Layered material

 

(57) Abstract:

The layered material is substrate-based optical fibers, mineral fibers or wood-based materials and are located in functional contact with the nanocomposite, which is obtained by surface modification of (a) colloidal inorganic particles, (b) one or more silanes of General formula I: Rx-Si-Ai4-xwhere the remains of a is identical or different and represent hydroxyl or hydrolytic otsepleniya group, except methoxy, residues R are the same or different and are hydrolytically not otsepleniya group and x is 0, 1, 2 or 3, with at least 50% of the silanes have the value of x 1; in the conditions of the Sol-gel process below stoichiometric amount of water, in terms of available hydrolyzable group, with the formation of nanocomposite Zola, if necessary, with further hydrolysis and condensation nanocomposite Zola before contacting with the substrate and subsequent curing. 15 C. p. F.-ly.

The invention relates to laminated materials, which differ in substrate-based optical fibers, mineral fibers or wood-based materials and m is (a) colloidal inorganic particles

b) one or more silanes of General formula (I)

Rx-Si-A4-x(I)

where And remains the same or different and represent hydroxyl or hydrolytic otsepleniya group, except metoxygroup, the residues R are the same or different and are hydrolytically not otsepleniya group and x is 0, 1, 2 or 3, with at least 50% of the silanes have the value of x 1;

in the conditions of the Sol-gel process below stoichiometric amount of water, in terms of available hydrolyzable group, with the formation of nanocomposite Zola, if necessary with further hydrolysis and condensation nanocomposite Zola before contacting with the substrate and subsequent curing.

The substrate can have a variety of physical forms, and the nanocomposite may also exist in various forms of distribution. For example, the nanocomposite in the form of a continuous coating or layer may completely or partially cover the substrate or in the form of a laminate to be between multiple substrates. Specific examples of the layered materials of this kind are having a heat-resistant impregnation of the fiber, yarn, yarn and semi-finished products, to form intermittent or point designated contacts between multiple substrates and bind, for example, in the matrix type substrate in the form of particles, flakes or fibers. Specific examples of the layered materials of the above type are insulating materials based on glass fibers or mineral fibers and wood-based materials, such as fibreboard, chipboard, joiner boards, plywood and lightweight building boards made of wood wool. For special purposes it is possible to apply the admixture of glass fibers and wood-based materials, such as chipboard with fire-resistant properties.

Examples of suitable substrates are glass fiber, natural or synthetic mineral fibres such as asbestos, mineral fibers, slavonica, and fibers of ceramic materials, including fibers made from oxide ceramics, wood materials such as cellulose, wood wool, wood flour, wood chips, paper, cardboard, wood boards, wood bars and wood laminates.

Under the substrates in the form of fibers involve as individual fibers, including hollow fibers and filamentary single crystals ("whiskers"), and the corresponding coils of the fibers, cords, ropes, yarn, and yarn, as well as semi-finished products, as cloth is s. Specific examples include glass wool, glass mats and mineral wool, such as slag wool, steel slag wool, mineral fiber and basalt fiber.

Used according to the invention, a nanocomposite is produced by surface modification of colloidal inorganic particles (a) with one or more silanes (b) if necessary in the presence of other additives (C) in the conditions of the Sol-gel process.

The details of the Sol-gel process is described: C. J. Brinker, G. C. Scherer: "Sol-Gel Science - The Physics and Chemistry of Sol-Gel Processing, Academic Press, Boston, San Diego, new York, Sydney 1990) and in patents Germany 1941191, 3719339, 4020316 and 4217432.

There are also specific examples used according to the invention silanes (b), as well as their hydrolytically tseplyaesh residues and hydrolytically not tseplyaesh residues R.

Preferred examples tseplyaesh hydrolytically groups And represent hydrogen, halogen (F, C1, Br and I, particularly C1 and Br), alkoxy (especially WITH2-4-alkoxy, such as, for example, ethoxy, n-propoxy, isopropoxy, butoxy), aryloxy (especially WITH6-10-aryloxy, for example, phenoxy), alkalilike (e.g., benzyloxy), acyloxy (especially C1-4-acyloxy, as, e.g. oppy (for example, mono - or disciline, -aryl and-aralkylamines with the above alkyl, aryl and Uralkalij residues), amide group (for example, benzamido) and aldoxime or ketoxime group. Two or three of balance And may together also form complexarray grouping with the Si atom, as in the case of, for example, Si-polyol as one of the complexes that are formed glycol, glycerin or pyrocatechin. Especially preferred residues And represent2-4-alkoxygroup, especially ethoxypropan. Metoxygroup less suitable for the purposes of the invention because they have too high reactivity (short processing time nanocomposite Zola) and can lead to nanocomposites and accordingly layered materials with insufficient flexibility.

Named hydrolyzable group And may, if necessary, to include one or more conventional substituents, such as halogen atoms or alkoxygroup.

Hydrolytically not otsepleniya residues R is chosen preferably from alkyl (especially C1-4-alkyl, such as methyl, ethyl, propyl and butyl), alkenyl (especially C2-4-alkenyl, as, for example, vinyl, 1-propenyl, 2-p is SUB>-aryl, such as phenyl and naphthyl) and the corresponding alkalinic and arylalkyl groups. These groups can also include, if necessary, one or more customary substituents, for example halogen, alkoxy-, hydroxy-, amino - or epoxy group.

The above-mentioned alkyl, alkeline and alkyline groups include the corresponding cyclic residues, such as, for example, cyclopropyl, cyclopentyl and cyclohexyl.

Especially preferred residues R are replaced if necessary WITH1-4-alkyl groups, especially methyl and ethyl, and replaced if necessary WITH6-10-aryl groups, especially phenyl.

Further, preferably, in the above formula (1) x had a value of 0, 1 or 2 and particularly preferably 0 or 1. Further preferably, at least 60, and particularly preferably at least 70% of the amount of silane of formula (1) have a value of x = 1. In certain cases it may be more preferably, if more than 80 or even more than 90% (e.g., 100%) silanes of the formula (1) have a value of x = 1.

Laminates according to the invention can be obtained, for example, from pure methyltriethoxysilane (MTAS) or General formula (1) are compounds of the following formulas: tetraethoxysilane Si(OC2H5)4, Tetra-n - or-isopropylidene Si(0-H - or ISO-C3H7)4tetraethoxysilane Si(OC4H9)4tetrachloride SiCl4tetraaceticacid Si(AOSN3)4methyltrichlorosilane CH3-Si13methyltriethoxysilane CH3-Si(OC2H5)3ethyltrichlorosilane2H5-Si13ethyltriethoxysilane2H5-Si(OC2H5)3propyltriethoxysilane3H7-Si(OS2H5)3phenyltriethoxysilane6H5-Si-(OS2H5)3triethoxysilylpropyl (C2H5O)3-Si-C3H6-C1, clear (CH3)2Si12dimethyldiethoxysilane (CH3)2Si (OC2H5)2dimethyldioxirane (CH3)2Si(OH)2, diphenyldichlorosilane (C6H5)2SiCl2diphenyldichlorosilane (C6H5)2Si(OS2H5)2triisopropylsilane (ISO-C3H7)3Si, vinyltriethoxysilane CH2= CH-Si(AOSN3)3, vinyltrichlorosilane CH2=SN-Si13vinyltriethoxysilane CH2=CH-Si(OC2H5)3silicochloroform Si13,
>= CH-CH2-Si(OC2H5)3allyltriethoxysilane CH2= CH-CH2-Si(AOSN3)3methacryloyloxyethyl CH2= C(CH3)COO-C3H7-Si-(OS2H5)3cyclohexenyltrichlorosilane N-C6H13-CH2-CH2-Si(OS2H5)3n-decyltriethoxysilane C8H17-CH2-CH2-Si(OS2H5)3glycidylmethacrylate

These silanes can be obtained with known methods; cf. In Noll, "Chemistry and technology of silicones", publisher Chemicals GmbH, vine-Khaimah/Bergstrasse (1968).

Referring to the above-mentioned components (a), (b) and (C), the amount of component (b) is usually from 20 to 95, preferably from 40 to 90 and particularly preferably from 70 to 90 weight. % expressed as polysiloxane formula: Rx SiO(2-0,5 x), which is formed by condensation.

Used according to the invention, the silanes of General formula (1) can be fully or partially applied in the form of forcompensation, i.e., compounds formed by partial hydrolysis of silanes of formula (1), or individually, or in mixtures with other hydrolyzable compounds. Similar, predominantly soluble in the reaction medium oligny) with the degree of condensation, for example, from about 2 to 100, particularly preferably from 2 to 6.

Used for hydrolysis and condensation of silanes of formula (1) amount of water is preferably from 0.1 to 0.9, particularly preferably from 0.25 to 0.75 mol of water per 1 mol of the available hydrolyzable groups. Often get particularly good results with 0,35 - 0,45 mole of water per 1 mol of the available hydrolyzable groups.

Specific examples of the colloidal inorganic particles (a) are sols and nanoscale dispersible powders (particle size is preferably up to 300, especially up to 100 nm and particularly preferably up to 50 nm) SiO2, TiO2, ZrO2, Al2O3V2ABOUT3CeO2, SnO2, ZnO, iron oxide or carbon (carbon black and graphite), especially SiO2.

The amount of component (a) in terms of components (a), (b) and (C) is usually from 5 to 60, preferably from 10 to 40 and particularly preferably from 10 to 20 wt.%.

To obtain nanocomposites nanocomposite as a possible component (C) can use other additives in an amount up to 20 wt.%, preferably up to 10 and particularly preferably up to 5 wt.%, for example, the curing catalysts such as metal salts and the alkoxide is, originalzitat, starch, polyethylene glycol and gum Arabic, pigments, dyes, flame retardant additives, compounds stekloobrazuyuschego elements (for example, boric acid, ester of boric acid, sodium methylate, potassium acetate, sec-butyl aluminum, and so on), corrosion funds and auxiliary funds to cover. The use of the binder according to the invention is less preferred.

The hydrolysis and condensation is carried out in the conditions of the Sol-gel process in the presence of acidic condensation catalysts (e.g., hydrochloric acid) at a pH value of preferably from 1 to 2 until it forms a viscous Sol.

Preferably in addition to the solvent, which is formed during the hydrolysis of alkoxygroup not to use an additional solvent. However, if desirable, can be used, for example, alcohol solvents, such as ethanol, or other polar, proton or aprotic solvents, such as tetrahydrofuran, dioxane, dimethylformamide or butylglycol.

To ensure a favorable morphology of the particles Zola and the viscosity of the obtained nanocomposite Sol is subjected preferably targeted subsequent reactions in which the reaction cm is determined as being is a one-day curing at room temperature or hours of heating to 60-80oC. forming a nanocomposite Sol with a viscosity of preferably from 5 to 500 mPas, particularly preferably from 10 to 50 mPas. Of course, the viscosity of the Sol by the addition of solvents or removing by-products of the reaction (e.g., alcohols) can be set to suitable for special purpose units. Additional reactions may be related also preferably with a decrease in the amount of the solvent.

Mass fraction in layered nanocomposites nanocomposite material is preferably from 0.1 to 80, especially from 1 to 40 and particularly preferably from 1 to 20 wt.%.

The Association of substrate and nanocomposites nanocomposite or the respective nanocomposites nanocomposite nanocomposite Zola carried out after at least the initial hydrolysis of the components (b) and in any case before the subsequent curing. Preferably nanocomposite Sol activate shortly before contact with the substrate supply further quantities of water.

The contacting can be accomplished in any well-known specialist and rational in this case means, for example, by simple mixing of the substrate and nanocomposite Zola, immersion, spraying, coating, squeegee, race nanocomposite Sol. To improve adhesion between the substrate and the nanocomposite, in many cases, it may be preferred substrate before contacting the nanocomposite or its precursor to be subjected to the usual preliminary surface treatment such as corona discharge, degreasing, handling primers, as aminosilane, epoxysilane, dressing starch or silicones, treatment with complexing agents, surfactants, etc.

Final curing may be preceded by a stage of drying at room temperature or slightly elevated temperature (for example, approximately 50oC).

Initial curing or pre-curing can be performed at room temperature, but is preferably by heat treatment at temperatures above the 50oWith, mostly above 100oC and particularly preferably at 150oC or higher. The maximum temperature curing depends, in particular, from the melting point or heat resistance of the substrate, but is usually from 250 to 300oC. The mineral substrates is also possible higher temperature curing, for example, €.

In addition to conventional thermal curing, for example, in an oven with air circulation also used other methods of curing, for example curing infrared radiation. Before curing the resulting composite may be subjected, if necessary, also forming.

The object of the present invention is also the use of the above nanocomposites nanocomposite coatings and/or hardening the above-mentioned substrates. The term "hardening" should include all the activities that are suitable for receiving the substrate in a more enhanced or a more compact form, and includes, for example, impregnation of the substrate nanocomposite, laying substrate in a matrix of the nanocomposites nanocomposite or bonding or connection of the substrates or parts of the substrates with the nanocomposite. Under the "floor" mean especially partial or complete substrate being covered by the nanocomposite to give the substrate or portions of special properties, such as resistance to oxidation, resistance, hydrophobicity, oleophobicity, hardness, impenetrability, electrical or thermal insulation.

The following examples have more to explain the present invention. In the examples we are talking about IP is and 30 wt.% and with a particle size of from 7 to 10 nm. In the examples below use the following abbreviations:

METEOS - methyltriethoxysilane

TEOC - tetraethoxysilane

FTAAS - phenyltriethoxysilane

EXAMPLE 1

A mixture of 65 mol.% METEOS, and 15 mol.% FTAAS, and 20 mol.% TEOS (or alternatively from 80 mol. % MTAS and 20 mol. % TEOS) are intensively mixed with kieselsol and hydrochloric acid as a catalyst, to obtain by hydrolysis and condensation of silanes nanocomposite Sol. Thanks to kieselsol while imposing such a quantity of water that 1 mol of hydrolyzable groups have to 0.8 mole of water. Approximately 5 minutes after receiving the Sol fill above a silanol mixture so that the total water content in the resulting mixture is 0.4 mol of water per 1 mol of alkoxygroup. The number kieselsol in the total solids content is about 14 wt.%.

After additional phase reactions approximate 12 hours at room temperature add to the above mixture, the amount of water to the total water content in the ash was 0.5 mol of water per 1 mol of alkoxygroup. After about 5 minutes, the mixture is ready for use.

Ready to apply mixture spray through spray ring on a at 200oC. Receive the elastic insulating material with improved fire properties compared to glass wool bound with phenolic resin.

EXAMPLE 2

68,7 ml METEOS (corresponds to 80% of the total number) and 19.2 ml of TEOS (corresponds to 20% of the total number) are mixed and half of this mixture is intensively stirred 11.7 ml kieselsol (respectively, 14.3 wt.% the number kieselsol) and 0,386 ml of concentrated hydrochloric acid. After 5 minutes in the initial mixture add the second half of a silanol of the mixture, and then stirred for another 5 minutes, then formed the Sol is subjected to an additional reaction (2-hour curing at room temperature). Get stable at storage forcontent with a solids content of SiO2about 300 g/l and 0.4 mol of water per 1 mole of the hydrolyzable groups. By concentrating on a rotary evaporator to provide a solids content of 60 weight. %.

Before using glue add 3.0 ml of isopropylate titanium and about 2.5 ml of water to achieve a water content of 0.5 mol of water per 1 mole of the hydrolyzable groups. Thus obtained mixture is mixed with wood shavings, so 15% of the mass consists of SiO2. to obtain a molded product, which looks like an ordinary pressed wood particle Board, but made without organic binder. The resistance of such plate as opposed to the fire resistance of conventional pressed chipboard greatly improved.

EXAMPLE 3

1. Getting Zola

172 ml MTAS mixed with 48 ml of TEOS. With vigorous stirring, add 29 ml kieselsol and 2 ml of sulfuric acid (35%). After about 5 minutes formed a translucent Sol, which is left to react for 4 hours at room temperature. After adding with stirring the remaining 3 ml of water the mixture is approximately 5 minutes ready for use.

2. The use of Zola

2.1 100 g of wood shavings mixed with 60 ml of Zola and pressed at a pressure of 7.1 MPa in the mold with a diameter of 12 cm for 10 minutes. Then, the extruded product in a heated press (heat lower and upper plates) is pressed at a pressure of 2.6 MPa and at a temperature of 100oWith about 3 hours. Get mechanically stable molded product with a quantity of wood chips 82 wt.%.

2.2 300 g granulated mineral fibers mixed with 10 ml of the above-mentioned Zola and pressed for 5 minutes at Dawley air for 8 hours at a temperature of 80oC. Obtain mechanically stable molded product containing granular mineral fiber 1 wt.%.

1. Layered material containing the substrate and being in contact with him nanocomposite derived from inorganic particles and silane in the conditions of the Sol-gel process, followed by curing, wherein the laminate includes a substrate based on glass fibers, mineral fibers or wood-based materials and nanocomposite obtained by surface modification of (a) colloidal inorganic particles, (b) one or more forces of General formula I

RX-Si-A4-x(I)

where the remains of a is identical or different and represent hydroxyl or hydrolytic otsepleniya group, except metoxygroup;

the residues R are the same or different and are hydrolytically not otsepleniya group;

x has a value of 0,1,2 or 3, with at least 50% of the silanes have the value x1;

in the conditions of the Sol-gel process below stoichiometric amount of water, in terms of available hydrolyzable group, with the formation of nanocomposite Zola, if necessary, with further hydrolysis and condensation of nanocomposition surface carried out in the presence of acidic condensation catalyst at a pH from 1 to 2.

3. Layered material under item 1 or 2, characterized in that the nanocomposite Sol obtained through many hours to multi-day additional reaction at temperatures from room temperature up to 120oC.

4. Laminate according to one of paragraphs. 1-3, characterized in that the colloidal inorganic particles (a) is selected from the sols and nanosolar, dispersible powders SiO2, TiO2, ZrO2,A12O3V2O3SEO2, SnO2, ZnO, iron oxide or carbon.

5. Laminate according to one of paragraphs. 1-4, characterized in that the nanocomposite Sol obtained by using additives, such as curing catalysts, organic binders, pigments, dyes, flame retardants, compounds stekloobrazuyuschego elements, corrosion of funds and/or auxiliary means for coating.

6. Laminate according to one of paragraphs. 1-5, characterized in that the nanocomposite obtained using from 5 to 60, preferably from 10 to 40 and particularly preferably from 10 to 20 wt. % the components (a).

7. Laminate according to one of paragraphs. 1-6, characterized in that the nanocomposite obtained using from 20 to 95, preferably from 40 to 90 and particularly site is>8. Laminate according to one of paragraphs. 5-7, characterized in that the nanocomposite obtained using no more than 20, preferably not more than 10 and especially preferably not more than 5 wt. % other additives (C).

9. Laminate according to one of paragraphs. 1-8, characterized in that the residues in formula I represent2-4-alkoxygroup, preferably ethoxypropan.

10. Laminate according to one of paragraphs. 1-9, characterized in that R in the formula I denotes substituted, if necessary, WITH1-4is an alkyl group and/or replaced, if necessary, 6-10-aryl group, preferably methyl, ethyl and/or phenyl group.

11. Laminate according to one of paragraphs. 1-10, characterized in that x in formula I has a value of 0,1 or 2, preferably 0 or 1.

12. Laminate according to one of paragraphs. 1-11, characterized in that at least 60 and preferably at least 70% of the components (b) silanes of the formula I are set to 1, preferably x= 1.

13. Laminate according to one of paragraphs. 1-12, characterized in that the surface modification of implemented from 0.1 to 0.9, preferably from 0.25 to 0.75 mol of water per 1 mol of the available hydrolyzable groups.

15. Laminate according to one of paragraphs. 1-14, characterized in that the curing is carried out thermally, preferably at temperatures of 50 - 300oC.

16. Laminate according to one of paragraphs. 1-11, characterized in that it is made in the form of a substrate coated with the nanocomposite soaked nanocomposite fabric or molded articles containing reinforced nanocomposite substrate material.

 

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