JP2002309088A - Composition containing silicon compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition containing silicon, excellent in heat resistance and mechanical characteristics. SOLUTION: This compound containing silicon comprises a polymeric compound having Si-H bond(s) and a compound having two or more hydroxyl groups in its molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silicon-containing composition comprising a polymer compound having a Si-H bond and a compound having a hydroxy group and having excellent heat resistance and mechanical properties.

[0002]

2. Description of the Related Art Many engineering plastics have been researched and developed as heat-resistant materials which are lightweight and have excellent mechanical properties and can be processed. The present inventors have found that a thermosetting silicon-based resin containing a repeating unit having a highly reactive carbon-carbon unsaturated bond and a Si-H bond in a molecule, although the mechanical properties are inferior to a polyimide-based resin. Have extremely high heat resistance (see JP-A-7-102).
069). On the other hand, silicones containing the same silicon-based resin and containing a siloxane bond are used in various fields such as mold release agents and sealing materials, but the practical use temperature is less than 300 ° C., and the heat resistance is not so high. There has been a demand for a silicon-containing resin that has heat resistance and excellent mechanical properties and can be used in the fields of electronics, precision machinery, and the like.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have made an intensive effort to develop a resin having both excellent heat resistance and mechanical properties, and have developed a polymer compound containing a Si-H bond and a hydroxy group. The present inventors have found that a silicon-containing composition comprising a compound having two or more compounds therein has excellent heat resistance and mechanical properties, and have reached the present invention.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a silicon-containing composition comprising a polymer compound having a Si-H bond and a compound having two or more hydroxy groups in a molecule.

Further, the present invention provides a compound represented by the general formula (1)

Embedded image (In the formula, R ¹ is oxygen or an alkylene group having 1 to 30 carbon atoms, alkenylene group, alkynylene group or divalent aromatic group, and represents a substituent such as a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. R ²
Is a hydrogen atom or an alkyl, alkenyl, alkynyl, alkoxy, or aromatic group having 1 to 30 carbon atoms, and may have a substituent such as a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. . The present invention relates to a silicon-containing composition comprising a polymer compound having a Si-H bond and a compound having two or more hydroxy groups in the molecule.

The present invention also relates to a silicon-containing composition comprising a polymer compound having a Si—H bond and a compound having two or more hydroxy groups in a molecule, having a temperature of 50.degree.
The present invention relates to a composition obtained by performing a heat treatment at 0 ° C. or lower.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below, but the present invention is not particularly limited to these production methods.

<Polymer Compound Having Si-H Bond> The polymer compound having at least one Si-H bond in a molecule in the present invention is represented by the general formula (1).
In the formula, R ¹ is oxygen or an alkylene group, alkenylene group, alkynylene group or divalent aromatic group having 1 to 30 carbon atoms, and has a substituent such as a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. You may. Examples of the alkylene group include a methylene group, a fluoromethylene group, an ethylene group, a propylene group, a tetramethylene group, and a tetrafluoroethylene group.Alkenylene groups include a vinylene group, a propenylene group, and a butadienylene group. Propynylene group, butynylene group, etc., as a divalent aromatic group, phenylene group, naphthylene group, biphenylene group, anthracenedil group,
Pyridinedyl group, thiophenedilyl group, fluorophenylene group, chlorophenylene group, methylphenylene group, silylphenylene group, hydroxyphenylene group, aminophenylene group, phenylenemethylenephenylene group,
Examples include a phenyleneoxyphenylene group, a phenylenepropylidenephenylene group, and a phenylene (hexafluoropropylidene) phenylene group. R ² is a hydrogen atom or a halogen atom having 1 to 30 carbon atoms, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, or an aromatic group which may have a substituent such as a hydroxyl group, an amino group, a carboxyl group, or an ether group. is there. Examples of the alkyl group include a methyl group, an ethyl group, a hexyl group, an octyl group, an octadecyl group, and a 3,3,3-trifluoropropyl group.
As an alkenyl group, a vinyl group, a propenyl group, etc., as an alkynyl group, an ethynyl group, a propynyl group, etc., as an alkoxy group, a methoxy group, an ethoxy group, a phenoxy group, etc., and as an aromatic group, a phenyl group, a naphthyl group,
Examples thereof include a 4-methylphenyl group, a 4-chlorophenyl group, a 4-methoxyphenyl group, an anthryl group, a hydroxyphenyl group, a fluorophenyl group, a methoxyphenyl group, and a hydroxynaphthyl group.

Specific examples of the polymer compound having a Si—H bond in the present invention include poly (dihydrogensiloxane), poly (methylhydrogensiloxane), poly (ethylhydrogensiloxane) and poly (phenylhydrogensiloxane). Siloxane), poly [(methylhydrogensiloxane) (dimethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (diethylsiloxane)] copolymer, poly [(methylhydrogensiloxane) (octylmethylsiloxane)] copolymer, poly [(Methylhydrogensiloxane) (phenylmethylsiloxane)] copolymer, poly [(methylhydrogensiloxane)
(Dimethoxysiloxane)] copolymer, poly [(dihydrogensiloxane) ((2-methoxyethoxy)
Methylsiloxane)] copolymer, poly [(dihydrogensiloxane) (phenoxymethylsiloxane)]
Copolymer, poly [(dihydrogensiloxane)
(Naphthylmethylsiloxane)] copolymer, poly [(dihydrogensiloxane) ((4-methoxyphenyl) dimethylsiloxane)] copolymer, poly (silyleneethylene) (chemical formula (2))

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Poly [silylene (methyl) methylene] (chemical formula (3))

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Poly (silyleneethynylene), poly (methylsilyleneethynylene), poly (phenylsilyleneethynylene), poly (silyleneethynylene-1,3-phenyleneethynylene) (chemical formula (4)),

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Poly (silyleneethynylene-1,4-phenyleneethynylene), poly (silyleneethynylene-1,
2-phenyleneethynylene, methylsilyleneethynylene-1,3-phenyleneethynylene (chemical formula (5)),

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Poly (methylsilyleneethynylene-1,4)
-Phenyleneethynylene), poly (methylsilyleneethynylene-1,2-phenyleneethynylene), poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) (chemical formula (6)),

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Poly (phenylsilyleneethynylene-1,
4-phenyleneethynylene), poly (phenylsilyleneethynylene-1,2-phenyleneethynylene), poly (hexylsilyleneethynylene-1,3-phenyleneethynylene), poly (vinylsilyleneethynylene-1,3)
-Phenyleneethynylene) (chemical formula (7)),

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Poly (ethynylsilyleneethynylene-1,
3-phenyleneethynylene), poly (2-propenylsilyleneethynylene-1,3-phenyleneethynylene),
Poly (2-propynylsilyleneethynylene-1,3-phenyleneethynylene), poly (trifluoromethylsilylyleneethynylene-1,3-phenyleneethynylene), poly (3,3,3-trifluoropropylsilyleneethynylene) -1,3-phenyleneethynylene), poly (4-methylphenylsilyleneethynylene-1,3-phenyleneethynylene), poly (4-vinylphenylsilyleneethynylene-1,3-phenyleneethynylene), poly [ Silyleneethynylene (5-methyl-1,3-phenylene) ethynylene], poly [phenylsilyleneethynylene (5-methyl-1,3-phenylene) ethynylene], poly [phenylsilyleneethynylene (5-silyl-1, 3-phenylene) ethynylene], poly [phenylsilyleneethynylene (5-hydroxy-1,3- Eniren) ethynylene, poly (silylene ethynylene-2,7-naphthylene ethynylene), poly (silylene ethynylene -
5,10-anthracene diethynylene), poly (phenylsilyleneethynylene-4,4′-biphenyleneethynylene) (chemical formula (8)),

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Poly (phenylsilyleneethynylene-1,
4-phenylenemethylene-1 ′, 4′-phenyleneethynylene), poly (phenylsilyleneethynylene-1,4-)
Phenylene-2,2-propylidene-1 ′, 4′-phenyleneethynylene), poly [phenylsilyleneethynylene-
1,4-phenylene-2,2- (1,1,1,3,3,3-hexafluoropropylidene) -1 ′, 4′-phenyleneethynylene], (chemical formula (9)),

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Poly (phenylsilyleneethynylene-1,
4-phenyleneoxy-1 ′, 4′-phenyleneethynylene) (chemical formula (10)),

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Poly (phenylsilyleneethynylene-2,
5-pyridinedylethynylene, poly (phenylsilyleneethynylene-2,5-thiophenedirylethynylene), poly (methylsilyleneethynylenemethyleneethynylene), poly [phenylsilylene-1,4-phenylene ( Phenylsilylene) ethynylene-1 ′, 3′-phenyleneethynylene] (chemical formula (11)),

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Poly [phenylsilyleneoxy (phenylsilylene) ethynylene-1 ′, 3′-phenyleneethynylene] (chemical formula (12));

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Poly [phenylsilyleneoxy (phenylsilylene) ethynylene-1 ′, 4′-phenyleneethynylene], poly [phenylsilyleneimino (phenylsilylene) ethynylene-1 ′, 3′-phenyleneethynylene]
(Chemical formula (13)),

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Poly [phenylsilyleneimino (phenylsilylene) ethynylene-1 ′, 4′-phenyleneethynylene], poly [(phenylsilylene) ethynyleneethynylene] (chemical formula (14)),

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Poly [(phenylsilylene) ethynylenemethyleneethynylene] (chemical formula (15))

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Chemical formula (16)

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Chemical formula (17)

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Chemical formula (18)

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Chemical formula (19)

Embedded image Chemical formula (20)

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Poly (silylene-1,3-phenyleneethynylene) (chemical formula (21))

Embedded image Poly (silylene-1,4-phenyleneethynylene), poly (silylene-1,2-phenyleneethynylene), poly (phenylsilylene-1,3-phenyleneethynylene)
(Chemical formula (22))

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Poly (phenylsilylene-1,4-phenyleneethynylene), poly (phenylsilylene-1,2-)
Phenyleneethynylene), poly (diphenylsilylene-
1,3-phenyleneethynylene), poly (methylsilylene-1,3-phenyleneethynylene) (chemical formula (2)
3)),

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Poly (methylsilylene-1,4-phenyleneethynylene), poly (methylsilylene-1,2-phenyleneethynylene), poly (phenylsilylene-1,3)
-Butadiynylene), poly (phenylsilylenemethyleneethynylene), poly (phenylsilylenemethyleneethynylenemethylene), poly (silylene-1,4-phenyleneethynylene-1 ′, 4′-phenylene), poly (methylsilylene-1) , 4-phenyleneethynylene-1 ′, 4′-phenylene), poly (phenylsilylene-1,4-phenyleneethynylene-1 ′, 4′-phenylene) and the like. Two or more of these polymer compounds having a Si—H bond may be used.

The Si—H represented by the general formula (1)
As a method for producing a polymer compound having a bond, a method of hydrolyzing a dialkoxysilane compound or a dichlorosilane compound, dehydrogenation of a diethynyl compound and a silane compound using a basic oxide, a metal hydride, or a metal compound as a catalyst are used. Copolymerization method (JP-A-7-90085, JP-A-190085)
0-120689, JP-A-11-158187), a method of performing dehydrogenation polymerization of an ethynylsilane compound using a basic oxide as a catalyst (JP-A-9-143271), and a method of reacting an organomagnesium reagent with dichlorosilanes (JP-A-Hei. 7-102069), a method of performing dehydrogenation copolymerization of a diethynyl compound and a hydrosilane compound using cuprous chloride and a tertiary amine as catalysts (Hua Qin Liu and John F. Ha)
rrod, The Canadian Journal of Chemistry, Vo
l. 68, 1100-1105 (1990)) and the like, but are not particularly limited to these methods.

<Hydroxy compound> Another compound having two or more hydroxy groups in the molecule can be classified into aliphatic hydroxys and aromatic hydroxys.

Specific examples of the aliphatic hydroxy of the compound having two or more hydroxy groups in the molecule include ethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, , 3-butanediol, 3,3-dimethyl-1,2-butanediol,
Pinacol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 2,5-hexanediol, 2-chloro-5-methyl-2,5-hexanediol, 1,7-heptane Diol, 2,6-
Heptanediol, 1,8-octanediol, 2-butyne-1,4-diol, 3-hexyne-1,6-diol, 3-hexyne-2,5-diol, 4-octyne-1,8-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 2-chloro-5-methyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7.9-tetramethyl-5-decyne-4,7-diol, 2,4-hexadiyne-1,6-diol, 3,5-octadiyne-
1,8-diol, 2,7-dimethyl-3,5-octadiyne-2,7-diol, 1,4-bis (1′-hydroxycyclopentyl) -1,3-butadiyne, 2-butene-1,4 -Diol, 3-hexene-1,6-diol, 3-hexene-2,5-diol, 4-octene-1,8-diol, 2,5-dimethyl-3-hexene-2,5-diol, 2 -Chloro-5-methyl-3-hexene-2,5-diol, 3,6-dimethyl-4-octene-3,6-diol, 2,4,7.9-tetramethyl-5-decene-4, 7-diol, hydroxypanaxidiol, 1-bromo-7-oxa-bicyclo (4.1.0) heptane-2,3,4,5-tetraol, diethanolamine, diisopropanolamine,
N, N′-bis (2-hydroxyethyl) ethylenediamine, 2-amino-4-octyne-1,8-diol,
2-amino-6-chloro-4-octyne-1,8-diol, 2-hydroxy-4-octyne-1,8-diol and the like can be mentioned.

Aromatic hydroxys include catechol, 3-fluorocatechol, 4-methylcatechol, 4-aminocatechol, resorcinol, 4-bromoresorcinol, 5-methoxyresorcinol, hydroquinone, methylhydroquinone, tetrafluorohydroquinone, 1,2
-Dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1-chloro-2,6-dihydroxynaphthalene, 1
-Amino-2,6-dihydroxynaphthalene, 4- (3
-Hydroxy-3-methylbutyn-1-yl) benzyl alcohol, 1,1,4,4-tetraphenyl-2-butyne-1,4 diol, 1,1,6,6-tetraphenyl-hexa-2,4 -Diyne-1,6-diol, 1,
1,1,8,8,8-hexaphenyl-octa-3,5
-Diyne-2,7-diol, 1,1,4,4-tetraphenyl-2-butene-1,4-diol, tetrahydroxy-p-benzoquinone, 3,5-dihydroxyacetophenone, anthracenediol, 1,2 Anthracene diol, 1,5-anthracene diol, 1,8
-Anthracenediol, 2,6-anthracenediol, 1,3-dihydroxyanthraquinone, 1,4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone, 1,6-dihydroxyanthraquinone,
1,7-dihydroxyanthraquinone, 1,8-dihydroxyanthraquinone, 2,3-dihydroxyanthraquinone, 2,6-dihydroxyanthraquinone, 2,7
-Dihydroxyanthraquinone, N-phenyldiethanolamine, N, N-bis (2-hydroxyethyl)-
M-chloroamine, 3- (N-benzyl-N-methylamino) -1,2-propanediol, 8-hydroxy-
4- (7-hydroxy-6-methoxy-2-oxo-1
A, 2,7,7A-tetrahydronaphtho [2,3B] oxyline, 4-amino-catechol, 5-aminoresorcinol, 1,2,4-benzenetriol, 4- (7-
(Hydroxy-2naphthyl) pyrogallol and the like. Compounds having two or more hydroxy groups in the molecule may be used alone or as a mixture of two or more.

<Composition> A method for preparing a composition containing a silicon compound comprising the polymer compound having a Si—H bond of the present invention and a compound having two or more hydroxy groups in the molecule is as follows. Can be illustrated. (A) a mortar, a Henschel mixer, a drum blender, a tumbler blender, and a polymer compound having a Si—H bond and a compound having two or more hydroxy groups in a molecule;
Knead using a ball mill ribbon blender or the like. (B) When the compound having two or more hydroxy groups in the molecule is a liquid, a polymer compound having a Si—H bond is added and uniformly dissolved or dispersed. (C) When the polymer compound having a Si—H bond is a liquid, a compound having two or more hydroxy groups in the molecule is added and uniformly dissolved or dispersed. (D) A compound having two or more hydroxy groups in a molecule is dissolved or suspended in an organic solvent in advance, and a polymer compound having a Si-H bond is added to the solution and uniformly dissolved or dispersed, or Use after removing the solvent. (E) A polymer compound having a Si—H bond is dissolved or suspended in an organic solvent in advance, and a compound having two or more hydroxy groups in a molecule is added to the solution, and the compound is uniformly dissolved or dispersed, or Use after removing the solvent. In (d) and (e), when the hydrosilane compound having a Si—H bond is dissolved in a compound having two or more hydroxy groups in the molecule, the organic solvent used may be a saturated fat such as hexane, heptane, or cyclohexane. Aromatic solvents, aromatic solvents such as benzene, toluene, xylene, ether solvents such as tetrahydrofuran, dioxane, monoglyme, diglyme,
Ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; aliphatic alcohol solvents such as methanol, ethanol and propanol; organic polar solvents such as N, N-dimethylimidazolidinone, N, N-dimethylformamide, dimethylacetamide, N-methylpyrrolidone Solvents and the like can be mentioned, and these can be used alone or in combination of two or more.

The thus obtained silicon-containing composition comprising the polymer compound having a Si--H bond and the compound having two or more hydroxy groups in the molecule further has a temperature of 50 to 700.degree. Heat cured in the range. In this case, if necessary, a curing agent can be added within a range that does not impair the purpose. For molding a polymer compound having a Si—H bond and a compound having two or more hydroxy groups in a molecule, and a composition to which a curing agent is added as necessary,
Various molding methods, for example, injection molding, compression molding, transfer molding, extrusion molding, and the like are used, and curing molding can be performed by maintaining a predetermined temperature at a predetermined temperature for a predetermined time. When the composition containing silicon is a solution, it is desirable to remove the solvent before curing.

The 5% weight loss temperature of the composition of the present invention is usually at least 250 ° C, preferably at least 300 ° C, more preferably at least 350 ° C.

The lower limit of the bending strength of the cured molded article of the composition of the present invention is usually 15 MPa or more, preferably 20 MPa.
The pressure is more preferably 25 MPa or more.

<Curing Agent> As the curing agent, metal alkoxides, metal amides, metal imides, metal hydrides, organometallic compounds, radical initiators, transition metal complexes, aliphatic amines, aromatic amines, Imidazoles and the like can be used.

Metal alkoxides include lithium methoxide, sodium ethoxide, potassium hexyl oxide, rubidium isopropoxide, cesium phenoxide, beryllium dimethoxide, magnesium diethoxide, beryllium butoxide, calcium phenoxide, strontium methoxy ethoxide, barium dioctyl Oxide, boron trimethoxide, aluminum triphenoxide, gallium trihexyl oxide, indium trimethoxide, yttrium triethoxide, titanium tetramethoxide, zirconium tetraethoxide, niobium pentaethoxide, chromium triethoxide, manganese dimethoxide, Iron triethoxide, manganese dimethoxide, cobalt dimethoxide, nickel diethoxide, copper diethoxide De, and lithium aluminum tetraethoxide is.

As metal amides, lithium amide, lithium trimethylsilylamide, sodium methylamide, potassium ethylamide, potassium phenylamide,
Rubidium isopropylamide, cesium butylamide, beryllium diamide, magnesium bis (butylamide), calcium bis (dihexylamide), strontium bis (isobutylamide), barium bis (allylimide) and the like.

As metal imides, lithium imide, lithium trimethylsilyl imide, sodium methyl imide, potassium ethyl imide, potassium phenyl imide,
Examples include rubidium isopropylimide, cesium butyl imide, beryllium diimide, magnesium bis (butyl imide), calcium bis (dihexyl imide), strontium bis (isobutyl imide), and barium bis (allyl imide).

As metal hydrides, LiH, CaH_Two, BH_Three,
AlH_Three, NaBH_Four, KBH_Four, LiAlH_Four, (CH_Three) _FourNBH_Four, LiBH (C2H
5), KBH (C6H5) 3, NaBH (OCH3), NaBH3CN, (I-C3H7) 2Al
H, LiAlH2 (OC2H5) 2, NaAlH_Two(C_TwoH_Five)_Two, SnH (n-C_FourH₉)_ThreeEtc.
No.

Examples of the organometallic compounds include methyl lithium, ethyl lithium, propyl sodium, allyl sodium, ethyl potassium, dimethyl beryllium, diethyl calcium, methyl magnesium iodide, di-t
-Butyl calcium, tri-t-butyl strontium,
Examples include phenyl barium, trimethyl aluminum, dimethyl zinc, di-n-butyl cadmium, lithium tetraethyl aluminum and the like.

Examples of the metal radical initiator include hydrogen peroxide, ammonium persulfate, benzoyl peroxide, cumene peroxide, cyclohexane peroxide, di-tert-butyl peroxide, t-butyl hydroperoxide, methyl ethyl ketone peroxide, and azobisiso-peroxide. Butyronitrile.

As the transition metal complex, RhCl (PPh_Three)_Three, RhCl
(PBu_Three)_Three, Rh_Four(CO)₁₂, [RhCl (CO)_Two] _Two, RhCl (CO) (PPh_Three)
_Two, [RhCl (COD)]_Two(Where COD is cyclooctadiene
Show. The same applies hereinafter), [CpRhCl_Two]_Two(Where Cp is cyclope
Antadienyl group or pentamethylcyclopentadienyl
Represents a hydroxyl group. The same applies hereinafter), Rh / C, RuCl (PPh_Three)_Three, RuCl_Two(P
Ph_Three)_Three, Ru (CO)_Five, Ru (CO)_FourPPh_Three, Ru_Three(CO)₁₂, Ru (PP
h_Three)_Five, [RuCl_Two(CO)_Three]_Two, RuClH (CO) (PPh_Three)_Three, RuH_Four(PP
h_Three)_Three, [CpRuCl_Two]_Two, Ru / C, Ru (COD) (COT) (where COT
Represents cyclooctatetraene. Hereinafter the same), Fe (CO)
_Five, Fe (CO)_Three(PPh_Three)_Two, Os_Three(CO)₁₂, OsH_Two(CO) (PPh_Three)_Three, Os /
C, Co_Four(CO)₁₂, HCo (CO)_Four, CoCl (PPh_Three)_Three, Ir_Four(CO)₁₂,
[IrCl (COD)]_Two, IrCl (PPh_Three)_Three, IrH_Five(PPh_Three)_Two, Ni (C
O)_Four, Ni (PPh_Three)_Four, NiCl_Two(PPh_Three)_Two, Pd (PEt_Three)_Two, Pd (PiP
r_Three)_Two, Pd (P (c-C₆H₁₁)_Three)_Two, Pd (PPh_Three)_Two, PdCl_Two(PMe_Three)_Two, P
dCl_Two(PEt_Three)_Two, PdCl_Two(PiPr_Three)_Two, PdCl_Two(PBu_Three)_Two, PdCl_Two(P
(c-C₆H₁₁)_Three)_Two, PdCl_Two(PPh_Three)_Two, PdCl_Two(PhNC)_Two, Pd (PPh_Three)
_Four, Pd (dba)_Two(In the formula, dba indicates dibenzylideneacetone
You. The same applies hereinafter), PdCl_Two(dba)_Two, Pd / C, PtCl (PPh_Three)_Two(CO
D), PtCl_Two(PPh_Three) _Two, PtCl_Two(PEt_Three)_Two, [PtCl_Two(CH_Two= C
H_Two)]_Two, PtCl_Two(COD)_Two, Pt (PPh_Three)_Four, Pt (PPh_Three)_Three, Pt (CO)
(PPh_Three)_Three, Pt / C, PtHCl (PPh_Three)_Two, H_TwoPtCl₆, K_TwoPtCl₆, Pt
(dba)_Two, Pt_Two(dba)_ThreeAnd the like.

As the aliphatic amine, ethylenediamine,
Examples thereof include diethylenetriamine, triethylenetetramine, dipropylenetriamine, monoethanolamine, and hexamethylenediamine.

Examples of the aromatic amine include phenylenediamine, diaminoanisole, toluenediamine, xylenediamine, diaminobisdiphenylmethane, α-methyldimethylamine and the like.

Examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole,
Phenylimidazole, 1-cyanoethyl-2-methylimidazole and the like can be mentioned.

None of the curing agents is limited to these. These metal alkoxides, metal amides, metal imides, metal hydrides, organometallic compounds, radical initiators, transition metal complexes, aliphatic amines, aromatic amines, imidazoles may be used alone or in combination of two or more. Can be used as a mixture. The amount is 0.001 to 1 g of the compound having two or more hydroxy groups in the molecule.
001 mmol to 200 mmol, preferably 0.00
01 mmol to 1 mmol, more preferably 0.00
It is from 01 mmol to 0.1 mmol.

<Curing Reaction> The temperature of the heat curing varies depending on the type of the polymer compound having a Si—H bond and the compound having two or more hydroxy groups in the molecule.
00 ° C, preferably 50 ° C to 500 ° C, more preferably 100 ° C to 300 ° C. The curing time varies depending on the type of the polymer compound having a Si—H bond and the compound having two or more hydroxy groups in the molecule, but is from 30 seconds to 10 seconds.
0 day, preferably 1 minute to 100 hours, more preferably 10 minutes to 24 hours. Heat curing treatment is air, nitrogen,
It can be carried out under a gas atmosphere such as argon or helium, at normal pressure, under pressure or under reduced pressure.

The curing reaction between a polymer compound having a Si—H bond and a compound having two or more hydroxy groups in a molecule is carried out in a reaction vessel in the presence or absence of a solvent in the presence of a radical initiator or a transition metal complex. Can also be performed. The amounts of each component in the reaction system are the same as those described above. In this case, the solvent is distilled off after the completion of the reaction,
Alternatively, a method such as removing the catalyst residue with an ion exchange resin, metal oxide or activated carbon can be employed.

[0052]

The present invention will be described below with reference to examples and comparative examples.

[0053]

Example 1 Poly (methyl hydrogen siloxane)
2.40 g and 2.20 g of hydroquinone were charged into a 20 ml sample tube, and suspended and mixed with a stirrer (Maximix II type, manufactured by Thermoline) for 2 minutes. Put in an aluminum mold, melt at 200 ° C for 10 minutes with a press machine,
Press molding was performed under a pressure of 2.9 MPa at 30 ° C. for 30 minutes. Td ₅ of the cured molded product of the composition containing silicon in an argon stream was 308 ° C. 1000
Weight loss at 53 ° C. was 53%. The cured product of the composition containing this silicon compound has a flexural strength of 1
It was 5 MPa.

[0054]

Comparative Example 1 Td ₅ of the poly (methyl hydrogen siloxane) used in Example 1 in an argon stream was 220 ° C. The weight loss at 1000 ° C. was 98%.

[0055]

Synthesis Example 1 Poly (phenylsilyleneethynylene-1,3) was prepared based on the method described in JP-A-7-90085.
-Phenyleneethynylene). Particle size is 30-6
144 g of 0-mesh magnesium hydroxide was charged into a quartz firing tube, and pyrolyzed at 350 ° C. for 3 hours under a reduced pressure of 0.3 mmHg to obtain 100 g of magnesium oxide.
Place a stirring blade inside the 2000 ml glass container,
The inside of the vessel was replaced with high-purity nitrogen gas. Subsequently, 50.4 g (0.4 mol) of the raw material diethynylbenzene, 43.2 g (0.4 mol) of phenylsilane, and 800 ml of toluene as a solvent were charged into the container, and 100 g of the previously obtained magnesium oxide was sealed with nitrogen while stirring. Added below.
1 hour at 30 ° C, 1 hour at 40 ° C, 1 hour at 50 ° C, 6
After stirring at 0 ° 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 further concentrating the reaction solution, the polymer was precipitated in 8000 ml of heptane, and 56.2 g of the desired product, poly (phenylsilyleneethynylene-1,3-phenyleneethynylene) (M
SP-1) was obtained. The yield was 61%. GPC
The weight average molecular weight in terms of polystyrene measured by (gel permeation chromatography) was 6,900.

[0056]

Example 2 MSP-1 obtained in Synthesis Example 1 was obtained at 2.30.
g and hydroquinone 0.28 g were pulverized and mixed in a pulverizer (A-10, manufactured by Squid Japan) for 1 minute. Put in an aluminum mold, melt at 150 ° C for 15 minutes with a press machine,
Press molding was performed under a pressure of 2.9 MPa at 30 ° C. for 30 minutes. Td ₅ of the cured molded product of the composition containing silicon in an argon stream was 478 ° C. 1000
Weight loss at 16 ° C. was 16%. The flexural strength of a cured product of the composition containing the silicon compound is 2
It was 5 MPa.

[0057]

Example 3 MSP-1 obtained in Synthesis Example 1 was converted to 2,30
g and 0.20 g of 1,6-dihydroxynaphthalene were pulverized and mixed for 1 minute by a pulverizer (A-10, manufactured by Squid Japan). Put into aluminum mold, 3mmHg with vacuum press
After melting at 200 ° C. for 10 minutes under reduced pressure, press molding was performed at 250 ° C. for 30 minutes under reduced pressure of 3 mmHg under a pressure of 2.9 MPa. Further, firing was performed in an electric furnace at 400 ° C. for 2 hours in an argon stream. Td ₅ of the cured molded product of the composition containing silicon in an argon stream was 530 ° C. The flexural strength of the cured molded article of the composition containing the silicon compound was 27 MPa.

[0058]

COMPARATIVE EXAMPLE 2 MSP-1 of Example 3 was treated in the same manner as in Example 3 except that 1,6-hydroquinone was not added.
A cured product of P-1 resin was produced. The flexural breaking strength of this MSP-1 cured molded product was 10 MPa.

[0059]

According to the present invention, a silicon-containing composition comprising a polymer compound having a Si-H bond and a compound having two or more hydroxy groups in a molecule contains silicon having excellent heat resistance and mechanical properties. A composition could be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Masayoshi Ito 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals, Inc. (reference) 4J002 CP041 CP131 CP211 EC046 EJ016 EN106

Claims (3)

[Claims] 1. A silicon-containing composition comprising a polymer compound having a Si--H bond and a compound having two or more hydroxy groups in a molecule. 2. A polymer compound having a Si--H bond is represented by the general formula (1): ## STR1 ## (In the formula, R ¹ is oxygen or an alkylene group having 1 to 30 carbon atoms, alkenylene group, alkynylene group and divalent aromatic group, and represents a substituent such as a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. R ²
Is a hydrogen atom or an alkyl, alkenyl, alkynyl, alkoxy, or aromatic group having 1 to 30 carbon atoms, and may have a substituent such as a halogen atom, a hydroxyl group, an amino group, a carboxyl group, or an ether group. . 2. The method according to claim 1, wherein the method is represented by: 3. A silicon-containing composition obtained by subjecting the silicon-containing composition according to claim 1 to a heat treatment at 50 ° C. or more and 700 ° C. or less.