation copolymerization of diethynyl and silane compounds using secondary amines as catalysts (Hua Qin Liu and John F. Harrod,
The Canadian Journal of Chemistry, Vol. 68, 1100-1
105 (1990)) and the like, but are not particularly limited to these methods.

[0049] Further, as the general formula R ⁴ _n Si (OR ⁵⁾ silicon-containing alkoxy compound represented by the _4-n, in particular,
Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentoxysilane, tetrahexoxysilane, tetraphenoxysilane, trimethoxysilane, triethoxysilane, dimethoxysilane, diethoxysilane, methyltrimethoxysilane, Dimethyldiethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyl Diethoxysilane, vinylmethyldiethoxysilane, vinylphenyldiethoxysilane, allyltrimethoxysilane, allyltriethoxy Silane, allyl methyl dimethoxy silane, allyl phenyl dimethoxy silane, allyl methyl divinyl silane, and allyl phenyl diethoxy silane and the like. These are used alone or in combination of two or more.

Next, a method for producing a silicon-containing composite material according to the present invention will be described. The silicon-containing polymer and the silicon-containing alkoxy compound are mixed in the presence or absence of a solvent to form a uniform mixed solution. Next, a gelation reaction is preferably performed in the presence of a catalyst, and thereafter, volatile components such as a solvent are distilled off to obtain a silicon-containing composite material. The use ratio of the silicon-containing polymer and the silicon-containing alkoxide compound,
It is in the range of 0.01 to 10000 parts by weight, preferably 0.1 to 1000 parts by weight, based on 100 parts by weight of the silicon-containing polymer. It is desirable to use a solvent, specifically, benzene, toluene, xylene, hexane, heptane, tetrahydrofuran, dioxane, monoglyme, diglyme, diethyl ether,
N-methylpyrrolidone, ethanol, propanol, isobutanol, carbon tetrachloride, acetone, dimethylformamide and the like. The conditions of the gelation reaction are not particularly limited, but are usually 1 to 200 in a temperature range of 0 to 200 ° C.
Performed for 100 hours. Catalysts that can be suitably used in this case include, for example, acidic compounds such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid, oleic acid, lactic acid, and toluenesulfonic acid, or lithium hydroxide, sodium hydroxide, and hydroxide. Potassium, barium hydroxide, ammonium hydroxide, methoxylithium, ethoxylithium, propoxylithium, butoxylithium, ethoxysodium, ethoxypotassium, propoxybarium,
It is an alkaline compound such as hexoxybarium.

Next, a method for producing a silicon-containing inorganic material according to the present invention will be described. The silicon-containing composite material obtained by the above method is heated at 700 to 3500 ° C. under reduced pressure or in an inert gas such as argon, helium, or nitrogen.
Preferably, it is obtained by firing in a temperature range of 1000 to 2500 ° C. In this case, various methods can be employed for the heating rate, the heating time, and the firing time depending on the purpose. In addition, a material having a specific shape can be used as the silicon-containing inorganic material before firing.

[0052]

The present invention will be described below with reference to examples and comparative examples. Example 1 A silicon-containing polymer; poly [(phenylsilylene) ethynylene-1,3-phenyleneethynylene] (hereinafter abbreviated as MSP) was synthesized based on the method described in JP-A-7-90085. A silica firing tube was charged with 72 g of magnesium hydroxide having a particle size of 30 to 60 mesh, and 0.3 g
Pyrolysis was performed at 350 ° C. for 3 hours under a reduced pressure of mmHg to obtain 50 g of magnesium oxide.

A magnetic stirrer was installed inside a 1 L glass container, and the inside of the container was replaced with high-purity nitrogen gas. Subsequently, 25.2 g of raw material 1,3-diethynylbenzene was placed in the container.
(200 mmol) and phenylsilane 21.6 g (20
0 mmol) and 400 ml of toluene as a solvent, and 50 g of the previously obtained magnesium oxide was added thereto with stirring under a nitrogen blanket. After stirring at 30 ° C for 1 hour, 40 ° C for 1 hour, 50 ° C for 1 hour, 60 ° C for 1 hour, and further at 80 ° C for 2 hours, the reaction solution was filtered through a glass filter to remove the catalyst. After the reaction solution was further concentrated, the polymer was precipitated in 2 L of heptane. The viscous precipitate was dried under reduced pressure at 60 ° C. for 24 hours to obtain 18.8 g of powdery MSP (weight average molecular weight in terms of polystyrene: 6800), and 13.0 g of liquid MSP by distilling the solvent from the solution. MSP (polystyrene reduced weight average molecular weight 1200) was obtained. Total yield was 68%.

4.6 g of liquid MSP and 22 g of tetraethoxysilane were mixed, and 3.1 ml of an aqueous solution of toluenesulfonic acid (30 wt%) and 26 ml of tetrahydrofuran were added with stirring. After stirring for 24 hours, depth 3m
m, and sealed for 72 hours.
For 160 hours, diameter 16mm, thickness 0.8mm
A yellow transparent gel (silicon-containing composite material (I), density 1.5 g / cm ³ ) was obtained. Silicon-containing composite material (I)
TGA (differential thermogravimetric analysis) measurement was performed at a heating rate of 10 ° C. /
min. Td _{5 in} argon (5% weight loss temperature) was 950 ° C. and Td _{5 in} air was 750 ° C.

Next, the silicon-containing composite material (I) was heated at 5 ° C./min for about 200 minutes in an argon stream, and further heated for 1 minute.
Baking was performed at 000 ° C. for 1 hour. Diameter 14mm, thickness 0.6
mm black disk-shaped product (silicon-containing inorganic material (I), density 2.0 g / cm ³ ) was obtained. 1 in pure oxygen atmosphere
A continuous isothermal holding experiment at 200 ° C. for 12 hours was performed. The weight loss after 12 hours was about 20%.

[0056] Td ₅ in an argon Comparative Example 1 MSP is 860 ° C., Td ₅ in air was 560 ° C.. In addition, when this MSP was fired at 1200 ° C. in argon and subjected to a continuous isothermal holding experiment at 1000 ° C. for 12 hours in a pure oxygen atmosphere, the weight loss after 12 hours was about 70%.

[0057]

According to the present invention, a new material having excellent heat resistance and combustion resistance can be produced and provided from a silicon-containing polymer having a specific structure and a silicon-containing alkoxy compound.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G046 MA14 MB08 MC01 MC04 4J002 CP02X CP04W CP04X CP05W CP06W CP08W CP09W CP13W CP13X CP15W 4J035 JA02 JB01 JB03

Claims (2)

[Claims] 1. A compound of the general formula (1) (In the formula, R ¹ and R ² are each independently a hydrogen atom, an aromatic group selected from an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, a phenyl group and a naphthyl group. R ³ may be a substituent selected from an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group, a phenylene group and a naphthylene group. Is an alkylene group having 1 to 30 carbon atoms, an alkenylene group, an alkynylene group, or an aromatic group, which is a halogen atom, a hydroxyl group, an amino group, And m may be 0 or 1.) and 100 parts by weight of a silicon-containing polymer having a repeating unit represented by the following formula: The general formula R ⁴ _n Si (OR ⁵⁾ in _4-n (wherein, R ^4, R ⁵ is an alkyl group having 1 to 30 carbon atoms, an alkenyl group, an alkynyl group, an aromatic chosen from phenyl or naphthyl group And may be the same, and R ⁴
May be a hydrogen atom. n is 0, 1, 2 or 3. ) The silicon-containing alkoxy compound represented by 0.01)
A silicon-containing composite material obtained by mixing 1 to 10,000 parts by weight with or without a solvent and then gelling. 2. A silicon-containing inorganic material comprising silicon, carbon and oxygen obtained by firing the silicon-containing composite material according to claim 1 at a temperature in the range of 700 to 3500 ° C. under reduced pressure or in an inert gas. .