JPH0598011A - Silicon-containing hybrid material - Google Patents

Abstract

PURPOSE:To provide a silicon-containing hybrid material having excellent heat resistance, burning resistance and toughness, light weight, high mechanical strengths and good moldability, and a process for producing the same. CONSTITUTION:The title material is prepared by effecting the hydrolytic condensation of an alkoxysilane and the ring opening polymerization of a cyclic silicon compound.

Description

Detailed Description of the Invention

[0001]

The present invention is obtained by carrying out a hydrolysis / condensation reaction of alkoxysilanes (component (A)) and a ring-opening polymerization reaction of a silicon-containing cyclic compound (component (B)). The present invention relates to a silicon-based hybrid material having excellent heat resistance, combustion resistance, and environmental resistance, lightweight and 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 is characterized by being obtained by carrying out a hydrolysis / condensation reaction of alkoxysilanes (component (A)) and a ring-opening polymerization reaction of a silicon-containing cyclic compound (component (B)). A hybrid material and a manufacturing method thereof.

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, ortho n-butyl silicate, ortho isoamyl silicate, ortho n-octyl silicate, ortho n-. Tetraalkoxysilane such as nonyl silicate and its partial hydrolysis-condensation product, methyltrimethoxysilane, methyltriethoxysilane, methyltrin-propylsilane, phenyltrimethoxysilane, phenyltriethoxysilane, ethyltrimethoxysilane and other trialkoxysilanes. And its partial hydrolysis-condensation products, vinyltrimethoxysilane, vinyltriethoxysilane, γ (methacryloxypropyl) trimethoxysilane, β (3,4-epoxycyclohexyl) ether Tilttrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, N-phenyl-
Trialkoxysilanes having functional groups such as γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane, and partial hydrolysis condensates thereof, dimethyldimethoxysilane, phenylmethyldimethoxysilane, diphenyl. Dialkoxysilanes such as dimethoxysilane, 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,
Monoalkoxysilanes having functional groups such as vinyldimethylmethoxysilane, γ (methacryloxypropyl) dimethylmethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-mercaptopropyldimethylmethoxysilane are available. can give.

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, dianidine, 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 silicon-containing cyclic compound used as the component (B) in the present invention is a component which imparts toughness, lightness and moldability to the silicon-based hybrid material obtained in the present invention. The silicon-containing cyclic compound is not particularly limited as long as the atoms forming the ring skeleton thereof include at least one silicon atom, and various compounds can be used.

First, as the polysiloxane silicon-containing cyclic compound having a ring skeleton composed of Si and O, compounds represented by the following chemical formulas 1 to 3 can be exemplified.

[0011]

[Chemical 1]

[0012]

[Chemical 2]

[0013]

[Chemical 3]

Examples of the polycarbosilane-based silicon-containing cyclic compound whose ring skeleton is composed of Si and C include compounds represented by the following chemical formulas 4 to 11. In the structural formula, black circles represent silicon atoms.

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

[0019]

[Chemical 8]

[0020]

[Chemical 9]

[0021]

[Chemical 10]

[0022]

[Chemical 11]

The polysilazane-based silicon-containing cyclic compound whose ring skeleton is composed of Si and N is shown below.
Compounds of

[0024]

[Chemical 12]

Examples of the polysilane-based silicon-containing cyclic compound having a ring skeleton made of Si include compounds represented by the following Chemical Formulas 13 to 16.

[0026]

[Chemical 13]

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

In addition, compounds represented by the following chemical formulas 17 to 18 can be exemplified.

[0031]

[Chemical 17]

[0032]

[Chemical 18]

The catalyst used in the ring-opening polymerization of the silicon-containing cyclic compound which is the component (B) of the present invention must be selected appropriately depending on the structure of the component (B). Can use the following:
H ₂ PtCl ₆ 6H ₂ O, PtCl ₂ , IrC
^{_{l 6 2 -, RuCl 4 2}} -, AuCl 4 -, PdC
l ₂ , RuI ₃ , Pt / C, (olefin PtCl ₂ ).
₂ , (Et ₂ S) ₂ PtCl ₂ , (Bu ₃ P) ₂ Pt ₂
Cl ₄ , (ph ₃ P) ₂ Pt (CH ₃ ) ₂ , PdB
r ₂ , AuCl ₃ , CuCl ₂ , CuCl, Na, K,
tBuOK, NaOMe, nBuLi, secBuL
i, tBuLi, RC≡CLi (R is a monovalent hydrocarbon group), CH ₃ MgBr, CH ₃ MgCl, EtMgB
r, nBuMgBr, WCl ₆ , IrCl ₃ , MoCl
₅ , ReCl ₅ , RuCl ₃ , TiCl ₄ , [IrCl
(COD)] ₂ (COD = 1,4-cyclooctadecadiene), OsCl ₃ , K ₂ RuCl _{5 and the} like can be exemplified, but the invention is not limited thereto. Et is an ethyl group, Bu is a butyl group, ph is a phenyl group, Pr is a propyl group, nBu is a normal butyl group, secBu is a secondary butyl group, and tBu is a tertiary butyl group.

The ratio of the weight of the component (A) and the weight (b) of the component (B) used in the present invention is a very important index for controlling the properties of the obtained silicon-based hybrid material. Since alkoxysilanes silicon content varies depending on the type, SiO ₂ was calculated assuming the alkoxysilane is engaged completely hydrolyzed and condensed (Si 1 each
It was assumed that the atoms were formally converted to SiO ₂ 1 units. ) It is convenient to use the weight ratio of the amounts (a) and (b). The weight ratio (a) / (b) can be preferably used in the range of 0.1 to 100. 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 reaction system comprising the components (A) and (B) of the present invention, the following reactions (1) to (4) proceed and finally the silicon-based hybrid material of the present invention is obtained. It is thought to be done. SiOR + H ₂ O → SiOH + ROH (1) SiOH + ROSi → SiOSi + ROH (2) SiOH + HOSi → SiOSi + H ₂ O (3) Silicon-containing cyclic compound → ring-opening polymerization reaction product (4) Of these reactions, increase in molecular weight of component (A) -Formulas (2)-(3) used in the crosslinking reaction, and then (B)
It is important to obtain the uniform and high-performance silicon-based hybrid material of the present invention by simultaneously carrying out the reaction of the formula (4) in which the molecular weight is increased by the ring-opening polymerization of the components.

If the reaction formulas of formulas (1) to (3) are significantly faster than the reaction formula (4), the resulting material will be a swollen gel.
When the reaction rates are opposite, separation and precipitation of the polymer produced by ring-opening polymerization often occur. The reactions of the formulas (1) to (3) include the concentration of alkoxysilane, the structure of the alkoxy moiety, the number of alkoxy groups on Si, the condensation reaction catalyst species / amount, the amount of water, the reaction temperature, the solvent species / amount, etc. It can be controlled by changing it. The reaction of the formula (4) can be controlled by changing the catalyst species / amount, solvent species / amount, reaction temperature and the like. Therefore, the reaction conditions can be appropriately selected in order to obtain the silicon-based hybrid material having the desired performance.

The silicon-based hybrid material of the present invention can be obtained by carrying out the reactions of the formulas (1) to (4) preferably simultaneously, but in order to obtain desired properties, (A) and ( It is desirable that the basic components of B) be compatible with each other. Further, in general, components such as a condensation catalyst required for the condensation reaction of the alkoxysilanes as the component (A), water and a catalyst required for the ring-opening polymerization reaction of the silicon-containing cyclic compound as the component (B) are contained in the reaction system. It is desirable that they are uniformly compatible with each other. 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 compatibility of the above components and further control the reaction temperature, a solvent can be used if necessary. The solvent is not particularly limited, but alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol; TH
Ether solvents such as F, 1,4-dioxane, 1,3-dioxane, diethyl ether, dibutyl ether;
Acetone, methyl ethyl ketone, and other ketone solvents; chloroform, methylene chloride, dichloroethane, chlorobenzene, and other halogen solvents; toluene, xylene, hexane, and other hydrocarbon solvents; acetonitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and other polar solvents Aprotic solvent; etc. can be specifically used. Of these, methanol,
Ethanol, isopropanol, n-butanol, TH
A solvent selected from F, 1,4-dioxane, and acetone is preferably one or more.

As a post-treatment step for obtaining the silicon-based hybrid material of the present invention, the reaction mixture or the mixture before the reaction may be formed into a film, a fiber, a plate, or a rod in a temperature range from room temperature to about 100 ° C. It also includes a step of shaping into a complicated shape 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 the components (A) and (B) as the main components. In addition to the basic components, various silicon-based hybrid materials can be prepared 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.

Specific examples of the additives / reinforcing agents that can be used in the present invention include Al (Oi-Pr) ₃ and Ti.
(Oi-Pr) ₄ , Ti (On-Bu) ₄ , B (OE
_{t) 3, Zr (Oi-} Pr) 4, Ti (OSiMe 3)
_{4, (Me 3 SiO) 2} Ti (Oi-Pr) 2, B (O
H) ₃ , (where i-Pr is an isopropyl group, n-B
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 can be used for various purposes. Concrete examples include aerospace structural materials used for artificial hygiene, space shuttles, space colonies, aircraft and rocket fuselage, engine peripheral parts, automobile skins, 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, railways, ships, materials for agricultural equipment such as tractors, housing・ Buildings, bridges, pedestrian bridges, ladders ・
Structural materials used for skyscrapers, deep underground structures, undersea structures, boats, yachts, skis, snowmobiles, glider aircraft, tennis rackets, golf shafts, etc.
Sports equipment such as fishing rods and tent props, microwave ovens,
Home appliances such as refrigerators, washing machines and personal computers, medical materials such as artificial bones, artificial teeth and artificial roots, cosmetic materials, sealing materials, adhesives, adhesives, adhesives,
Paint, modifier, plasticizer, masking material, mold release material, defoaming material, fiber treatment material, electrical insulation material, semiconductor encapsulation material, ceramic fiber and precursor for molded body, 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 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, but are not limited to, functional glass for chemical use such as enzyme immobilization and solidification of radioactive waste.

[0043]

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 1-L 4-necked flask, stirring blade with motor, 200-
A reactor equipped with a dropping funnel equipped with a ml pressure equalizing tube, a three-way cock, a cooling tube and a glass stopper was prepared. The inside of the system of this reactor was dried under reduced pressure. 200 ml of dry THF was charged into the flask. 143 g of chloromethyldimethylchlorosilane (LS-230, manufactured by Shin-Etsu Chemical Co., Ltd.) on the dropping funnel.
(1.0 mol) was charged. About 10 ml of the chlorosilane and magnesium (shaving magnesium for Grignard reaction. Purchased from Wako Pure Chemical Industries, Ltd.) in a flask, about 1.0 of the total amount of 26.7 g (1.1 mol).
g was added to the flask. Then 2 drops of methyl iodide were pipetted in at room temperature to start the reaction. About 1-2
The reaction started after a few minutes and the temperature of the solution temporarily rose to about 60 ° C. When the heat generation became mild, the remaining chlorosilane was dropped from the dropping funnel over about 10 minutes. Further, 450 ml of dry THF was added. The remaining magnesium was added in about 2-3 g portions every about 15 minutes. With the addition of magnesium, a large amount of salt was formed and stirring became difficult, so 300 ml of dry THF was added. The reaction temperature was maintained at about 30-50 ° C. After the total amount of magnesium was added, the mixture was reacted at about 60 ° C. for 3 hours. The resulting reaction mixture was filtered to remove the salt formed and excess magnesium. The filtrate was washed with water, and the organic layer was dried over anhydrous calcium chloride. Calcium chloride was removed by filtering the organic layer, the filtrate was distilled to remove the solvent, and 1,1,3,3-tetramethyl-1,3-disilacyclobutane (bp 77-80) was then distilled under reduced pressure. ℃ / 50Torr) About 2
3 g (0.16 mol, yield 32%) was obtained.

Example 1 A 500-ml 5-necked flask was equipped with a motorized stirring rod, 2
Three dropping funnels with a 5-ml pressure equalizing tube and a cooling tube with a three-way cock were attached, and the system was replaced with nitrogen. Ethyl silicate 40 (produced by Colcoat Co., Ltd., a mixture of condensates of tetraethoxysilane as shown in the following chemical formula 19) in a flask, and a condensate having a complex structure such as branched or cyclic other than chain It is considered. From technical data.)

[0045]

[Chemical 19]

200 g, (1) 1, synthesized in Production Example 1
1,3,3-tetramethyl-1,3-disilacyclobutane 8.0g solution dissolving (55.6 mmol) of 1,4-dioxane _{10ml, (2) H 2 PtCl} 8 · 6
H ₂ O isopropanol 10 wt% solution 28.81 μL
A solution of 10 ml of isopropanol in (3)
A solution prepared by dissolving 10 ml of 0.5 N HCl aqueous solution in 10 ml of 1,4-dioxane was charged into each of three dropping funnels. The flask was placed in an oil bath at 70 ° C, and the contents were simultaneously added dropwise from three dropping funnels 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 to a depth of 8 mm in a 100 × 25 × 15 mm mold which was previously covered with a Teflon sheet. This was dried at room temperature for 1 week and at 50 ° C. for 3 days to obtain a plate-shaped silicon-based hybrid material having a thickness of about 2.5 mm.
This material was as strong as ordinary glass and did not undergo brittle fracture.

Comparative Example 1 A glass-like molded product was obtained in the same manner as in Example 1 except that the dropping solutions (1) and (2) used in Example 1 were not used. This molded body had a strength similar to that of glass, but was brittle.

[0049]

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 hydrolysis / condensation reaction of alkoxysilanes (component (A)) and a silicon-containing cyclic compound (component (B)).
And a ring-opening polymerization reaction of (1).