JPH05105763A - Silicon-based hybrid material - Google Patents

Abstract

PURPOSE:To obtain the subject lightweight and high-toughness material excellent in resistance to heat, combustion and environment, having high mechanical strength and good molding prcessability by reaction of an alkoxysilane with an organic polymer having SiH groups in the molecule. CONSTITUTION:The objective hybrid material suitable as e.g. a structural material for aerospace applications or medical material is obtained by reaction of (A) an alkoxysilane such as orthomethyl silicate or orthoethyl silicate with (B) an organic polymer having at least two SiH groups in the molecule such as ether polymer in the presence of a catalyst such as tetrabutyl titanate.

Description

Detailed Description of the Invention

[0001]

The present invention relates to heat resistance, combustion resistance and environment resistance obtained by reacting alkoxysilanes with an organic polymer having at least two SiH groups in the molecule in the presence of a catalyst. TECHNICAL FIELD The present invention relates to a silicon-based hybrid material having excellent properties, light weight, high toughness, high mechanical strength, and good moldability.

[0002]

2. Description of the Related Art At present, various types of materials are used as silicon materials in view of their characteristics and required performance. Silicon-containing ceramics such as silicon carbide, silicon nitride, and silicon oxide, and various silicates are materials having excellent mechanical strength, chemical stability, and thermal stability. However, these inorganic silicon compounds are generally hard and brittle, and have extremely poor moldability, so that their use is limited. In addition, so-called organosilicon polymers such as polysiloxane, polycarbosilane, polysilane, and polysilazane, which contain silicon in the main chain skeleton, are generally superior in molding processability to inorganic silicon compounds, but their mechanical strength is remarkably high. Because it is inferior, its range of use is limited.

[0003]

Means for Solving the Problems As a result of earnest research in view of such circumstances, the present inventors have solved these problems and are excellent in heat resistance and combustion resistance, lightweight and tough, and have high mechanical strength. The present invention provides a silicon-based hybrid material having excellent moldability. That is, it relates to a silicon-based hybrid material obtained by reacting an alkoxysilane with an organic polymer having at least two SiH groups in the molecule in the presence of a catalyst.

The alkoxysilanes used in the present invention are components for imparting heat resistance, combustion resistance, environmental resistance, and high strength to the silicon-based hybrid material obtained in the present invention, and there is no particular limitation, and various kinds are used. The alkoxysilanes represented by the formula (1) or their partial hydrolysis-condensation products can be preferably used. R _n Si (OR ′) _4-n (1) (In the formula, R is a monovalent organic group having 1 to 50 carbon atoms, which may be the same or different, and may contain a functional group. R'represents a monovalent hydrocarbon group such as methyl, ethyl, and n-propyl, and n represents an integer selected from 0, 1, 2, and 3.)

Specific examples include orthomethyl silicate, orthoethyl silicate, ortho n-propyl silicate, ortho i-propyl silicate, ortho n-.
Tetraalkoxysilanes such as butyl silicate, orthoisoamyl silicate, ortho n-octyl silicate, ortho n-nonyl silicate and their partial hydrolysis-condensation products, methyltrimethoxysilane, methyltriethoxysilane, methyltrin-propylsilane, phenyltriphenylsilane Trialkoxysilanes such as methoxysilane, phenyltriethoxysilane, ethyltrimethoxysilane and their partial hydrolysis-condensation products, vinyltrimethoxysilane, vinyltriethoxysilane, γ (methacryloxypropyl) trimethoxysilane, β (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltrimetho Shishiran, N- phenyl -γ-
Trialkoxysilanes having functional groups such as aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane, and partial hydrolyzed condensates thereof, dimethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxy. Dialkoxysilanes such as silane, dimethyldiethoxysilane, diphenyldiethoxysilane, diethyldimethoxysilane, vinylmethyldimethoxysilane, γ (methacryloxypropyl) methyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-amino Propylmethyldimethoxysilane, γ-
Dialkoxysilanes having functional groups such as mercaptopropylmethyldimethoxysilane, trimethylmethoxysilane, phenyldimethylmethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, monoalkoxysilanes such as octyldimethylmethoxysilane, vinyldimethylmethoxysilane, γ Examples thereof include monoalkoxysilanes having a functional group such as (methacryloxypropyl) dimethylmethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane.

Of these, at least 3 in one molecule
Orthosilicates having 3 or more alkoxy groups, trialkoxysilanes and their partial hydrolysis-condensation products are preferably used. These alkoxysilanes and their partial hydrolysis-condensation products may be used alone or in combination of two or more.

At least 2 in the molecule used in the present invention
The organic polymer having individual SiH groups is a component that imparts toughness, lightness, and moldability to the silicon-based hybrid material obtained in the present invention, and the main chain skeleton is essentially C, O,
Any so-called organic main chain skeleton composed of N or the like can be used without particular limitation.

The SiH group may exist randomly in a pendant type in the main chain of the organic polymer, or may exist at the molecular end. The number of SiH groups may be at least two in the molecule, but is preferably 2 or more and 30 or less. When the number of SiH groups is one, the strength of the silicon-based hybrid material obtained by the present invention is not sufficient, and SiH
If there are more than 30 groups, the toughness of the resulting silicon-based hybrid material will be insufficient and the material will become extremely brittle.

Although the molecular weight is not particularly limited, it is generally 1000 to 5 in view of compatibility with alkoxysilanes and performance of the obtained silicon-based hybrid material.
Those of about 00000 are preferably used.

The main chain skeleton of the organic polymer used here may be linear, ladder-like, branched or cage-like. A linear or ladder-shaped material is preferably used in consideration of the reactivity with the alkoxysilanes and the performance of the obtained silicon-based hybrid material.

A specific example will be described below. First,
Examples of the ether-based polymer used in the present invention include

[Chemical 1] Etc. are specifically mentioned as a structural unit of the main chain skeleton.

In the polyether polymer, not only one kind of these structural units may be bonded, but two or more kinds of structural units may be bonded in a mixed form. Specific examples of the polymer include polyoxyethylene, polyoxypropylene, polyoxytetramethylene, and polyoxyethylene-polyoxypropylene copolymer.
Further, the polyether polymer may be linear or branched. As the polyester polymer, the main chain skeleton constituting the polymer is produced, for example, by polycondensing a polybasic acid and a polyhydric alcohol by a method such as a direct esterification method or a transesterification method. Specifically, the following components may be polycondensed, but the components are not limited thereto.

[Dihydric alcohol] ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, dipropylene glycol [trivalent or higher polyhydric alcohol] Alcohol] glycerin, trimethylolmethane, trimethylolpropane, pentaerythritol

[Divalent carboxylic acid] Phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, polybutadienedicarboxylic acid, oxalic acid, malonic acid, succinic acid, adipic acid,
Sebacic acid, maleic acid, fumaric acid, cyclopentanedicarboxylic acid [polyvalent carboxylic acid having a valence of 3 or more] trimellitic acid, butanetricarboxylic acid, pyromellitic acid, and also anhydrides of the above carboxylic acids, acyl halides and the like. Can be used similarly to.

The main chain skeleton of the polymer can also be produced by ring-opening polymerization of lactone. Examples of the lactone include β-propiolactone, pivalolactone,
α-methyl-β-propiolactone, δ-valerolactone, methyl-δ-valerolactone, dimethyl-δ-valerolactone, ε-caprolactone, δ-methyl-ε-caprolactone, dimethyl-ε-caprolactone and the like. . The polyester polymer may be linear or branched.

As the hydrocarbon-based polymer, the monomer components constituting the polymer include olefins having 2 to 12 carbon atoms and acetylenes, conjugated dienes, vinyl ethers, aromatic vinyl compounds and the like. To be Specific examples include ethylene, acetylene, propylene, 1-butene, 2-butene, isobutylene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, pentyne, 4
-Methyl-1-pentene, hexene, hexine, vinylcyclohexane, butadiene, isoprene, chloroprene, cyclopentadiene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methylstyrene, dimethylstyrene, monochlorostyrene, dichlorostyrene, β- Examples include pinene, indene, cyclopentadiene and the like. Among these, propylene, 1-butene, 2-butene, isobutylene,
Butadiene, isoprene and the like are preferable. Radical polymerization method, ionic polymerization method, coordination ionic polymerization method, living cationic polymerization method (so-called inifer method) proposed by Kennedy et al. Thus, various hydrocarbon polymers can be obtained. When the diene and acetylene are used for the polymerization, the double bond remains in the main chain or the side chain, which can be used to introduce a hydrosilyl group later. Also, hydrogenated products may be used.

As examples of hydrocarbon polymers, polyisobutylene, ethylene-propylene copolymer, 1,2
-Polybutadiene, 1,4-polybutadiene, hydrogenated polybutadiene, polyisoprene, hydrogenated polyisoprene, etc. may be mentioned, but not limited thereto. The hydrocarbon-based polymer may be linear or branched.

As the acrylic acid ester-based polymer, the monomer components constituting the polymer include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate and i-butyl acrylate. , Sec.-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, tridecyl acrylate, stearyl acrylate, cyclohexyl acrylate, benzyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate,
2-butoxyethyl acrylate, 2-phenoxyethyl acrylate, ethylcarbitol acrylate, allyl acrylate, glycidyl acrylate, dimethylaminoethyl acrylate, acrylic acid, sodium acrylate, trimethylolpropane triacrylate, 1,
Acrylic acid and acrylic acid ester monomers such as 4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and pentaerythritol triacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, t- Butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, propyl methacrylate, benzyl methacrylate, isopropyl methacrylate, sec.-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, allyl methacrylate, ethylene glycol methacrylate, triethylene glycol methacrylate, tetraethylene glycol methacrylate, 1,3-butylene glycol methacrylate, trimethylolpropane methacrylate , 2-ethoxyethyl methacrylate, 2-methoxyethyl methacrylate, dimethylaminoethyl methyl chloride salt methacrylate, methacrylic acid and methacrylic acid ester monomers such as methacrylic acid and sodium methacrylic acid. Further, in addition to the (meth) acrylic acid ester-based monomer, vinyl monomers such as acrylamide, acrylonitrile, vinyl acetate, styrene, ethylene, propylene, isobutylene, butadiene, isoprene and chloroprene can be used as a copolymer component.

A radical polymerization method, an ionic polymerization method, and a GTP method (Group Transfer Polymerization) proposed by Du Pont Co. are used by combining one or more of the above-mentioned monomer components.
Various acrylic acid ester-based polymers can be obtained by the method described in (4). The polymer may be linear or branched.

Various carbonate-based polymers can be used in the present invention. The polycarbonate-based polymer in the present invention is a structure in which the molecular weight of a hydroxy compound is increased through one or more carbonate bonds. Means a polymer having

The polycarbonate-based polymer is a generally used polymerization reaction, that is, (1) a method of reacting a dihydroxy compound with phosgene, (2) a method of synthesizing by an ester exchange reaction between an alkylene carbonate and a dihydroxy compound, (3) ) It can be produced using a method of synthesizing by transesterification of a dialkyl carbonate and a dihydroxy compound. Examples of the dihydroxy compound used at this time include 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-ethyl-1,6-
Hexanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,
2'-bis- (4-hydroxycyclohexyl) -propane, p-xylenediol, p-tetrachloroxylenediol, 1,4-dimethylolcyclohexane, 3
(4), 8 (9) -bis- (hydroxymethyl) -tricyclodecane dimethylol, bis-hydroxymethyl tetrahydrofuran, di (2-hydroxyethyl) dimethylhydantoin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, Propylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol,

[0022]

[Chemical 2]

[0023]

[Chemical 3]

And the like. The polycarbonate-based polymer produced by using these dihydroxy compounds may be linear or may be branched by using a polyfunctional hydroxy compound together during the polymerization.

The hydrosilyl group contained in the polymer used in the present invention may be in the molecule or at the terminal of the molecule. It is preferable that the hydrosilyl group is present at the molecular end because the effective network chain length of the obtained silicon-based hybrid material becomes longer, and flexibility and molding processability can be effectively imparted.

The hydrosilyl group as used in the present invention generally means
There is no particular limitation as long as it has a Si-H bond, and the formula (1)

[0027]

[Chemical 4]

As a specific example, -Si (H)_n
(CH₃)_3-n, -Si (H)_n(C₂H_Five)_3-n, −
Si (H)_n(C₆H_Five)_3-n(N = 1 to 3), -Si
H₂(C₆H₁₃) Etc. containing only one silicon atom
Dorosilyl group, -Si (CH ₃)₂Si (CH₃)
₂H, -Si (CH₃)₂CH₂CH₂Si (CH₃)
₂H, -Si (CH₃)₂SiCH₃H₂,

[0029]

[Chemical 5] A hydrosilyl group containing two or more silicon atoms, such as

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

Examples thereof include hydrosilyl groups derived from various chain-like, branched-like, and cyclic polyvalent hydrogen siloxanes. Of the above various hydrosilyl groups, considering the reactivity of the hydrosilyl group,
The following are preferred.

[0035]

[Chemical 10]

[0036]

[Chemical 11]

From the viewpoint that the reactivity of the polymer (reactivity of the hydrosilyl group) is large and the compatibility with other polymers is good, hydrogen is bonded to silicon atoms in the polysiloxane due to the cyclic polysiloxane. Groups are particularly preferred.

The binding mode of the hydrosilyl group and the organic polymer is not particularly limited. The carbon-silicon bond or carbon-silicon bond carbon is further bonded to the main chain skeleton of the organic polymer through urethane, ester, ether and carbonate bonds.

The method for producing the hydrosilyl group-containing organic polymer used in the present invention is not particularly limited, and any method may be used. For example, (1) Si- in the molecule
An organic polymer having a Cl group is treated with a reducing agent such as LiAlH ₄ or NaBH _{4 to change} the Si-Cl group in the polymer to Si.
-H group, (2) a method of reacting an organic polymer having a functional group X in the molecule with a compound having a functional group Y reactive with the functional group X and a hydrosilyl group at the same time in the molecule, (3) By selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to an alkenyl group-containing organic polymer,
A method is conceivable in which the hydrosilyl group is left in the molecule of the polymer or at the molecular terminal after the reaction.

The ratio of the alkoxysilanes used in the present invention to the organic polymer is a very important index for controlling the properties of the obtained silicon-based hybrid material. Since the silicon content of the alkoxysilanes varies depending on the type, the calculation is made on the assumption that the alkoxysilanes are completely hydrolyzed and condensed. SiO ₂ (Each 1 Si atom is formally converted into 1 SiO ₂ unit). It is convenient to use the weight ratio of the amount to the organic polymer (assuming that). The weight ratio (weight of SiO ₂ / organic polymer) is usually 0.1 to 10
It can be preferably used in the range of 0. The range is more preferably 0.2 to 80, particularly preferably 0.5 to 50. If the weight ratio is less than 0.1, the strength of the obtained silicon-based hybrid material is insufficient, and if it is more than 100, the obtained silicon-based hybrid material becomes brittle.

In the present invention, in the reaction between the alkoxysilanes and the organic polymer having at least two SiH groups in the molecule, the respective reactions represented by the formulas (2) to (7) proceed, and the post-treatment step is carried out. Finally, the silicon-based hybrid material of the present invention can be manufactured by the above process.

[0042]

[Chemical 12]

Although the above reaction is extremely slow under neutral and non-catalytic conditions, the reaction rate can be controlled by using various catalysts. The type of catalyst that promotes the reaction is slightly different depending on the difference in each reaction type, but the following catalysts can be used. Hydrochloric acid, sulfuric acid,
Inorganic acids such as phosphoric acid and chloroplatinic acid; sodium hydroxide,
Inorganic bases such as calcium hydroxide; Titanate esters such as tetrabutyl titanate and tetrapropyl titanate; Dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate,
Tin carboxylates such as tin naphthenate; Reaction products of dibutyltin oxide and phthalates; Dibutyltin diacetylacetonate; Aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate and other organoaluminum compounds Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine,
Monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,4,6-tris (dimethylamino) Methyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8
-Diazabicyclo (5,4,0) undecene-7 (DB
U) or other amine compounds or salts thereof with carboxylic acids or the like; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds; silanes having amino groups. Examples of the coupling agent include compounds such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane. Further, other known silanol condensation catalysts such as acidic catalysts and basic catalysts can be used. These catalysts may be used alone or in combination of two or more.

In carrying out the reaction between the alkoxysilanes and the organic polymer containing at least two SiH groups in the molecule, since the two components are generally hydrophobic, they are insoluble in water and non-uniform. It will be in a state. When the reaction is carried out in this state, the water concentration locally rises and gelation occurs partially, and in many cases only a heterogeneous material can be obtained. Therefore, it is preferable to use a solvent in order to uniformly mix the three components of the alkoxysilanes, the organic polymer and water. Specifically, alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol and ethyl cellosolve, and ether solvents such as tetrahydrofuran and 1,4-dioxane can be preferably used.

As a post-treatment step for obtaining the silicon-based hybrid material of the present invention, a reaction mixture of alkoxysilanes and an organic polymer having at least two SiH groups in the molecule is treated at a temperature from room temperature to about 100 ° C. The process includes a step of forming into a film shape, a fiber shape, a plate shape, a rod shape or other complicated shapes within a range, and a step of removing volatile components from the reaction mixture. Of these, curing shrinkage and compaction of the molded body occur in the step of removing volatile components, so that the step has a great influence on the performance of the obtained silicon-based hybrid material. Generally, it is preferable to gradually remove the volatile components in order to minimize the strain remaining inside the molded body. At that time, changing the temperature / pressure may be used. Further, firing may be performed for the purpose of improving the physical properties of the obtained silicon-based hybrid material.

The silicon-based hybrid material of the present invention is produced by using alkoxysilanes and an organic polymer as main components. In addition to the basic components, various silicon-based hybrid materials can be adjusted for the purpose of adjusting the characteristics of the obtained silicon-based hybrid material. Additives and reinforcing agents can be used. The additives / reinforcing agents can be added as required at the time of the reaction of the above-mentioned basic components, at the stage where their condensation reaction has progressed to a certain extent, at the stage of removing volatile components, and the like.

As specific examples of additives and reinforcing agents that can be used in the present invention, various metal alkoxides or hydroxides other than alkoxysilanes may be used in combination. Specific examples of these compounds are Al (OiP
r) ₃ , Ti (OiPr) ₄ , Ti (OnBu) ₄ , B
(OEt) ₃ , Zr (OPr) ₄ , Ti (OSiM
e ₃ ) ₄ , (Me ₃ SiO) ₂ Ti (OiPr) ₂ , B
Various metal alkoxides such as (OH) ₃ , hydroxides, glass fibers, alumina fibers, carbon fibers, boron fibers, silicon carbide fibers, silicon nitride fibers, tyranno fibers, and other inorganic fibers, aramid fibers,
Nylon fiber, vinylon fiber, polyester fiber, polyarylate fiber, ultra high molecular weight polyethylene fiber, poly-
Chop-shaped, yarn-shaped, woven-shaped or mat-shaped organic fibers such as p-benzamide and polyamide hydrazide, asbestos, mica, talc and mixtures thereof, calcium carbonate, alumina, silica, clay, titanium oxide , Carbon black and the like.

The silicon-based hybrid material of the present invention thus obtained can be used for various purposes. Concrete examples are aerospace structural materials used for satellites, space shuttles, space colonies, aircraft and rocket fuselage, engine peripheral parts, automobile outer plates, cylinder heads, wheel caps, propeller shafts, engine surroundings. Materials / Interior materials / Bicycle tire frames / Linear motor car materials / Other structural materials used in various transportation equipment such as automobiles, motorcycles, bicycles, tricycles, railroads, ships, agricultural equipment such as tractors, housing, etc. Structural materials used for buildings, bridges, pedestrian bridges, ladders, skyscrapers, deep underground structures, undersea structures, boats, yachts, skis, snowmobiles, etc.
Sports equipment such as glider aircraft, tennis rackets, golf shafts, fishing rods, and tent posts, household appliances such as microwave ovens, refrigerators, washing machines, personal computers, medical materials such as artificial bones, artificial teeth and artificial roots, and cosmetics Materials, sealing materials, adhesives, adhesives, adhesives,
Paints, modifiers, plasticizers, masking materials, mold release materials, defoaming materials, fiber treatment materials, electrical insulation materials, semiconductor encapsulation materials, ceramic fibers and precursors for molded products, RIM / LIM / injection / extrusion / blowing・ Molding material for compression, shape memory material, optical fiber, laser disk optical memory film, photochromic glass, optical switch, refractive index distribution glass, heat ray blocking glass, reflector, antireflection glass, optical-related functionality such as optical disk substrate Functional glass for electromagnetic fields such as glass, TV image pickup tube devices, solid state batteries, delay line glass, displays, etc., heat-resistant materials, photomask substrates, functional glass for heat-related applications such as adhesion and adhesion, high temperature separation and purification,
Examples thereof include functional glass for chemicals such as enzyme immobilization and solidification of radioactive waste, but are not limited to these.

[0049]

EXAMPLES The present invention will be specifically described below with reference to examples, but the contents of the present invention are not limited thereto. Production Example 1 A SiH group-containing polypropylene oxide was synthesized according to the description in Example 1 of JP-A-3-200807. 26.3 g of 1,3,5,7-tetramethyltetracyclosiloxane LS-8600 was placed in a 1 liter 4-neck flask equipped with a stirring rod with a motor, a dropping funnel with a 500 ml pressure equalizing pipe, a thermometer, a nitrogen introducing pipe, and a cooling pipe. (10
9 mmol) was charged. The flask was placed in an oil bath at about 75 ° C. Next, allyl ether terminated polypropylene oxide 2 having a number average molecular weight of 9900 (measured by GPC)
00 g (allyl group content: 43.8 mmol) and 45 μl of chloroplatinic acid catalyst solution (8.7 × 10 ⁻³ mmol, 2)
^{X10 -4} mol vs allyl group) with dry toluene 22
A solution dissolved in 5 ml was added to the dropping funnel for about 2 minutes per minute.
The mixture was added dropwise at a rate of 5 ml for about 2.5 hours. Immediately after the completion of the dropping, it was confirmed by the IR spectrum of the reaction solution that the allyl group of 1 was almost consumed. Then raise the bath temperature to 80 ° C to complete the reaction and
Reacted for hours. Toluene and excess 1, in the reaction system
8,3,5,7-tetramethyltetracyclosiloxane
By removing under reduced pressure at 0 ° C. for 1 hour, 208 g of a pale yellow viscous Si—H group-containing polypropylene oxide was obtained. Molecular weight (GPC) = 16800 (Mn), 47000
(Mw), viscosity = 160 poise (40 ° C.), Si—H value = 0.0491 mol / 100 g (alkali decomposition method)

Production Example 2 A SiH group-containing polypropylene oxide was synthesized according to the description of Example 3 in JP-A-3-200807. 300ml- equipped with a stirring rod with a motor, a dropping funnel with a 100ml pressure equalizing pipe, and a cooling pipe with a three-way cock
A 4-necked flask was prepared. 21.2 g of 1,3,5,7-tetramethyltetracyclosiloxane LS-8600
(0.088 mol) was charged into the flask. 40 g of allyl carbonate-terminated amorphous polycaprolactone having a number average molecular weight of 4,400 (measured by GPC), 36 μl of an acid catalyst solution (6.9 × 10 ⁻³ mmol, 2 × 10 ⁻⁴ mol)
(vs allyl group) dissolved in 50 ml of toluene was added dropwise at 70 ° C. over about 2 hours. 70 after the dropping
After stirring at ℃ for 1 hour, the residual allyl group in the reaction solution was checked by IR spectrum to be 1645 cm ^-1.
It was confirmed that the absorption derived from ν _{c = c} disappeared. Toluene and excess 1,3,5,7-tetramethyltetracyclosiloxane were removed under reduced pressure at 80 ° C. for 1 hour to remove Si—H group-containing amorphous polycaprolactone 4
2 g was obtained as a colorless transparent viscous liquid. Molecular weight (GPC) = 8750 (Mn), 17800 (M
w), Si-H value = 0.218 mol / 100 g (alkali decomposition method)

Example 1 Ethylsilicate 40 (manufactured by Colcoat Co., Ltd., a mixture of condensates of tetraethoxysilane as shown by the following formula, which has a complex structure such as branched or cyclic other than chain It is believed that.)

[0052]

[Chemical 13]

To a solution of 50 g dissolved in 150 ml of isopropanol, 20 g of a 30 wt% polypropylene oxide THF solution having a SiH group synthesized in Preparation Example 1 was added at room temperature, and the mixture was stirred well until it became substantially uniform. 6 ml of 0.3 N HCl aqueous solution was added to the mixed solution at room temperature with vigorous stirring. Evolution of hydrogen and a mild exotherm were observed. After reacting at room temperature for a total of 1 hour, the reaction solution was poured to a depth of 20 mm in a 100 × 25 × 25 mm mold frame preliminarily covered with a Teflon sheet. This was dried at room temperature for 1 week and at 50 ° C. for 3 days to obtain a colorless transparent glassy silicon-based hybrid material having a thickness of about 3 mm. This material was as strong as ordinary glass and did not undergo brittle fracture.

Example 2 A colorless transparent glassy silicon-based hybrid material was prepared in exactly the same manner as in Example 1 except that 15 g of a 30 wt% THF solution containing the amorphous Si-containing polycaprolactone prepared in Preparation Example 2 was used. Obtained. This material was as strong as glass and did not undergo brittle fracture.

Comparative Example 1 A glass-like molding was obtained in exactly the same manner as in Example 1 except that the organic polymer having at least two SiH groups in the molecule was not used. This molded body had a strength similar to that of glass, but was brittle.

[0056]

According to the present invention, it is possible to provide a silicon-based hybrid material which is excellent in heat resistance, combustion resistance and environment resistance, is lightweight and has high toughness, high mechanical strength and good moldability.

Claims (1)

[Claims] 1. A silicon-based hybrid material obtained by reacting an alkoxysilane with an organic polymer having at least two SiH groups in the molecule.