JPH05105760A - 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 processability by impregnating a silicon-based polymer with a silicate followed by condensation reaction. CONSTITUTION:The objective hybrid material suitable e.g. as a structural material for aerospace applications such as artificial satellites or space shuttles is obtained by impregnating (A) a silicate such as sodium orthosilicate or sodium calcium metasilicate with (B) a silicon-based polymer such as polysiloxane or polycarbosilane followed by condensation reaction in the presence of a catalyst such as hydrochloric acid or dibutyltin dilaurate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention is obtained by impregnating a silicate and / or a silicic acid derived from the silicate (component (A)) into a silicon-based polymer (component (B)) to carry out a condensation reaction. The present invention relates to a silicon-based hybrid material having excellent heat resistance, combustion resistance, environment resistance, lightweight and 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 is characterized by being obtained by impregnating a silicate and / or a silicic acid derived from the same (component (A)) into a silicon-based polymer (component (B)) to cause a condensation reaction. The present invention relates to a silicon-based hybrid material and a method for manufacturing the same.

The silicates 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 particular limitation, and various types can be used. Specifically, (1) sodium orthosilicate, potassium orthosilicate, sodium orthosilicate Na ₄ SiO ₄ , potassium orthosilicate K ₄ SiO
₄ , magnesium orthosilicate Mg ₂ SiO ₄ , beryllium orthosilicate Be ₂ SiO ₄ , olivine group (F
e, Mg) ₂ SiO ₄ , garnet group Mg ₃ Al ₂ Si ₃
O ₁₂ , Ca ₃ Al ₂ Si ₃ O ₁₂ , Zircon ZrSiO
₄ , Netho (ortho) silicates, such as ortholiths, quartzite, ortholite, mullite, topaz, cruciate, sapphirine, norbergite, chondroite, fume stone, clinocline fumestone wedge, chloritoid, ( 2) Orthoclase group, green lensite group,
Lawsonite, Panberry stone and other solo silicates,
(3) Cyclosilicates such as Quinseite, tourmaline, and beryl, (4) Dectosilicates such as feldspars, semi-feldspars, zeolites, (5) inosilicates, (6) lithium metasilicate Li ₂ SiO ₃ , sodium metasilicate Na ₂ Si
O ₃ , potassium metasilicate K ₂ SiO ₃ , magnesium metasilicate MgSiO ₃ , sodium metasilicate calcium Na ₂ SiO ₃ —CaSiO ₃ , calcium metasilicate CaSiO ₃ , magnesium metasilicate calcium CaMgSi ₂ O ₅ , barium metasilicate BaSi
O ₃ , manganese metasilicate MnSiO ₃ , iron metasilicate FeSiO ₃ , cobalt metasilicate CoSiO ₃ , lead metasilicate PbSiO ₃ , CaMgSi ₂ O ₆ -MgSi
₂ O ₆ solid solution, CaMgSi ₂ O ₆ —FeSi ₂ O ₆ solid solution and other metasilicates and solid solutions thereof, and (7) phyllosilicates such as muscovite group and biotite group.

Of these, lithium metasilicate Li ₂
SiO ₂ , sodium metasilicate Na ₂ SiO ₃ , potassium metasilicate K ₂ SiO ₃ , magnesium metasilicate MgSiO ₃ , sodium metasilicate calcium Na ₂
SiO ₃ -CaSiO _3, calcium metasilicate CaS
iO ₃ , magnesium calcium metasilicate CaMgS
i ₂ O ₅ , sodium orthosilicate and potassium orthosilicate are preferably used. Further, an aqueous solution of sodium silicate (so-called water glass) is particularly preferably used.

Furthermore, silicic acids derived from the above-mentioned silicates can also be used. Examples of the catalyst used in the condensation reaction of the silicate (A) and / or the silicic acid derived from the component (A) include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and chloroplatinic acid; sodium hydroxide, calcium hydroxide and the like. Inorganic bases; tetrabutyl titanate,
Titanate esters such as tetrapropyl titanate;
Dibutyltin dilaurate, dibutyltin maleate,
Tin carboxylates such as dibutyltin diacetate, tin octylate and tin naphthenate; Reaction products of dibutyltin oxide and phthalate ester; Dibutyltin diacetylacetonate; Aluminum trisacetylacetonate, Aluminum trisethylacetoacetate, Diisopropoxyaluminum ethyl Organoaluminum compounds such as acetoacetate; chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, Triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylami Propylamine, xylylenediamine, triethylenediamine, dianidine, diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo (5,4,0) Undecen-7 (DBU)
Amine compounds such as or salts with carboxylic acids thereof; low molecular weight polyamide resins obtained from excess polyamine and polybasic acid; reaction product of excess polyamine and epoxy compound; silane coupling having amino group Examples of the 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.

The silicon-based polymer 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 molecular weight of the silicon-based polymer is not particularly limited, but in consideration of swelling with silicates and / or silicic acids derived from them (component (A)) and the performance of the resulting silicon-based hybrid material. Generally, those of about 1000 to 500,000 are preferably used.

The main chain skeleton of the silicon-based polymer used here may be linear, ladder-like, branched or cage-like. In consideration of the impregnation with the component (A) and the performance of the obtained silicon-based hybrid material, a linear or ladder-shaped one is preferably used. Examples of the silicon-based polymer used in the present invention include polysiloxanes, polycarbosilanes, polysilanes as shown below,
Examples thereof include polysilazanes, and silicon-based polymers having two or more main chain skeletons in one molecule.

Polysiloxanes, polycarbosilanes,
Polysilanes and polysilazanes are represented by the following formula (1), formula (2), formula (3), and formula (4), respectively.

[0011]

[Chemical 1]

R ¹ and R ² are H or have 1 to 20 carbon atoms.
Are monovalent organic groups or functional groups, and may be the same or different. Examples of R ¹ and R ² include the structures shown in Chemical formula 2 below.

[0013]

[Chemical 2]

R ³ is H or a monovalent organic group having 1 to 10 carbon atoms. Examples of R ³ include the structures shown in Chemical formula 3 below.

[0015]

[Chemical 3]

A is a divalent organic group having 1 to 20 carbon atoms and may contain a functional group. As A,
Each structure shown in Chemical formula 5 is exemplified.

[0017]

[Chemical 4]

[0018]

[Chemical 5]

The repeating unit of the silicon-based polymer used in the present invention may be a single unit of the formulas (1) to (4) or two or more types. The silicon-based polymer used in the present invention may be one type or a mixture of two or more types. The ratio of the silicates and / or the silicic acids (component (A)) derived therefrom and the silicon-based polymer used in the present invention is a very important index for controlling the properties of the obtained silicon-based hybrid material. is there. Since the component (A) has a different silicon content depending on its type, it is convenient to use the same weight ratio of SiO ₂ and silicon-based polymer as the number of moles of silicon atoms contained in the component (A) used. The weight ratio (weight of SiO ₂ / silicon-based 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 silicates of component (A) and / or
Alternatively, it is desirable that the silicic acid derived therefrom and the condensation catalyst generally required for the condensation reaction be impregnated in the silicon-based polymer as the component (B) to be in 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 uniformity of the above-mentioned components, and further to control the reaction temperature, a solvent can be used if necessary. Specific examples of the solvent include methanol, ethanol, isopropanol, and n-.
Alcohol solvents such as propanol and n-butanol; ether solvents such as THF, 1,4-dioxane, 1,3-dioxane, diethyl ether and dibutyl ether; ketone solvents such as acetone and methyl ethyl ketone; chloroform, methylene chloride , Dichloroethane, chlorobenzene and other halogen-based solvents; toluene,
Hydrocarbon solvents such as xylene and hexane; acetonitrile, dimethylformamide, dimethylacetamide,
Examples thereof include, but are not limited to, polar aprotic solvents such as N-methylpyrrolidone.

From the viewpoint of reacting in a homogeneous system, among various silicates, alkali metal salts are water-soluble and can be preferably used. Further, silicates other than alkali metal salts may be used because they become water-soluble alkali salts by melting with alkali. Alternatively, an aqueous solution of silicates may be neutralized and a silicic acid solution extracted with a solvent may be used to react with the solution in the presence or absence of a catalyst. As the neutralizing agent used in this case,
Sulfuric acid, hydrochloric acid, acetic acid, etc. are used, and as an extraction solvent, alcoholic solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, t-butanol, ethyl cellosolve, THF, ether solvents such as dioxane, A ketone solvent such as acetone or methyl ethyl ketone, preferably THF, isopropanol, t-butanol or acetone can be used, but the solvent is not limited thereto.

In general, since the component (B) used in the present invention is hydrophobic, when it is reacted with an aqueous solution of silicates, it becomes inhomogeneous and partially gels to give only a non-homogeneous material. There are many. Therefore, from the viewpoint of maintaining the homogeneity of the reaction, it is preferable to carry out the reaction using a solution of silicic acid obtained by neutralizing and extracting the silicate. In the condensation reaction of the silicates and / or the silicic acids derived therefrom of the present invention, the condensation reaction is not completed even after the reaction is completed, and a silanolate group (—SiOM, M represents a metal) and / or
Alternatively, silanol groups (hereinafter referred to as residual silicon groups) often remain in the reaction system. The residual silicon group is further condensed when the volatile components are removed in a later step described later, but in many cases the residual silicon group is not completely consumed. However, the objects of the present invention can be generally achieved.

The presence of the residual silicon group in the final material may not be desirable depending on the application. In this case, various chlorosilanes, alkoxysilanes, silanols, etc. are used to remove the residual silicon group in the reaction system. Can be trapped. Examples of chlorosilanes include Me ₃ SiCl, PhMe ₂ SiCl, Ph ₂ Me.
SiCl, Me ₂ SiCl ₂ , PhMeSiCl ₂ , P
h ₂ SiCl ₂ , MeSiCl ₃ , PhSiCl ₃ , C
1Me ₂ SiC ₆ H ₄ SiMe ₂ Cl, ClMe ₂ Si
OSiMe ₂ Cl, ClMe ₂ SiCH ₂ SiMe ₂ C
l, ClMe ₂ SiCH ₂ CH ₂ SiMe ₂ Cl, Cl
_{Me 2 SiSiMe 2 Cl, Cl 2} MeSiSiMe 2
Cl, C1 ₂ MeSiSiMeCl _2, both ends SiMe
₂ Cl polydimethylsiloxane, etc.

To exemplify the alkoxysilanes, M
e ₃ SiOMe, PhMe ₂ SiOMe, Ph ₂ MeS
iOMe, Me ₂ Si (OMe) ₂ , PhMeSi (O
Me) ₂ , Ph ₂ Si (OMe) ₂ , MeSi (OM
e) ₃ , PhSi (OMe) ₃ , MeOMe ₂ SiC ₆ H
₄ SiMe ₂ OMe, MeOMe ₂ SiOSiMe ₂ O
Me, MeOMe ₂ SiCH ₂ SiMe ₂ OMe, Me
OMe ₂ SiCH ₂ CH ₂ SiMe ₂ OMe, MeOM
e ₂ SiSiMe ₂ OMe, (MeO) ₂ MeSiSi
Me ₂ OMe, (MeO) ₂ MeSiSiMe (OM
e) ₂ , polydimethylsiloxane having SiMe ₂ OMe at both ends, and the like. If silanols are exemplified, Me ₃ Si
OH, PhMe ₂ SiOH, Ph ₂ MeSiOH, HO
Me ₂ SiC ₆ H ₄ SiMe ₂ OH, HOMe ₂ SiO
SiMe ₂ OH, HOMe ₂ SiCH ₂ SiMe ₂ O
H, HOMe ₂ SiCH ₂ CH ₂ SiMe ₂ OH, HO
Examples thereof include Me ₂ SiSiMe ₂ OH and polydimethylsiloxane having SiMe ₂ OH at both ends, but are not limited thereto.

Since HCl is generated when these trapping agents, especially chlorosilanes, are used, triethylamine or pyridine may be used for neutralization. As a post-treatment step for obtaining the silicon-based hybrid material of the present invention, a silicon-based polymer (component (B)) is impregnated with silicates and / or silicic acids derived therefrom (component (A)) and condensed. Reaction mixture from 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 silicates and / or silicic acids derived therefrom and a silicon-based polymer as main components.
In addition to the basic components, various additives / reinforcing agents can be used for the purpose of adjusting the properties of the obtained silicon-based hybrid material. 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 (Oi-Pr) ₃ , 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 thus obtained silicon-based hybrid material of the present invention has excellent heat resistance and combustion resistance, is lightweight and has high toughness, and has high mechanical strength and moldability.
It can be used for various purposes. To give a concrete example, artificial hygiene, space shuttle, space colony,
Aerospace structural materials used for aircraft and rocket fuselage / engine peripheral parts, automobile outer plates / cylinder heads / wheel caps, propeller shafts, engine peripheral 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, houses, buildings, bridges, pedestrian bridges, ladders, skyscrapers, deep underground Structural materials used for structures, undersea structures, etc., sports equipment such as boats, yachts, skis, snowmobiles, glider aircraft, tennis rackets, golf shafts, fishing rods, tent props, microwave ovens, refrigerators, washing machines, personal computers. Home appliances such as artificial bones and teeth
Medical materials such as artificial tooth roots, cosmetic materials, sealing materials, adhesives, adhesives, adhesives, paints, modifiers, plasticizers, masking materials, mold release materials, defoaming materials, fiber treatment materials, electricity Insulating materials, semiconductor encapsulation materials, ceramic fibers and precursors for molded bodies, molding materials such as RIM / LIM / injection / extrusion / blowing / compression, shape memory materials, optical fibers, laser disks, optical memory films, photochromic glass,
Optical-related functional glass such as optical switches, refractive index distribution glass, heat-shielding glass, reflectors, anti-reflection glass, optical disk substrates, TV imaging tube elements, solid state batteries, delay line glass, electromagnetic-related functionality such as displays These include glass, heat-resistant materials, photomask substrates, heat-related functional glass such as adhesion and adhesion, and chemical-related functional glass such as high-temperature separation and purification, enzyme fixation, and solidification of radioactive waste. It is not limited.

[0030]

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 1 500 L of 0.80 mol / L sodium silicate aqueous solution in 0.64 mol / L sulfuric acid 1.1 L (0.74 mol)
l (SiO ₂ 0.40 mol, Nippon Kagaku Kogyo JIS3
The original product was used as it was. ) Was added dropwise with stirring to neutralize. Then add tetrahydrofuran (THF) to the solution.
After adding 800 ml and stirring at room temperature for 2 hours, the mixture was transferred to a separating funnel, 400 g of sodium chloride was added, and the mixture was shaken. The upper layer was separated, anhydrous sodium sulfate was added, and the mixture was left overnight and dehydrated and dried. This was filtered to obtain 600 ml of silicic acid-THF solution. This SiO ₂ concentration is 0.086 g
/ Ml.

Production Example 2 8.4 g (0.1 mol) of 1,5-hexadiene and a 10 wt% isopropanol solution of chloroplatinic acid catalyst 10.4
In a solution prepared by dissolving μL (2 × 10 ⁻³ mmol, 1 × 10 ⁻⁵ mol per 1 mol of olefin) in 30 mL of dry chloroform, 19.4 g (0.1 mo) of the compound of the following chemical formula 6 was used.
A solution prepared by dissolving l) in 10 mL of dry chloroform was slowly added dropwise at room temperature under a nitrogen atmosphere. The dropping rate was adjusted so that a mild exothermic reaction was maintained during the dropping. After completion of dropping, the reaction solution was stirred at room temperature for 1 hour. The platinum catalyst used was removed by passing the reaction solution through a silica gel column. When the volatile components were evaporated, a crude Si-terminated polymer was obtained as a platinum solid. The crude polymer was purified by reprecipitation from methylene chloride / methanol and dried under reduced pressure to obtain about 19.5 g (about 70% yield) of Si group-terminated polycarbosilane polymer having the structural formula of the following Chemical formula 7. G
The number average molecular weight measured by PC was 4,500, and the weight average molecular weight was 10,000.

[0032]

[Chemical 6]

[0033]

[Chemical 7]

Example 1 A 500-ml 3-necked flask was equipped with a motorized stirring rod, and 2
A 5-ml dropping funnel with a pressure equalizing tube and a Dean stack type cooling tube were attached, and the system was replaced with nitrogen. 600 ml of the silicic acid-THF solution obtained in Production Example 1 and 50 g of dimethylsiloxane-silphenylene copolymer (PS095, manufactured by Chisso Corporation) were charged into the flask. Next, 20 mL of 0.3N alcoholic HCl solution was charged into the dropping funnel. The flask was placed in an oil bath at 60 ° C., and the catalyst solution was dropped 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 80 ° C. for 3 hours while distilling off the solvent.

The resulting 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 4 mm. This material was as strong as ordinary glass and did not undergo brittle fracture.

Example 2 A colorless transparent glassy hybrid material was obtained in the same manner as in Example 1 except that 50 g of polycarbosilane produced in Production Example 2 was used. This material was as strong as 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 silicon-based polymer was not used. This molded body had a strength similar to that of glass, but was brittle.

[0037]

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 silicate and / or a silicic acid derived therefrom (component (A)) is a silicon-based polymer ((B)).
A silicon-based hybrid material obtained by impregnating a component) and conducting a condensation reaction.