JPH05125191A - Silicon-based hybrid material - Google Patents

Abstract

PURPOSE:To obtain a lightweight silicon-based hybrid material having excellent heat resistance, flame resistance, environmental resistance, high toughness, moldability and processability by impregnating an alkoxysilane, etc., into an organic polymer and hydrolyzing and condensing the alkoxysilane. CONSTITUTION:(A) An alkoxysilane, preferably an alkoxysilane of the formula (R is 1-50C monofunctional organic group; R' is monofunctional hydrocarbon group such as methyl, ethyl or n-propyl; (n) is 0-3) or its partial hydrolyzate condensate (containing preferably three or more alkoxy groups such as tetraethoxysilane), a condensation catalyst, water and optionally a solvent are impregnated into (B) an organic polymer, preferably polyether-based, acrylic ester-based or polyester-based polymer in a weight ratio of (SiO2/B weight) of 0.1-100, preferably 0.2-80, especially preferably 0.5-50 and the component A is hydrolyzed and condensed to give a silicon-based hybrid material having excellent mechanical strength and moldability and processability.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat resistance obtained by impregnating an organic polymer (component (B)) with an alkoxysilane (component (A)) to cause a hydrolysis / condensation reaction.
The present invention relates to a silicon-based hybrid material having excellent combustion resistance, environment resistance, light weight, high toughness, high mechanical strength, and good moldability, and a method for producing the same.

[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.

So-called organosilicon polymers such as polysiloxanes, polycarbosilanes, polysilanes and polysilazanes, which contain silicon in the main chain skeleton, are generally superior in molding processability to inorganic silicon compounds, but their mechanical strength is high. Because it is much inferior, its range of use is limited.

[0004]

As a result of earnest research in view of such circumstances, the present invention has solved these problems and has improved heat resistance,
The present invention provides a silicon-based hybrid material having excellent combustion resistance, light weight, high toughness, high mechanical strength, and good moldability, and a method for producing the same. That is, the present invention provides a silicon-based hybrid material, which is obtained by impregnating an organic polymer (component (B)) with an alkoxysilane (component (A)) to cause a hydrolysis / condensation reaction. The manufacturing method is related.

The alkoxysilanes used as the component (A) in the present invention are components for imparting heat resistance, combustion resistance, environment resistance and high strength to the silicon-based hybrid material obtained in the present invention. There is no limitation, and various types can be used, and the alkoxysilane represented by the formula (1) or its partial hydrolysis-condensation product can be preferably used.

R _n Si (OR ′) _4-n (1) 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. Good. R'is a monovalent hydrocarbon group such as methyl, ethyl and n-propyl. n is 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, phenyltrimethoxy Trialkoxysilanes such as silane, phenyltriethoxysilane, and 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-aminopropyltrimethoxysilane, N-phenyl-γ-
A trialkoxysilane having a functional group such as aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and a partial hydrolysis condensate thereof, dimethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane. , Dialkoxysilanes such as dimethyldiethoxysilane, diphenyldiethoxysilane, diethyldimethoxysilane, vinylmethyldimethoxysilane,
γ- (methacryloxypropyl) methyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-
Dialkoxysilanes having functional groups such as mercaptopropylmethyldimethoxysilane, trimethylmethoxysilane, phenyldimethylmethoxysilane, triphenylmethoxysilane, triethylmethoxysilane, monoalkoxysilanes such as octyldimethylmethoxysilane,
Monoalkoxysilanes having functional groups such as vinyldimethylmethoxysilane, γ- (methacryloxypropyl) dimethylmethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane. Can be given.

Of these, at least 3 in one molecule
Tetraalkoxysilanes and trialkoxysilanes having one or more alkoxy groups and their partially hydrolyzed condensates are preferably used. These alkoxysilanes and their partially hydrolyzed condensates may be used alone or in combination of two or more. Examples of the catalyst used in the hydrolysis / condensation reaction of the alkoxysilanes as the component (A) include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and chloroplatinic acid; inorganic bases such as sodium hydroxide and calcium hydroxide; tetra. Titanic acid esters such as butyl titanate and tetrapropyl titanate; tin carboxylates such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate; reaction products of dibutyltin oxide and phthalate ester; dibutyltin diacetyl. Acetonates; Organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium tetraacetylacetate Over DOO, chelate compounds such as titanium tetraacetyl acetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine,
Cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenylguanidine, 2,
4,6-tris (dimethylaminomethyl) phenol,
Morpholine, N-methylmorpholine, 2-ethyl-4-
Methylimidazole, 1,8-diazabicyclo (5,5
4,0) amine compounds such as undecene-7 (DBU) or salts thereof with carboxylic acids; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction of excess polyamine with epoxy compound Products; silane coupling agents having an amino group, for example, compounds such as γ-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane can be exemplified. Further, other known silanol condensation catalysts such as acidic catalysts and basic catalysts can be used. These catalysts may be used alone or 2
You may use together 1 or more types.

The organic polymer used as the component (B) in the present invention is a component which imparts toughness, light weight and moldability to the silicon hybrid material obtained in the present invention.
The molecular weight of the organic polymer is not particularly limited, but is generally about 10 in consideration of swelling with alkoxysilanes and the performance of the obtained silicon-based hybrid material.
Those of about 00 to 500,000 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. The organic polymer used in the present invention is not particularly limited, and C,
It is composed of H, N, O, S and halogen atoms. The main chain skeleton is also not particularly limited, and those having various main chain skeletons can be used.

Specific examples include polyether polymers such as polyoxyethylene, polyoxypropylene, polyoxytetramethylene and polyoxyethylene-polyoxypropylene copolymers, and dibasic acids such as adipic acid. Polyester-based polymers obtained by condensation with glycol or ring-opening polymerization of lactones, ethylene-propylene-based copolymers, polyisobutylene, copolymers of isobutylene and isoprene, etc., polychloroprene, polyisoprene, isoprene and butadiene, Acrylonitrile, copolymers with styrene, etc., polybutadiene, butadiene with styrene, copolymers with acrylonitrile, etc., polyisoprene, polybutadiene, isoprene or polybutadiene obtained by hydrogenating copolymers with butadiene, acrylonitrile, styrene, etc. Polyacrylic acid ester obtained by radical polymerization of monomers such as reffin polymer, ethyl acrylate and butyl acrylate, acrylic acid ester such as ethyl acrylate and butyl acrylate and acrylic acid with vinyl acetate, acrylonitrile, methyl methacrylate and styrene Ester-based copolymers, graft polymers obtained by polymerizing vinyl monomers in the organic polymers, polysulfide-based polymers, condensation polymerization of nylon 6, hexamethylenediamine and adipic acid by ring-opening polymerization of ε-aminocaprolactam. By nylon 6
6, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of ε-aminoundecanoic acid, nylon 12 by ring-opening polymerization of ε-aminolaurolactam, two or more components of the above nylons Examples thereof include polyamide-based polymers such as copolymerized nylon having, for example, polycarbonate-based polymers produced by condensation polymerization of bisphenol A and carbonyl chloride, diallyl phthalate-based polymers and the like. Among the polymers having the main chain skeleton, polyether polymers, acrylic acid ester copolymers, polyester polymers, hydrocarbon polymers, and polycarbonate polymers are preferable.

The organic polymer used in the present invention may be one kind or a mixture of two or more kinds. The ratio of the alkoxysilanes and the organic polymer used in the present invention 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, it is convenient to use the weight ratio of SiO ₂ and organic polymer in the same mole number as the silicon atoms contained in the alkoxysilanes used. The weight ratio (weight of SiO ₂ / organic polymer) is 0.1 to 1
It can be suitably used in the range of 00. 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 order to obtain the desired properties of the silicon-based hybrid material of the present invention, the alkoxysilanes as the component (A), the condensation catalyst generally required for the condensation reaction, and water are
It is desirable to impregnate the organic polymer as the component (B) into a uniform state. When the reaction is carried out in a heterogeneous state, the concentration of a certain component is locally increased and a partial gelation occurs, often resulting in only a heterogeneous material.

Therefore, in order to improve the impregnating property and the uniformity of the above components, and further to control the reaction temperature, a solvent can be used if necessary. The solvent is not particularly limited, but methanol, ethanol, isopropanol, n-
Alcohol solvents such as propanol and n-butanol; ether solvents such as THF, 1,4-dioxane, 1,3-dioxane and 1,2-dimethoxyethane;
A ketone solvent such as acetone or methyl ethyl ketone; a polar aprotic solvent such as acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone; or the like can be specifically used. Of these, methanol, ethanol, isopropanol,
A solvent selected from one or more selected from n-butanol, THF, 1,4-dioxane, and acetone is preferable.

As a post-treatment step for obtaining the silicon-based hybrid material of the present invention, a reaction mixture obtained by impregnating an organic polymer with alkoxysilanes and polymerizing the reaction mixture is used at room temperature to 10
It includes a step of forming into a film shape, a fibrous shape, a plate shape, a rod shape or other complicated shapes in a temperature range of about 0 ° C., 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, and for the purpose of adjusting the characteristics of the silicon-based hybrid material obtained in addition to the basic components. Various additives and reinforcing agents can be used. The additives / reinforcing agents can be added as necessary at the stage where the condensation reaction has proceeded to a certain extent, the stage of removing volatile components, and the like.

Specific examples of additives and reinforcing agents that can be used in the present invention include Al (OiPr) ₃ and Ti.
(OiPr) ₄ , Ti (OnBu) ₄ , B (OE
t) ₃ , Zr (OiPr) ₄ , Ti (OSiM
e ₃ ) ₄ , (Me ₃ SiO) ₂ Ti (OiPr) ₂ , B
(OH) ₃ , (where iPr is an isopropyl group, nB
u is a normal butyl group, Et is an ethyl group, Me is a methyl group), and various alkoxides or hydroxides, glass fiber, alumina fiber, carbon fiber, boron fiber, silicon carbide fiber, silicon nitride fiber , Inorganic fiber such as Tyranno fiber, aramid fiber, nylon fiber, vinylon fiber, polyester fiber, polyarylate fiber, ultra high molecular weight polyethylene fiber, poly-p
-Benzamide, made of organic fibers such as polyamide hydrazide, chopped, yarn-shaped, woven, mat-shaped, asbestos, mica, talc and the like and mixtures thereof, calcium carbonate, alumina, silica, clay,
Examples thereof include titanium oxide and carbon black.

The silicon-based hybrid material of the present invention thus obtained has excellent heat resistance and combustion resistance, is lightweight and has high toughness, high mechanical strength, and moldability, and therefore is used in various applications. be able to. To give a concrete example,
Artificial hygiene, space shuttles, space colonies, aircraft and rocket fuselage, aerospace structural materials used for engine peripheral parts, automobile outer panels, cylinder heads, etc.
Wheel caps, propeller shafts, engine peripheral materials, interior materials, bicycle tire frames, linear motor car materials, other automobiles, motorcycles, bicycles, etc.
For structural materials used in various transportation equipment such as tricycles, railroads, ships, agricultural equipment such as tractors, houses, buildings, bridges, pedestrian bridges, ladders, skyscrapers, deep underground structures, undersea structures, etc. Structural materials used, sports equipment such as boats, yachts, skis, snowmobiles, glider aircraft, tennis rackets, golf shafts, fishing rods, tent props, household appliances such as microwave ovens, refrigerators, washing machines, personal computers, artificial bones, etc. Medical materials such as artificial teeth and artificial roots, cosmetic materials, sealing materials,
Adhesives, adhesives, adhesives, paints, modifiers, plasticizers, masking materials, mold release materials, defoamers, fiber treatment materials, electrical insulation materials, semiconductor encapsulation materials, ceramic fibers and precursors for molded products Body, molding material such as RIM / LIM / injection / extrusion / blow / 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 Functional glass for optical applications such as glass and optical disk substrates, functional glass for TV imaging tube elements, solid state batteries, delay line glass, electromagnetic fields such as displays, heat-resistant materials, photomask substrates, thermal applications such as adhesion and adhesion Functional glass, functional glass for chemicals such as high temperature separation and purification, enzyme fixation, solidification of radioactive waste, etc. can be mentioned, but is not limited to these. Not intended to be.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples, but the contents of the present invention are not limited thereto. Example 1 500-mL 3-neck flask with motorized stir bar, 2
A 5-mL dropping funnel with a pressure equalizing tube and a cooling tube with a 3-way cock were attached, and the system was replaced with nitrogen. 200 g of tetraethoxysilane and polyethylene (average molecular weight 300
0) Charge 200 g, water 20 mL, THF 30 mL,
A solution prepared by dissolving 20 mL of a 0.5 N HCl solution in 10 mL of THF was placed in a dropping funnel. The flask was placed in an oil bath at 70 ° C., and the catalyst solution was added dropwise from the dropping funnel while stirring the contents well. The dropping was completed in about 1 hour. Further, a viscous solution was obtained by reacting at 70 ° C. for 2 hours.

The obtained viscous reaction solution was poured into a mold of 100 × 25 × 25 mm, which was previously covered with a Teflon sheet, to a depth of 10 mm. 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 5 mm. This material was as strong as ordinary glass and did not undergo brittle fracture.

Comparative Example 1 A glass-like molded body was obtained in the same manner as in Example 1 except that the organic polymer was not used. This molded body had a strength similar to that of glass, but was brittle.

[0022]

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

Claims (1)

[Claims] 1. A silicon-based hybrid material, which is obtained by impregnating an organic polymer (component (B)) with an alkoxysilane (component (A)) to cause a hydrolysis / condensation reaction.