DE2520079A1 - INORGANIC-ORGANIC PLASTICS AND A PROCESS FOR THEIR MANUFACTURING - Google Patents

Description

Bayer Aktiengesellschaft Central area

9 ^ O Π Π 7 Q Patents, trademarks

L Ό L UU / a _and licenses

509 Leverkusen, Bayerwerk GM / ßn / AM

May 5, 1975

Inorganic-organic plastics and a process for their production

It is already known that insulating materials can be obtained using mineral grains and synthetic resins. Also processes for the production of synthetic concrete from porous mineral materials and foamable mixtures are state of the art (German Auslegeschrift 1 239 229).

In these cases, the mineral material is always cemented or glued through the plastic. The so produced Plastic concrete materials, however, have the disadvantage of inhomogeneity, which can be mechanically stressed to different degrees Areas. Furthermore, considerable amounts of expensive, organic plastic are often required, whereby the fire behavior is mostly negatively influenced.

The leaning of commonly used for building purposes Concrete materials with organic, porous plastics is just as well known as the procedure, concrete mixes propellants to add or to generate gases in situ in order to obtain porous materials with a reduced bulk density.

Disadvantages of these largely inorganic materials are the relatively high brittleness compared to organic

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Foam form poor thermal insulation as well as the relative long setting times.

It is also known to combine components made of porous organic plastics with solid, fire-resistant, mostly inorganic or to produce metallic cover layers.

Due to their organic nature, these materials have the disadvantage of being used in construction without fire-retardant top layers not to be useful.

It is also known to use cement masses made from water cement, a silica filler and an organic compound to produce a plurality of isocyanate groups (German Offenlegungsschrift 1 924 468). Main disadvantages of this porous Cement masses are the still quite long setting time of 5-6 hours and the not very good thermal insulation. A predominant one These materials are used in screed coverings.

It has also been proposed to produce foams from isocyanates and alkali silicates (German Offenlegungsschrift 1 770 384). According to this procedure, foams, which have the disadvantages, are generally strong to be water-containing and to have too low mechanical strength in relation to their bulk density.

Heat-resistant foams can be made from foamable or already cellular thermoplastics in the presence from aqueous alkali silicate solutions (German Auslegeschrift 1 494 955). Disadvantages of this method are the heat required to cause the thermoplastics to foam, the problem of curing the alkali silicate solutions and the water content of the resulting composite material.

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It is also known (German Offenlegungsschrift 2 227 1 ^ 7), inorganic-organic plastics aqueous silicate solutions and prepolymers containing ionic groups, e.g. containing ionic groups Polyisocyanates to produce. The silicates present in aqueous solution must have one Go through the hardening process. This hardening stage is avoided in the present process.

The invention is based on the object of avoiding the disadvantages of the known materials described above and also to produce inorganic-organic plastics, in particular foams, which the advantages of fast setting times, high compressive strength in relation to the bulk density, good heat and Have sound insulation as well as good flame retardancy and excellent fire resistance duration.

This object is achieved with the inorganic-organic plastics made available according to the invention.

The present invention relates to a novel inorganic-organic plastic, in particular foam, obtainable by reacting a mixture of

2-95 percent by weight, based on the total mixture,

aqueous silica sol, preferably with a content of 20 - 60 percent by weight silica,

5-98 percent by weight, based on the total mixture,

organic polyisocyanate, with the exception of non-ionically hydrophilic polyisocyanate prepolymers,

0-93 percent by weight, based on the total mixture,

water-binding aggregates.

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The reaction mixture can optionally also contain blowing agents, catalysts, emulsifiers and / or stabilizers as well as other auxiliary materials such as flame retardant substances, contain organic and inorganic fillers.

An inorganic-organic plastic, in particular foam, obtainable by reaction is preferred of a mixture

20 - 80 percent by weight, based on the total mixture,

Silica sol, preferably with a content of 20-60 percent by weight Silica,

10 - 80 percent by weight, based on the total mixture,

organic polyisocyanate, with the exception of non-ionically hydrophilic Polyisocyanate prepolymers,

10 - 70 percent by weight, based on the total mixture,

water-binding aggregates.

The present invention also relates to a process for producing an inorganic-organic Plastic, especially foam, through implementation an organic polyisocyanate with aqueous silica oil and water-binding end η additives, as well optionally additives, which consists of a reaction mixture consisting of 2-95 percent by weight, based on the total mixture,

aqueous silica sol, preferably with a content of 20 - 60 percent by weight silica, 5-98 percent by weight, based on the total mixture,

organic polyisocyanate, with the exception of non-ionically hydrophilic Polyisocyanate prepolymers,

0-93 percent by weight, based on the total mixture,

water-binding aggregates,

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In the production of foamed materials it is preferred according to the invention that inorganic or organic Propellants of the type known per se can also be used.

It is also advantageous to use activators which accelerate the isocyanate reaction, as well as foam stabilizers and / or emulsifying aids to be used.

Organic, fire-retardant additives and polymeric substances are also often used according to the invention.

It has been found that the use of inert inorganic and / or organic, particulate and / or fibrous materials may be useful.

According to the invention, compounds with isocyanate-reactive hydrogen atoms with a molecular weight are advantageous 62-10 000 also used.

Silica sol refers to aqueous, colloidal silica solutions

to understand the bluish opalescent depending on the type

to have a milky, cloudy appearance. They contain uncrosslinked, spherical particles made of highly pure amorphous silica. The silica particles hydroxylated on the surface

generally have no internal porosity. The size

of the particles is in the sub-microscopic, colloidal range

and can be 7 - mn 200, but it is preferably 10 -. 50 nm in individual cases may also go down to 2 nm, the diameter of the particles, but are also agglomerates having a particle diameter> 200 μ possible.

The silicic acid content is generally between

20 and 60 percent by weight, preferably between 25 and 40.

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Commercially available silica sols can contain a trace of sodium or other alkali metal ions or an acid to stabilize the colloidal system. The pH value is usually 3 to 12. Colloid silicas are produced either by peptizing a silicic acid hydrogel or by gradually destabilizing alkali silicates. For further literature see:

Kirk-Othmer; Encyclopedia of Chemical Technology, Volume 18 (1969), pp. 61-72. R.K. Her; The Colloid Chemistry of Silica and Silicates, Cornell University Press, New York, 1955. J.G. Vail; Soluble Silicates, Vol. I and II, Reinhold, New York, 1952.

In addition to the silica sols mentioned, you can, too Aqueous solutions of alkali silicates can also be used, which generally have a solids content of 20-60 percent by weight exhibit. The aqueous solutions of alkali silicates usually referred to as "water glass" are used known solutions of sodium and / or potassium silicate in water in question, as for example in the German Offenlegungsschrift 2 227 147.

Organic polyisocyanates to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those used, for example. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1, 3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatoniethyl-cyclohexane (DAS 1 202 785), 2,4 - and 2,6-hexahydrotoluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or-4,4-phenylene diisocyanate, perhydro-2,4 ¹ - and / or ^^ '- diphenylmethane diisocyanate, 1 , 3- and 1,4-phenylene diisocyanate, 2,4- and 2, G-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene

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1,5-diisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanate, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in British patents 874 430 and 848 671, perchlorinated aryl polyisocyanates, as described, for example, in German Auslegeschrift 1 157, polyisocyanates containing carbodiimide groups, as described in German Patent 1,092,007, diisocyanates as described in American U.S. Patent 3,492,330, allophanate groups containing polyisocyanates, as for example in British patent specification 994 890, Belgian patent specification 761 626 and published Dutch patent application 7 102 524, containing isocyanurate groups Polyisocyanates, such as those in German patents 1,022,789, 1,222,067 and 1,027,394 as well as in German Offenlegungsschriften 1 929 034 and 2 004 048, polyisocyanates containing urethane groups, such as are e.g. in the Belgian patent 752 261 or in the American Patent 3 394 164 are described, acylated urea groups containing polyisocyanates according to German Patent 1 230 778, polyisocyanates containing biuret groups, such as those in the German Patent 1 101 394, in British patent specification 889 050 and in French patent specification 7 017 514, Polyisocyanates produced by telomerization reactions, such as those described in Belgian patent specification 723 640 are, ester group-containing polyisocyanates, such as those in British Patents 965,474 and 1,072,956, in the American patent 3,567,763 and in the German patent 1,231,688, reaction products are mentioned of the above-mentioned isocyanates with acetals according to German Patent 1,072,385.

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It is also possible to use the isocyanate group-containing distillation residues obtained in the technical production of isocyanates, optionally dissolved in one or more of the aforementioned polyisocyanates to be used. It is also possible to use any desired mixtures of the aforementioned polyisocyanates to use.

The technically easily accessible polyisocyanates, for example 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent condensation, are generally preferred Phosgenation can be produced ("crude MDI") and carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups of the polyisocyanates containing biuret groups ("modified polyisocyanates" ).

Polyisocyanates containing ion groups are particularly preferred, ionic groups of different chemical constitution come into consideration. Examples are:

-S-

—Ρ—

Sulphonic acid and / or sulphonate groups are very particularly preferred containing polyisocyanates.

Such isocyanates are produced according to an older proposal by the fact that liquid multicomponent mixtures of aromatic polyisocyanates, which have an NCO content of 10-42 wt .- ^ and a viscosity of 50-10 000 cP at 25 ⁰ C, with 0.1 up to 10 wt .- # sulfur trioxide or an equivalent amount of oleum, sulfuric acid or chlorine Le A 1 6 450 - β -

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sulfonic acid mixed and allowed to react at -20 to +200 ⁰ C and the sulfonation products obtained in this way optionally wholly or partially neutralized with a basic compound (German patent application P 22 27 111.0)

Polyisocyanate prepolymers containing nonionic hydrophilic groups are not considered according to the invention.

Starting components to be used according to the invention are also known water-binding additives of organic nature or of an inorganic nature, preference being given to inorganic materials such as water cements, synthetic anhydrite, gypsum or quick lime can be used.

Portland cement, quick-setting cement, blast furnace Portland cement, in particular, are used as water cement burnt cement, sulphate-resistant cement, wall cement, natural cement, lime cement, gypsum cement, pozzolan cement and Calcium sulfate cement is used.

According to the invention, inert filler materials can also be used can also be used.

The filler materials can be organic or inorganic, preferably fibrous or particulate or any Mixtures thereof, e.g., sand, alumina, aluminosilicates, magnesia, and other particulate refractories Materials, metal fibers, asbestos, glass fibers, rock wool or mineral fibers, aluminum silicate, calcium silicate fibers and other fibrous refractories, sawdust or wood flour, coke and other organic or carbonaceous Particles, paper pulp, cotton waste, cotton, jute, sisal, hemp, flax, rayon or synthetic fibers, e.g. polyester, Polyamide and acrylonitrile fibers and other organic fibrous materials.

According to the invention, highly volatile inorganic and / or organic substances are often used as blowing agents. as

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Methanol, ethanol, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, also butane, hexane, heptane or diethyl ether are possible. A propellant effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen, for example azo compounds such as azoisobutyronitrile. Further examples of propellants and details of the use of propellants are described in the Kunststoff-Handbuch, Volume VII, edited by Viewg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, for example on pages 109 and 109, 453 to 455 and 507 to 510 . However, the water contained in the mixture can also take over the function of the propellant. Further, fine metal powders, for example calcium, magnesium, aluminum or zinc may be used by hydrogen evolution with sufficient alkaline water glass ate propellant, at the same time exert a hardening and strengthening effect.

According to the invention, catalysts are also often used. Catalysts to be used are those of the type known per se, for example tertiary amines, 'such as triethylamine, tributylamine, N-methyl-morpholine, N-ethyl-morpholine, N-cocomorpholine, Ν, Ν, Ν ¹ , N'-tetramethyl- ethylenediamine, 1,4-diaza-bicyclo- (2,2,2) -octane, N-methyl-N'-dimethylaminoethylpiperazine, Ν, Ν-dimethylbenzylamine, bis (N, N-diethylaminoethyl) adipate, N, N -Diethylbenzylamine, pentamethyldiethylenetriamine, Ν, Ν-dimethylcyclohexylamine, Ν, Ν, Ν ¹ , N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole and in particular also hexahydrotriazine derivatives.

Hydrogen atoms active towards isocyanate groups tertiary amines are e.g. triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine,

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Ν, Ν-Dimethyl-ethanolamine, and their reaction products with Alkylene oxides such as propylene oxide and / or ethylene oxide.

Silaamines with carbon-silicon bonds are also used as catalysts, as described, for example, in German patent specification 1 229 290, in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyl-disiloxane.

Nitrogen-containing bases such as tetraalkylammonium hydroxides and alkali metal hydroxides such as Sodium hydroxide, alkali phenolates such as sodium phenolate or Alkali alcoholates such as sodium methylate are suitable. Also hexahydrotriazines can be used as catalysts.

According to the invention, organic metal compounds, in particular organic tin compounds, can also be used as catalysts be used.

The organic tin compounds are preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin salts of carboxylic acids, such as dibutyl tin diacetate ,, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate into consideration.

Further representatives of catalysts to be used according to the invention and details about the mode of operation of the catalysts are given in the Kunststoff-Handbuch, Volume VII by Viewg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 96 to 102.

The catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of isocyanate, used.

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According to the invention, surface-active additives (emulsifiers and foam stabilizers) can also be used. The sodium salts of castor oil sulfonates, sodium salts of sulfonated paraffins, for example, are used as emulsifiers of fatty acids or salts of fatty acids with amines such as oleic diethylamine or stearic diethanolamine, Also alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or fatty acids such as ricinoleic acid or polymeric fatty acids can be used as surface-active additives can also be used.

Water-soluble polyether siloxanes are particularly suitable as foam stabilizers. These connections are in general constructed in such a way that a copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical is. Such foam stabilizers are described, for example, in US Pat. No. 2,764,565.

According to the invention, reaction retarders, for example acidic substances such as hydrochloric acid or organic acid halides, furthermore cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes, and pigments or dyes and flame retardants of the type known per se, e.g. trischloroethyl phosphate or aminonium phosphate and polyphosphate can also be used , inorganic salts of phosphoric acid, chlorinated paraffins, also stabilizers against aging and weathering, plasticizers and fungistatic and bacteriostatic substances, fillers such as barium sulfate, kieselguhr, soot or whiting chalk can also be used.

Further examples of surface-active additives and foam stabilizers as well as cell regulators, reaction retarders, which may be used according to the invention,

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Stabilizers, flame retardants, plasticizers, Colorants and fillers as well as fungistatic and bacteriostatic substances as well as details on the use and the mode of action of these additives are in Kunststoff-Handbuch, Volume VI, edited by Viewg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113.

Starting components which are preferably also to be used according to the invention are also compounds having at least two isocyanate-reactive hydrogen atoms with a molecular weight of generally 62-10,000. In addition to amino groups, thiol groups or compounds containing carboxyl groups, this is preferably understood to mean polyhydroxy ! compounds, in particular compounds containing two to eight hydroxyl groups, especially those with a molecular weight 400 to 10,000, preferably 1,000 to 6,000, e.g. at least two, usually 2 to 8, preferably but polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyesteramides containing 2 to 4 hydroxyl groups, as they are known per se for the production of homogeneous and cellular polyurethanes. These connections are usually in an amount of up to 1 - 30 wt .-%, based on the mixture of polyisocyanate, silica sol ■ and water-binding aggregate, also used.

The possible polyesters containing hydroxyl groups are, for example, reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polybasic, preferably dibasic, carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally substituted, for example by halogen atoms, and / or unsaturated. Examples include: succinic acid, adipic acid, suberic acid, azelaic acid, Sebacin- Le A ^{16 4} 50 13

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acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydr © phthalic anhydride, glutaric anhydride, Maleic acid, maleic anhydride, fumaric acid, dimeric and trimeric fatty acids such as oleic acid, if appropriate as a mixture with monomeric fatty acids, dimethyl terephthalate,

Terephthalic acid bis-glycol ester. Examples of polyhydric alcohols include ethylene glycol, propylene glycol (1,2) and - (1,3) »butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1, 8), neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol,

Glycerin, trimethylolpropane, hexanetriol (1,2,6), butanetriol (1 , 2,4), trimethylolethane, pentaerythritol, quinite, mannitol and sorbitol, methylglycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, dipropylene glycol and polybutylene glycols in question. The polyesters can have a proportion of terminal carboxyl groups. Polyesters made from lactones, for example E-caprolactone or hydroxycarboxylic acids, for example ω-hydroxycaproic acid, can also be used. According to the invention, the abovementioned low molecular weight polyols can also be used. Low molecular weight amines such as alkylenediamine are also possible.

The at least two »usually two to eight, preferably two to three, which come into consideration according to the invention Polyethers containing hydroxyl groups are those of the type known per se and are, for example, by polymerizing Epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, e.g. in the presence of BF ^, or by attaching it Epoxides, optionally in a mixture or in succession, on starting components with reactive hydrogen atoms such as Alcohols or amines, e.g. water, ethylene glycol, propylene glycol- (1,3) or - (1,2), trimethylolpropane, 4,4'-dihydroxydiphenylpropane, aniline, ammonia, ethanolamine, ethylenediamine

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manufactured. Sucrose polyethers, such as those found in the German Auslegeschrifts 1 176 358 and 1 064 938 are described according to the invention. Multiple those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups present in the polyether) have primary OH groups. Polyethers modified by vinyl polymers, such as those formed by the polymerization of styrene or acrylonitrile in the presence of polyethers (American patents 3,383,351 » 3,304,273, 3,523,093, 3,110,695, German patent specification 1,152,536) are also suitable, as are OH groups comprising polybutadienes.

Polythioethers include, in particular, the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols. Depending on the co-components, the products are polythio mixed ethers, polythio ether esters, pplythio ether ester amides.

Suitable polyacetals are, for example, the compounds which can be prepared from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxydiphenyldimethylmethane, hexanediol and formaldehyde. Polyacetals suitable according to the invention can also be prepared by polymerizing cyclic acetals.

Polycarbonates containing hydroxyl groups are those of known type into consideration, for example by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol, tetraethylene glycol with diaryl carbonates, for example diphenyl carbonate or Phosgene, can be produced.

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Among the polyesteramides and polyamides wallow e.g. those made of polyvalent saturated and unsaturated carboxylic acids or their Anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures, Mostly linear londeate.

Polyhydroxy compounds already containing urethane or urea groups and optionally modified natural polyols, such as castor oil, carbohydrates, starch, are also usable. Addition products of alkylene oxides with phenol-formaldehyde resins or with urea-formaldehyde resins can also be used according to the invention.

Representatives of this erfindungegemäfi to be used Compounds are, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32 - 42 and pages 44 - 54 and Volume II, 1964, pages 5-6 and 198 - 199, as well as in the Kunststoff-Handbuch, Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71.

^ Plastics are made / The inventive production of the inorganic-organicV is usually such that the reaction components described are mixed with one another in one or more stages in a batchwise or continuous mixing device and the resulting mixture is usually outside the mixing device in molds or on suitable substrates / foam up and freeze. The reaction temperature, which is between about ⁰ ° C. and 200 ^° C., preferably between 50 ^° C. and 160 ^° C., can either be achieved by preheating one or more reaction components before the mixing process or by heating the mixing apparatus itself or the one produced Reaction mixture heats up after mixing. Combinations of these or other procedures are of course also suitable for setting the reaction temperature. In most cases, sufficient heat develops during the reaction itself so that the reaction temperature

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start of the reaction to values above 10O ⁰ C can rise.

When mixing the components, the procedure is generally that the water-binding aggregate first the polyisocyanate or the. Silica sol. or both the polyisocyanate and the silica sol are metered in. The water-binding aggregate can also be added to the mixture of isocyanate and silica sol afterwards without any disadvantage be added or vice versa.

Auxiliaries such as propellants, catalysts, stabilizers, Emulsifiers, flame retardants and inert fillers can be added to the various reactants. Preferably, however, the blowing agent is added to the isocyanate and the catalyst to the silica sol.

The mixing of the reaction components is carried out preferably at room temperature, but the processing temperature may well be also -2O ⁰ C to + 8O ⁰ C.

The quantitative ratio of the three reaction components polyisocyanate, silica sol and the water-binding aggregate has already been mentioned. It can vary within wide limits, e.g. between 5: 2: 93 parts by weight and 5: 95: 0 parts by weight and 98: 2: 0 parts by weight. Materials with optimal properties, in particular high strength, elasticity, heat resistance and good fire-resistant properties, is obtained when the proportion of silica sol

between 20 and 80 wt .- ^, based on the

Total mixture, organic polyisocyanate between 10 and 80 wt .-? 6, based on the total mixture, and water-binding Aggregates between 10 and 70 wt .-%, related to on the total misconduct. This area is therefore preferred.

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From the point of view of both a superior property picture as well as high economic efficiency, mixtures are made of

20-70% by weight, based on the total mixture, aqueous

Silica sol,

10-50% by weight, based on the total mixture, organic

Polyisocyanate, with the exception of non-ionic hydrophilic polyisocyanate prepolymers,

20-70% by weight, based on the total mixture, water-binding Aggregates

especially preferred.

From the stated proportions it can be seen that for the production of inorganic-organic plastics of polyisocyanate, silica sol and water-binding filler, the quantitative ratio is not critical. This is for continuous Production is particularly advantageous because it is not necessary to pay attention to an exact dosage. So let yourself Use robust conveying devices such as gear pumps and Monho pumps or screws.

The properties of the inorganic-organic plastics according to the invention, in particular the foams, ζ.B. For a given recipe, their density depends on the details of the mixing process, e.g. shape and number of revolutions the stirrer, design of the mixing chamber, etc. and the selected reaction temperature when initiating foaming somewhat dependent. The density can be between approximately

10 and 200 kg / nr vary. However, they are preferred

with foamed materials ploh densities between 20 and

800 kg / m ³ .

An inorganic-organic foam according to the invention can have a closed-pore or open-pore character

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but mostly it is largely open-pored and has compressive strengths between 0.1 and 150 kp / cm ^{at densities between 20 and 800 kg / m 5.}

Foamable reaction mixtures can also be poured into cold or heated molds and allowed to harden in these molds, be it relief or solid or hollow molds, at room temperatures or temperatures up to 20O ⁰ C, optionally under pressure.

When using this foam molding technique, Molded parts with compacted edge zones and completely pore-free, smooth surfaces are obtained. Here is the co-use of reinforcing elements, be it inorganic and / or organic or metallic wires, fibers, fleeces, foams, Fabrics, scaffolding, etc. are entirely possible. The molded parts that are accessible in this way can be used directly as components or, for example, in the form of directly or subsequently by lamination with metal, glass, plastic, etc. manufactured sandwich moldings are used.

In addition to their favorable fire behavior, these materials are characterized by the fact that they are subsequently applied Organic or inorganic compounds, e.g. paints, plaster of paris, putty or sand compounds, adhere extremely well.

Of course, the foamed materials according to the invention can be used also produce blocks that are broken down into panels or lightweight building blocks by subsequent sawing and, if necessary laminated in the manner described above or provided with defc layers by other techniques can. However, the embodiment in which the desired molded parts are produced directly is preferred.

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A n porous materials ι The compressive strengths achieved according to the invention / are largely dependent on the mixing ratio of the starting components and the resulting density, for example, densities between 200 and 600 kg / nr and compressive strengths of 10 to 100 kp / cm when using a mixture approximately equal parts of polyisocyanate,. Silica sol and water-binding filler achieved with the simultaneous use of approx. 5 wt. - $> (based on the total amount) of a low-boiling blowing agent.

Important advantages according to the invention are the short mixing times; mixing takes place discontinuously Operation within 15 seconds to a maximum of about 5 minutes, as well as rapid curing, which in general takes less than 30 minutes.

During production, these advantages allow short mold downtimes and thus rapid manufacturing cycles to be achieved.

According to the invention, excellent fire-retardant materials are obtained if the sum of the inorganic constituents is more than 30 percent by weight, but preferably more than 50 percent by weight, based on the total mixture.

The machinability of a device according to the invention offers considerable advantages foamed / So it can be, for example sawing, screwing, nailing, drilling and milling excellently and thus has a wide range of possible applications.

Depending on the composition and structure, the inorganic-organic plastics according to the invention are able to absorb water and / or absorb water vapor or also have considerable diffusion resistance to water and / or water vapor.

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2 5? η Ο 7 9

The materials according to the invention open up new possibilities in civil engineering and in the manufacture of prefabricated parts and elements.

Examples of possible applications are the production of wall elements in prefabricated construction, lost formwork, Roller shutter boxes, window sills, railway and subway thresholds, curbs, stairs, the foaming of joints and the Called back foaming of ceramic tiles.

The compositions according to the invention can also advantageously be used to bind gravel, pieces of marble, etc. You can get such decorative panels as they are, for example, as facade elements Find use.

The invention is explained in more detail below with the aid of examples:

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2570079

Examples: Output connections

A) polyisocyanate component:

P 1: polyphenyl-polymethyleri-polyisocyanate,

obtained by aniline-formaldehyde condensation and subsequent phosgenation. Viscosity at 25 ° C 400 cP, NCO content: 31% by weight (2-core content: 45.1% by weight, 3-core content: 22.3% by weight - ⁰ %, content of higher-core polyisocyanates 32, 6 % By weight).

P 2: sulfonated polyphenyl polymethylene polyisocyanate

(P 1) obtained by aniline-formaldehyde condensation and subsequent l'hosgenation and sulfonation with gaseous sulfur trioxide (sulfur content: 0.98% by weight, NCO content: 30.2% by weight, viscosity at 25 ^° C.: 1200 cP).

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B) silicate component: S 1 ·; Sodium water glass (44% solids,

Molar weight ratio Na ₂ O / SiO ₂ = 1: 2) (from Henkel)

P. 2: silica sol,

S 3:

B.iyer- 100 Kieseiso! approx. 30 ° / o SiOj-Cchalt ") approx. 0.1 5% Ni, O-Gch.ilt ^h ) approx. 9jO PH value 1.20 «/ cm» DiJuc "2-3 cp Viscosity ^c ) approx. 100 mVg -, pe /. Surface ") 25-30 μm Particle size anionic lollD ^ CMItÜt milky cloudy colour odorless odor

a) determined by drying the brine at 110 ⁰ C

li) determined by titration.

c) reads with the Haake-Kunelfall viscometer.

d) BEI ^- -ViVn, determined according to Urunaucr, l-.mmctt. Plate.

tr) F <. 'vivti> rti; eh.ilt. which is composed of silica and basic aluminum chloride.

Silica sol, - 200 Uayer- approx. 30 ° / o Silica sol approx. 0.15 Vo SiOt GEKaIT ») approx 9.0 Na ₂ O content ^b ) 1.20 g / crn » PH value 3-4cp density 140-18OmVg Viscosity ^c ) 15-20 ηψ spe / .. surface ^d ) anionic Particle size transparent lono ^ cnita't odorless colour GeriK'h

a) determined by drying the brine at 110 ⁰ C

b) determined by titration.

c) lu'Minimt with the Haake-Kugclfall viscometer.

d) BET-> XVrt, determined according to lirunauer, Lmmett, Teller.

c) Fi'MMt) ft '); eh.ilt. which is composed of silica and basic aluminum diloride.

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S4:

Silica sol, 200E Bayer
Kicsclsol approx. 30 ° / o
approx. 0.15%
approx 9.0
1.20 g / cm »
approx. 4 ep SiO.-Gchalt ")
Na..C) -Cchalt ')
pi 1 value
DlJltC
Viscosity ^c ) approx. 200 m * / g spcv. Surface «) 12-15πιμ Particle size anionic
slightly opalescent
odorless Ionogcnita't
colour
GeruJi

a) It is determined by drying the brine at 10 ° C

b) determined by titration.

c) determined with the Haakc-KuRclfall viscometer.

d) ΒΕΊ host, determined according to Brunauer. I'.mmctt, plate.

<) Solid ^ -hali. which is composed of silica and basic alumintum diloride.

S 5:

Silica sol,

Bayer-Kicsclsol

SiO ₁ content ·)

NaiO-Gchalt ^b )

PH value

ÜiJitc

Viscosity")

spcv. Surface · ')

Particle size

lonogeneity

colour

Smells

200S

approx. 30 ° / o «)

approx. 3.4

approx. 1.20 g / cm "

2-3cp

cationic slightly cloudy odorless

a) determined by drying the brine at RO ⁰ C

b) determined by titration.

c) determined with the Haakc-Kugclfall viscometer.

d) BET value, determined according to Brunauer, Emmett, Teller.

e) Substance content. which is composed of silica and basic aluminum diloride.

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C) additives

Z 1: emulsifier, 50% aqueous solution of Na-

Salt of a sulfochlorinated paraffin mixture C -C (Mersolat K 30)

Z 2: 33 1/3% aqueous solution of di-ammonium

hydrogen phosphate, (NH ₄ ) ₂ HPO ₄

Z 3: catalyst consisting of 75% by weight of N, N-di-

methylaminoethanol and 25% by weight of diazabicyclooctane.

Z 4: stabilizer, polyether polysiloxane (OS 710, Bayer AG)

Z 5: chlorinated paraffin (Witaclor 63, Dynamit Nobel)

Chlorine content: 62-64% by weight Viscosity: at 20 ° C: approx. 40,000 cP

Example 1-8 :

The examples are summarized in the following table. Component I and component II were mixed thoroughly by themselves and then mixed together in a paper cup using a high-speed mixer. If Z (Di-ammonium hydrogen phosphate solution) this was separated as component III directly after the two were combined other components added.

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It means:

t = stirring time (mixing time of the mixture of component I

and component II as well as, if appropriate, components

t = lay time, period from the start of mixing to

Start of foaming

t. = Setting time, period from the start of mixing to

at the end of the foaming process (in general, this is also the time when the Hardening)

All amounts are given in parts by weight (g).

Hard inorganic-organic foams are obtained from in general regular, albeit often coarse-pored structure, which is characterized by high compressive strength and excellent fire behavior distinguish. Volume weight and compressive strength were determined one day after production.

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Example 1-8

ro

Table 1:

VJl

component

Component 2

Component 3

Example P 2 lime

1 200 100 2 200 100 3 200 100 4th 200 100 5 200 100 6th 175 100 7th 175 100 8th 175 100

Trichloro triethyl catalyst silicate emulsifier component t t t

fluoramine Z 3 comp. Zl Z 2 (sec) (sec) (sec)

methane S 3

100 - 5 20th 65 140 100 - 5 20th 50 120 100 - 5 25th 50 140 100 0.2 5 20th 53 130 100 - 8th 20th 60 120 100 - 5. 20th 47 80 100 0.2 - 20th 85 125 100 0.2 5 20th 60 135

1) quick lime, CaO

r φ

.ρ-

Table 1 continued;

Gi Example volume weight compression strength

ⁿ kp / m speed (kp / cm ^)

2 cn

° 3

CD ^J

co 4

ία? ι 5

S Sa 6

S ₇

284 44.8 297 46, 8 324 19.5 338 43.1 386 69, 1 390 63.0 438 57.0 356 50.6

Example 9-18:

The examples are summarized in the following table. The foams were produced according to Examples 1-8, wherein the lower-viscosity component in each case was added to the higher-viscosity component.

The abbreviations correspond to those in example 1-8, all quantities are in g.

Volume weights and compressive strengths of the hard inorganic-organic foamed plastics obtained, which are generally regular Have cell structure, were determined one day after production.

Due to their excellent fire behavior, these materials are of particular interest as thermal insulating construction materials for the building sector.

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Table 2:

Example 9-18

VJI

Example P 2 Z 5

component

Trichlor cement ¹ ^ lime ² * Sl fluoromethane component 2

S3 Zl triethyl cement
on in

ι 9 170 20th 10 OO
■ C- ΰιο 170 20th 15th CO ¹ 11 150 20th 15th ίο 12th 150 20th 20th 13th 200 20th 10 14th 150 20th 20th 15th 200 20th 30th 16 200 20th 30th 17th 200 20th 25th 18th 200 20th 25th

100

100

1) quick-setting cement "Fondu Lafarge ¹¹

2) quick lime, CaO

50 100 0.2 5 50 100 0.2 4th 50 100 0.2 5 75 75 0.2 3 75 75 0.2 3 100 50 0.2 4th 100 50 0.2 2 100 50 0.2 2 100 50 0.2 2 100 50 0.2 2

100

Continuation of Table 2;

Ul

example

tp t t. Room compression strength

(sec) (see) (see) weight _

kg / m kp / cm

he" I. ο co (Q co -fc- I. CO O iD (JI

9 10 11 12 13 14

15 16

17 18

20th 22nd 40 292 20th 33 58 291 20th 22nd 35 265 15th 24 37 236 15th 30th 45 293 15th 18th 20th 262 15th 35 52 128 20th 35 60 277 15th 33 53 157 15th 18th 28 189

29.9 18.4 24.2 18.7 26.2 31.1 6.6 25.7

11.7 15, 3

N> CD CD --J CD

Example 19:

To a mixture consisting of 150 parts by weight. cement (PZ 350 F according to DIN 1164), 150 parts by weight. Construction sand (washed Rhine sand, 0-3 mm) and 175 parts by weight. water a mixture of 100 wt. -TJ.en. Silicate component S 3 and 50 parts by weight of the polyisocyanate component P 2 given and the total mixture mixed intensively for 2 minutes using a high-speed stirrer. The pourable mass was poured in a layer thickness of 20 mm, began to solidify 10 minutes later and the test specimen could be demolded after 35 minutes while preserving the contours. The obtained inorganic-organic composite was accessible 3 hours after production.

example TD. '.

For a mixture of 100 parts by weight. Polyisocyanate P 1 and 100 parts by weight. Cement according to Example 30 were used within of 2 minutes 200 wt. Stir in silicate component S 3. A trowelable compound was obtained that was one layer thick of 20 mm. The mass began to solidify 20 minutes later and could below 1 hour after the start of mixing Retaining the contours are demolded. Another hour later, the inorganic-organic composite plastic was accessible.

Example 21 '·

To a mixture consisting of 250 parts by weight. Silicate component S 3, 50 parts by weight. Water and 40 parts by weight. Cement according to

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Example 30 were 30 wt. Polyisocyanate P 2 given and the whole mixture for 1 min _e mixed by a Schnellröhrers. A pourable mass was obtained, which was poured in a 20 mm layer thickness, began to solidify 1 hour later and after 3 1/2. walkable ws.i.%

Example £ &;

To a mixture consisting of 200 parts by weight. Silicate component S 3 and 400 parts by weight. Building sand according to Example 30 were successively 100 wt. Polyisocyanate P2 and 3.5 Wt. Triethylamine added and the total mixture mixed intensively for 5 minutes using a high-speed stirrer and in a layer thickness of 20 mm crossed out. Within the next 30 minutes, the mass began to set and increased in volume by approx. 5% 3 hours later solidified to form a rock-hard, yet elastic, porous, inorganic-organic composite.

Example 23:

For a mixture of 100 parts by weight. Polyisocyanate P 2 and 100 parts by weight. Cement according to Example 30 were 100 wt. Ie. Silicate component S 2 given and the total mixture mixed well for 1 min. A trowelable compound was obtained that was 20 mm thick was painted out, began to set 50 minutes after production and after a further 2 hours to a walk-in inorganic-organic Composite was hardened.

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Claims (16)

Claims; 1. Process for the production of an inorganic-organic plastic, in particular foam, by reaction of an organic polyisocyanate with aqueous silica sol and water-binding additives, and possibly additives, which consists in that one a reaction mixture consisting of 2-95 percent by weight, based on the total mixture, aqueous silica sol, preferably with a content of 20-60 Weight percent silica, 5-98 percent by weight, based on the total mixture, organic polyisocyanate, with the exception of non-ionic hydrophilic polyisocyanate prepolymers, 0-93 percent by weight, based on the total mixture, water-binding aggregates, used" 2. The method according to claim 1, characterized in that a propellant is also used. 3. The method according to claim 1-2, characterized in that one accelerates the isocyanate reaction Activator also used. 4. The method according to claim 1-3, characterized in that there is a foam stabilizer and / or a Emulsification aid used. Le A 16 450 - 32 - 509848/0957 5. The method according to claim 1-4, characterized in that organic, fire-retardant additives are used. 6. The method according to claim 1-5, characterized in that a polymeric substance is also used. 7. The method according to claim 1-6, characterized in that one inert inorganic, particulate and / or fibrous material is also used. 8. The method according to claim 1-7, characterized in that one inert organic, particulate and / or fibrous material is also used. 9 "Method according to claims 1-8, characterized in that that compounds with isocyanate-reactive hydrogen atoms are also used, . Process according to Claim 1, characterized in that the polyisocyanate used is a polyisocyanate containing ion groups used. 11. The method according to claim 1o, characterized in that «The polyisocyanate containing ion groups is a sulfonic acid / or Is polyisocyanate containing sulfonate groups. 12. The method according to claim 1, characterized in that the water-binding filler is water cement, synthetic Anhydrite, gypsum or quick lime are used. Le A 16 450 - 33 - 13. The method according to claim 2, characterized in that a halogenated hydrocarbon with a boiling point below 10O ⁰ C is used as the blowing agent. .A method according to claim 3, characterized in that a tertiary amine is used as the activator. 15 _# The process of claim 7, characterized in that co-used glass fibers as the inert material. 16. Inorganic-organic plastics, available from Reaction of a mixture 2-95 percent by weight (preferably 20-80 percent by weight), based on the total mixture, aqueous silica sol, preferably with a content of 20-60 percent by weight silica, 5-98 percent by weight (preferably 10-80 percent by weight) based on the total mixture, organic Polyisocyanate, with the exception of non-ionic hydrophilic polyisocyanate prepolymers, 0-93 percent by weight (preferably Ό-70 percent by weight), based on the total mixture, water-binding aggregates. Le A 16 450 - 34 - 509848/0957