EP0000579A1 - Process for the preparation of inorganic-organic synthetic resins - Google Patents

Abstract

Process for the production of inorganic-organic plastics of high strength, elasticity, heat resistance and flame resistance consisting of a polymer-silica gel composite material present as a colloidal xerosol by mixing a) an organic polyisocyanate b) an aqueous basic solution and / or an aqueous basic suspension with contents of inorganic solid of 20-80% by weight, preferably 30-70% by weight, c) a flowable inorganic compound, and optionally d) catalysts and other additives and allowing the mixture thus obtained to react, characterized in that the mixing is carried out in such a way that component a) and b), if appropriate with the addition of all or part of component d), is first reacted to form a stable primary dispersion and then component c), if appropriate with the addition of all or part component d), under training a final dispersion is added.

Description

Inorganic-organic plastics based on polyisocyanates and aqueous alkali silicate solutions are known; see e.g. DT-OS 1 770 384, 2 227 147, 2 359 606, 2 359 607, 2 359 606, 2 359 609, 2 359 610, 2 359 611, 2 359 612, DT-AS 2 325 090 and 2 310 559.

In this way, plastics can be produced which, due to their inorganic content, have an improved fire resistance, especially compared to pure organic substances, and which, depending on the composition and reaction conditions, can be foamed or non-foamed, hard or soft, brittle or flexible. Due to the great variability of the properties, these inorganic-organic plastics offer a wide range of possible applications.

These combination plastics have in common that the organic and the inorganic phase must be mixed with one another for their production. This creates dispersions of the type W / O (water in oil) or O / W (oil-in-water).

The plastics resulting from a W / O type dispersion are particularly interesting. They have high mechanical strengths, even when exposed to moisture, because the hardened, coherent organic phase envelops and thus fixes the likewise hardened aqueous, inorganic, incoherent phase. The perfect coherent organic phase of these plastics also depends on the improved fire resistance of such systems due to the amount of water enclosed.

Attempts have been made to produce the described plastics by mixing the reaction components in one batch or in a continuously operating mixing device in one or in several stages and then allowing the resulting dispersion to solidify.

In this way, however, products are generally obtained which increasingly lose their mechanical strength as the proportion of inorganic component increases and, in extreme cases, even have a sand-like character and cavities. However, these products with a high inorganic content are particularly interesting for economic reasons and because of their increased fire resistance.

The invention is based, to avoid the disadvantages described above and to produce inorganic-organic plastics, even with high amounts of inorganic components, the task.

• a) einem organischen Polyisocyanat
• b) einer wäßrigen basischen Lösung und/oder einer wäßrigen basischen Suspension mit Gehalten an anorganischem Feststoff von 20-80 Gew.-%, vorzugsweise 30-70 Gew.-%,
• c) einer fließfähigen anorganischen Verbindung, und gegebenenfalls
• d) Katalysatoren und weiteren Zusatzmitteln und Ausreagierenlassen des so erhaltenen Gemischs,

jadurch gekennzeichnet, daß die Vermischung in der Weise vorgenommen wird, daß zunächst die Komponenten a) und b), gegebenenfalls unter Zusatz der ganzen Menge oder eines Teils der Komponente d), zu einer stabilen Primärdispersion umgesetzt und anschließend die Komponente c), gegebenenfalls unter Zusatz der ganzen Menge oder eines Teils der Komponente d), unter Ausbildung einer Enddispersion zugegeben wird.This object is achieved with the method according to the invention. The present invention thus relates to a process for the production of inorganic-organic plastics of high strength, elasticity, heat resistance and flame resistance, consisting of a polymer-silica-gel composite material present as a colloidal xerosol by mixing

• a) an organic polyisocyanate
• b) an aqueous basic solution and / or an aqueous basic suspension with an inorganic solid content of 20-80% by weight, preferably 30-70% by weight,
• c) a flowable inorganic compound, and optionally
• d) catalysts and other additives and allowing the mixture thus obtained to react,

characterized in that the mixing is carried out in such a way that components a) and b), if appropriate with the addition of all or part of component d), are first reacted to form a stable primary dispersion and then component c), if appropriate under The addition of all or part of component d) is added to form a final dispersion.

It is preferred according to the invention that the final dispersion has a viscosity range of 600-6000 cP before the start of curing at room temperature and consists of 50-90% by weight of inorganic aqueous phase and 10-50% by weight of organic phase.

The process according to the invention can be carried out continuously or preferably batchwise. After the discontinuous procedure, the stable primary dispersion is first prepared from polyisocyanate, aqueous basic solution or suspension and, if appropriate, further additives, such as activators, emulsifiers and blowing agents, and then the inorganic compound (component c)) is added. After the continuous mode of operation, the primary dispersion is generated in advance in a prechamber in accordance with the discontinuous mode of operation by means of a special mechanical arrangement; the mixing with the inorganic compound (component c)) takes place continuously in a downstream mixing head.

According to the invention, mixing of the individual components, e.g. carried out in the order that first a spatially and temporally from components a) and b), optionally with the addition of all or part of component d), a dispersion is produced with the aid of a mixing unit and to this dispersion in a spatially and temporally then arranged mixing unit, component c), if necessary with the addition of all or a part of component d), is added.

• 1) Es werden zwei RUhrwerksmischköpfe benutzt.
• 2) Es werden zwei Mischaggregate benutzt, die aus zwei nacheinander auf einer angetriebenen Achse angebrachten Mischorganen bestehen, wobei die Komponenten a) und b) [und ggf. d)] am oberen Teil der angetriebenen Achse eindosiert werden, die Komponente c)[und ggf. d)] dagegen im unteren Teil der Achse.
• 3)Die Mischaggregate bestehen aus zwei nacheinander angeordneten statischen Mischvorrichtungen, wobei die Komponenten a) und b) [und ggt. d)] am ersten statischen Mischer eindosiert werden und nach dem Passieren der ersten Mischstrecke im zweiten statischen Mischer mit der Komponente c) [und ggf. d)] vermischt werden.
• 4)Als erstes Mischaggregat wird ein Rührwerksmischkopf benutzt und als zweites Mischaggregat ein statischer Mischer.
• 5) Als erstes Mischaggregat wird ein statischer Mischer und als zweitea Mischaggregat ein Rührwerksmischkopf benutzt.

There are various possibilities for the technical implementation of this successive mixing:

• 1) Two agitator mixing heads are used.
• 2) Two mixing units are used, which consist of two mixing elements mounted one after the other on a driven axle, components a) and b) [and possibly d)] being metered into the upper part of the driven axle, components c) [and if necessary d)] on the other hand in the lower part of the axis.
• 3) The mixing units consist of two static mixing devices arranged one after the other, components a) and b) [and ggt. d)] are metered into the first static mixer and, after passing through the first mixing section in the second static mixer, are mixed with component c) [and, if appropriate, d)].
• 4) An agitator mixing head is used as the first mixing unit and a static mixer as the second mixing unit.
• 5) A static mixer is used as the first mixing unit and an agitator mixing head as the second mixing unit.

The discontinuous variant is recommended when using such inorganic compounds as component c), which e.g. gel aqueous alkali silicate solutions spontaneously. In this case, polyisocyanate and e.g. aqueous alkali silicate produced a stable primary dispersion and then added component c).

Longer mixing times, which are often desirable, can be achieved by the batch process in that the activator required for curing is added only after the scabilized primary dispersion has been prepared.

Inorganic compounds according to component c) which do not or only very slowly gel aqueous alkali silicates can be used either by the continuous or by the batch process.

Starting components (component a) to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, as described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example acetylene 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-isocyanto-3 , 3,5-trimethyl-5-isocyantomethyl-cpclonexan (DT-AS 1 202 785, US Pat. No. 3,401,190), 2,4- and 2,8-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diPhenylethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2, 6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-1,5-diisocyanate, triphenylm ethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in the GB-PS 874 430 and 848 671 are described, m- and p-isocyanatophenylsulfonyl-isocyanates according to US Pat. No. 3,454,606, perchlorinated aryl polyisocyanates as described, for example, in DT-AS 1 157 601 (US Pat. No. 3,227,138) polyisocyanates containing carbodiimide groups, as described in German Patent 1,092,007 (US Pat. No. 3,152,162), diisocyanates as described in US Pat. No. 3,492,330, polyisocyanates containing allophanate groups, as described, for example, in US Pat in British patent specification 994 890, BE-PS 761 626 and published Dutch patent application 7 102 524, polyisocyanates containing isocyanurate groups, as described, for example, in US Pat. No. 3,001,973, in DT-PS 1 022, 789, 1 222 067 and 1 027 394 and in DT-OS 1 929 034 and 2 004 048, polyisocyanates containing urethane groups, as described, for example, in Belgian patent specification 752 261 or in American patent specification 3 394 164, have acylated urea groups de Polyisocyanates according to polyisocyanates according to DT-PS 1 230 778, polyisocyanates containing biuret groups, such as those in DT-PS 1 101 394 (US Pat. Nos. 3 124 605 and 3 201 372) and in GB-PS 889 050 polyisocyanates prepared by telomerization reactions, such as are described, for example, in US Pat. No. 3,654,106; polyisocyanates containing ester groups, such as are described, for example, in GB Pat. Nos. 965,474 and 1,072,956, in US Pat. No. 3,567,76 , 3 and in which DT-PS 1 231 688 are mentioned, reaction products of the above-mentioned isocyanates with acetals according to DT-PS 1 072 385, polyisocyanates containing polymeric fatty acid residues according to US Pat. No. 3,455,883.

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

The technically easily accessible polyisocyanates, e.g. 2,4- and 2,6-toluyien diisocyanate as well as any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and carbodiimide groups, Urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups containing pelyisocyanates ("modified polyisocyanates").

According to the invention, particular preference is given to polyisocyanates containing ionic groups, as described in DT-OS 2 227 147, for example sulfonated polyisocyanates (DT-OS 2 227 111, 2 359 614, 2 359 615), polyisocyanates containing carboxylate groups (DT-OS 2 359 613). Also preferred according to the invention are nonionic-hydrophilic polyisocyanates as described in DT-OS 2 325 909, furthermore polyisocyanates containing polar groups according to DT-OS 2 359 608 and phenolic OH groups containing polyisocyanates as described in DT OS 2 359 616.

The above-mentioned, particularly preferred polyisocyanates are preferably made from polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ('crude MDI'), and from the distillation residues obtainable therefrom by distillation of two-core products, which generally have a viscosity between 50 and 50,000 P / 25 ° C, an NCO content of 28-33 percent by weight and a functionality> 2.

According to the invention, aqueous basic solutions or suspensions containing are also used as starting components (component b)). of inorganic solids of 20-80% by weight, preferably 30-70% by weight, especially aqueous alkali silicate solutions or alkaline stabilized silica sols, but also liquid-flowable basic suspensions of finely divided fillers. The aforementioned aqueous basic solutions or suspensions are often salted in combination.

Aqueous solutions of alkali silicates are to be understood as the solutions of sodium and / or potassium silicate in water which are usually referred to as "water glass". Raw technical solutions, which are e.g. Calcium silicate, magnesium silicate, borates and aluminates can be used.

The molar ratio Me ₂ O / SiO ₂ (Me = alkali metal, zR Na, K.) Is not critical and can vary within the usual limits; preferably it is 1: 1.6 to 1: 3.3. If the water content of the plastic initially obtained by reaction with the polyisocyanate plays a subordinate role because en does not interfere or because it can be easily removed by drying, then only weakly alkaline sodium silicate can be used, of which, for example, 20-35% by weight .-% solutions prepared. Preferably, however, 32-54% by weight silicate solutions are used which only have sufficient alkalinity to have the viscosity of less than 500 poise required for problem-free processing. Ammonium silicate solutions, for example solutions of guanidine silicate, can also be used, but these are less preferred. It can be real or colloidal solutions.

The choice of concentration mainly depends on the wiped end product. Compact or closed-cell materials are preferably made with concentrated silicate solutions, which are adjusted to low viscosity if necessary by adding alkali hydroxide. In this way, 40-70% by weight solutions can be prepared. On the other hand, silicate solutions with a 30-35% by weight content are preferred for the production of light-pored foams in order to achieve low viscosities, sufficiently long reaction times and low densities. Even when using finely divided inorganic fillers in larger quantities, silicate solutions with a content of 30-35% are preferred.

Further detailed information on alkali metal silicate solutions which can be used according to the invention can be found in James G. Vail 'Soluble Silicates, their properties and uses', Reinhold Publishing Corporation, New York 1952.

Flowable inorganic compounds are to be understood as component c), e.g. - In extreme cases - water or water-insoluble or sparingly soluble inorganic compounds which are brought into a flowable state and which have at least 50% by weight of a particle size of less than 50 microns (preferably 50% by weight of less than 10 microns). Inert mineral fillers or also hydraulic mineral binders are particularly suitable here, in particular aqueous suspensions of fillers which have a solids content of between 20 and 80% by weight. If the dry fillers already meet the particle size criteria according to the invention (at least 50% by weight less than 50 microns), they can be mixed directly with water to form a suspension. If the particles are coarser, an aqueous coarse suspension of the fillers can also be converted into a fine suspension usable according to the invention by known methods of wet grinding.

Particularly preferred aqueous suspensions are those which are stable to sedimentation and show viscous, rapid flow behavior, as is known, for example, from paper coating slips. To produce such filler suspensions, it is therefore advantageous to use the methods known for the preparation of such coating slips.

• 1. Verwendung extrem feinteiliger Füllstoffe kleiner als 20 Mikron, mindestens 50 Gew.-% kleiner als 2 Mikron. Ganz besonders günstig sind Füllstoffe, deren Teilchengröße zu 80% zwischen 0,5 und 2 Mikron liegt, wie dies z.B. bei einer Reihe von Calciumcarbonat-Typen der Fall ist.
• 2. Verwendung oberflächenmodifizierter Füllstoffe, die durch die Modifizierung hydrophiliert und dadurch besser dispergierbar sind.
• 3. Herstellung der Dispersion unter Anwendung agglomeratzerstörender Scherkräfte, wie dies z.B. bei der Herstellung von Pigmentpasten und bei pigmentierten Lacksystem üblich ist, z.B. Abreiben auf dem Dreiwalzenstuhl, einer Sandmühle oder dergleichen.
• 4. Mitverwendung von Dispergierhilfsmitteln und Dispersionsstabilisatoren, wie z.B. Salzen der Phosphorsäure, Pyrophosphorsäure, Metaphosphorsäure, Polyphosphorsäuren,phosphorigen Säuren, Oligokieselsäuren, Polykieselsäuren, organischen hochmolekularer Polysäuren, wie z.B. Poly (meth) acrylsäuren, copolymeren Poly (meth) acrylsäuren, Polymaleinsäuren, copolymere Polymaleinsäuren, wasserlösliche Derivate, der Zellulose, Stärke, Alginsäuren sowie Pflanzengummen. Auch die üblichen oberflächenaktiven Verbindungen, wie Emulgatoren, Netzmittel und Tenside kommen in Betracht.
• 5. Mitverwendung von Verdickungsmitteln, wie Zellulosederivaten, Polyacrylamid, Alginaten, Pflanzengummen, wasserlöslichen Polymeren, z.B. Polyäthylenoxid.
• 6. Mitverwendung von hoch- und niedermolekularen Di- oder Polyalkoholen oder Di- bzw. Polyaminen.

Stabilized suspensions preferred according to the invention are those which do not sediment appreciably within one day and show rapid viscous flow behavior. In the context of the present invention, aqueous filler suspensions are considered to be 'stabilized' if the dispersed fillers are dispersed as agglomerate-free individual particles by one or more of the measures listed below:

• 1. Use of extremely finely divided fillers smaller than 20 microns, at least 50% by weight smaller than 2 microns. Fillers with a particle size of 80% between 0.5 and 2 microns, as is the case with a number of types of calcium carbonate, are particularly favorable.
• 2. Use of surface-modified fillers which are hydrophilized by the modification and are therefore more dispersible.
• 3. Production of the dispersion using shear forces which destroy agglomerates, as is customary, for example, in the production of pigment pastes and in the case of pigmented coating systems, for example rubbing on a three-roll mill, a sand mill or the like.
• 4. Use of dispersing aids and dispersion stabilizers, such as salts of phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acids, phosphorous acids, oligosilicic acids, polysilicic acids, organic high molecular weight polyacids, such as poly (meth) acrylic acids, copolymeric poly (meth) acrylic acids, polymaleic acids, copolymeric polymaleic acids, water-soluble derivatives, cellulose, starch, alginic acids and vegetable gums. The usual surface-active compounds, such as emulsifiers, wetting agents and surfactants, are also suitable.
• 5. Use of thickeners, such as cellulose derivatives, polyacrylamide, alginates, plant gums, water-soluble polymers, for example polyethylene oxide.
• 6. Use of high and low molecular weight di- or polyalcohols or di- or polyamines.

Suspensions which are produced with the addition of 0.05 to 20% by weight, based on filler, of one or more of the additives listed under 4.5 and 6 are particularly preferred. At the same time, although less economical from the point of view of economy, the use of surface-modified and thus hydrophilized fillers is, which generally eliminates the need for additives.

If the filler suspension is stabilized by organic additives, its amount should not exceed 5%, based on filler, in order not to deteriorate the fire behavior of the inorganic-organic plastics.

In particular, if suspensions contain additives according to 4 and / or 5. and / or 6 and are additionally produced according to the criteria mentioned under 1 and 3, this results in outstanding sedimentation-stable suspensions with flow behavior matched to the processing process.

If filler suspensions stabilized by additives are used, fillers are preferably used which have at least 90% by weight of a particle size of less than 20 microns and at least 50% by weight of a particle size of less than 10 microns.

Of course, the filler suspension can also be prepared immediately before the addition, e.g. by metering dry fillers and water into a feed line to the mixing room in which the polyisocyanate is mixed with aqueous alkali silicate and by means of a mixing device, e.g. a screw within this feed line, the aqueous filler suspension is generated in situ.

The use of hydraulic binders, in particular cement, generally requires suspension in water or aqueous alkali silicate immediately before processing with the isocyanate component, so that the setting process and any gelation process possibly caused by cement expediently take place in the finished plastic.

The filler suspensions used preferably have a viscosity above 100 cP in order to ensure rheological behavior which is favorable for processing. On the other hand, they should be easy to flow and should in no way have crumbly consistency. A viscosity of 10,000 cP is preferably not exceeded. A good and very intimate relationship Mixing with the polyisocyanate in conventional processing equipment should be ensured. On the other hand, the content of fillers in the aqueous suspension should be as high as possible in order not to introduce more water than is absolutely necessary into the plastic. Depending on the particle size and the shape of the filler particles, the filler concentration is between 20 and 80%. A content of 30-70% is preferred. Lower concentrations generally have to be chosen if non-spherical fillers are also used, such as asbestos, talc, clays or special iron oxides. Component c) can also be identical to component b) in some cases.

According to the invention, volatile organic substances are optionally used as blowing agents. As organic blowing agents come e.g. Acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether are also suitable. A blowing effect can also be achieved by adding compounds which decompose at temperatures above room temperature with the elimination of gases, for example nitrogen. Azo compounds such as azoisobutyronitrile can be achieved.

The water contained in the aqueous basic solution or suspension can also take on the function of the blowing agent. Fine metal powders, e.g. Calcium, magnesium, aluminum or zinc serve as a blowing agent through the development of hydrogen with sufficient alkaline water glass, while at the same time exerting a hardening and strengthening effect.

According to the invention, catalysts are also often used. Suitable catalysts to be used include those of the type known per se, e.g. tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholirl, N-cocomorpholine, N, N, N ', N'-tetramethyl-ethylenediamine, 1,4-diaza-bicyclo- (2.2 , 2) octane, N-methyl-N'-dimethylaminoethyl piperazine, N, N-dimethylbenzylamine, bis (N, N-diethylaminoethyl) adipate, N, N-diethylbenzylamine, bentamethyldiethylenetriamine, N, N-dimethylcyclohexylamine , N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-ß-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole and in particular also hexahydrotriazine derivatives.

Tertiary amines which have hydrogen atoms active against isocyanate groups are e.g. Triethanolamine, triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethylethanolamine and their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.

Silaamines with carbon-silicon bonds, such as those e.g. in German Patent 1,229,290, in question, e.g. 2,2,4-trimethyl-2-silamorpholine, 1,3-diethylaminomethyl-tetramethyldisiloxane.

Suitable catalysts are also nitrogen-containing bases such as tetraalkylammonium hydroxides, alkali metal hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali metal alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts. According to the invention, organic metal compounds, in particular organic tin compounds, can also be used as catalysts.

Preferred organic tin compounds are tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) acetate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin salts of carboxylic acids, such as e.g. Dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.

Further representatives of catalysts to be used according to the invention and details on the mode of action of the catalysts are in the plastics manual, volume VII, edited by Vieweg 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.

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

Water-soluble polyether siloxanes are particularly suitable as foam stabilizers. These compounds are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide is linked to a polydimethylsiloxane radical. Such foam stabilizers are e.g. in U.S. Patent 2,764,565.

According to the invention, reaction retarders, e.g. acidic substances such as hydrochloric acid or organic acid halides, also cell regulators of the type known per se such as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes and flame retardants of the type known per se, e.g. Tris-chloroethyl phosphate or ammonium phosphate and polyphosphate, inorganic salts of phosphoric acid, chlorinated paraffins, further stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances, fillers such as barium sulfate, diatomaceous earth, soot or sludge chalk are also used.

Further examples of surface-active additives and foam stabilizers to be used according to the invention, as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungistatic and bacteriostatic substances, and details on the use and action of these additives are given in the Plastics Manual, Volume VII by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113. The mixing of the reaction components is preferably carried out at room temperature.

The choice of the mixing process largely depends on the type of filler used. Examples of fillers which are preferably used as aqueous suspensions by the batch process according to the invention, since they partially contain aqueous alkali silicates. Gelling spontaneously are: calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, chalk, lime, dolomite, calcium sulfate, gypsum and anhydride. Examples of fillers which can be mixed both by the batch and the continuous process are those which do not or only slowly gel aqueous alkali silicates and which are therefore suspended as an aqueous suspension or in aqueous alkali silicate, are used in the process according to the invention. Examples include: iron oxides, aluminum oxides, quartz powder, clays, asbestos, glasses in powder form, silicate minerals, and water cements such as red ribbon cement, fast-setting cement or alumina cement. From the quantitative ratios of 50-90% by weight of inorganic-aqueous phase and 10-50% by weight of organic phase, it can be seen that the quantitative ratio is not critical for the production of such plastics according to the invention.

To interpret the technical advantages according to the invention, it is assumed that the primary dispersion produced in the meantime by the process according to the invention is extremely stable and that further additives do not endanger this stable state beyond the reaction and curing time. According to the previous state of the art, on the other hand, dispersions are generally obtained which, with an increasing proportion of inorganic components and changing the W / O phase structure, undergo unstable dispersion states which, after curing, can result in disturbances in the structure of the inorganic-organic plastic.

This is because inorganic substances, introduced using conventional mixing techniques, can initiate segregation processes and thereby prevent the production of technically useful inorganic-organic plastics. It is believed likely that such additives will gel the inorganic phase and / or that the organic and inorganic phase will not mix sufficiently due to the premature crosslinking reaction with the polyisocyanate.

The plastics according to the invention, including foams, open up new possibilities in building construction and civil engineering as well as in the manufacture of finished parts and elements.

Examples of possible applications include the manufacture of convertible elements in prefabricated buildings, lost formwork, roller shutter boxes, window sills, railroad and subway sleepers, curbs, stairs, the foaming of joints and the back-foaming of ceramic tiles.

The foam concrete can also be used advantageously to bind gravel, marble, etc. You can get decorative panels such as those used as facade elements.

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

Examples

(Unless otherwise noted,% figures are percentages by weight).

• a) Polyisocyanatkomponente
  • A₃: Von rohem Phosgenierungsprodukt eines Anilin/Formaldehyd-Kondensats wird soviel Diisocyanato-diphenylmethan abdestilliert, daß der Destillationsrückstand bei 25°C eine Viskosität von 400 cP aufweist. (2-Kernanteil: 45,1 Gew.-%, 3-Kernanteil:, 22,3 Gew.-%, Anteil an höherkernigen Polyisocyanaten: 32,6 Gew.-%) NCO-Gehalt: 30-31 Gew.-%.
  • A₁: Mit gasförmigem Schwefeltrioxid sulfoniertes A₃ (Schwefelgehalt: 0,96 %, NCO-Gehalt: 30,5 %, Viskosität bei 25°C: 24000 cP, Herstellung s. DT-OS 2 227 111).
  • A₂:Entsprechend mit Chlorsulfonsäure sulfoniertes A₃ (Schwefelgehalt: 0,9 %, NCO-Gehalt: 30,2 % Viskosität bei 20°C: 2000 cP).
• b) Silikatkomponente
  • B₁: Natriumwasserglas, 44 % Feststoff, Molgewichtverhältnis _.Na₂0: Si0₂= 1:2
  • B₂: Natriumwasserglas, 48,6 % Feststoff, Molgewichtverhältnis Na₂0 : SiO₂ = 1:2
• c) Polyäther
  • C₂: Auf n-Butanol gestarteter Polyäthylenoxid-monoalkohol OH-Zahl: 49,2
  • C₁: Auf Äthylendiamin gestarteter Polypropylentetraalkohol OH-Zahl: 63o
• d) Suspensionen
  • D₁: In 1000 g einer 54 %igen Natriumsilikatlösung mit einem Si0₂/Na₂0-Verhältnis von 2,0 werden bei Raumtemperatur 1000 g eines Filterschlamms des Typs Eisenoxidschwarz 32o der Firma Bayer AG mit einem Feststoffgehalt von 62% unter einer vorherrschenden Teilchengröße von 0,2_/u (das Pigment beseitzt Kugelform) eingerührt. Die entstandene sedimentationsstabile Suspension hat folgende Zusammensetzung:
    31 Gew.-% Eisenoxid
    27 Gew.-% Natriumsilikat
    42 Gew.-% Wasser
  • D₂: In 2,5 kg Wasser, 1oo g einer 30%igen wäßrigen Lösung eines hochmolekularen Di-Kaliumsalzes eines Maleinsäure-Styrol-Copolymerisats mit Carboxylat- und Sulfonatgruppen und 209 g 30 %ige wäßrige Eisen (III)-chlorid-Lösung wurden 2,5 kg Weißkalkhydrat (Teilchengröße: 80 % <30_/u; Weißkalkhydrat der Firma Arminia-Hydroka) suspendiert. Feststoffgehalt: 47 %

Starting materials:

• a) polyisocyanate component
  • A ₃ : So much diisocyanatodiphenylmethane is distilled off from crude phosgenation product of an aniline / formaldehyde condensate that the distillation residue at 25 ° C. has a viscosity of 400 cP. (2-core fraction: 45.1% by weight, 3-core fraction :, 22.3% by weight, proportion of higher-core polyisocyanates: 32.6% by weight) NCO content: 30-31% by weight .
  • A ₁ : A ₃ sulfonated with gaseous sulfur trioxide (sulfur content: 0.96%, NCO content: 30.5%, viscosity at 25 ° C: 24000 cP, production see DT-OS 2 227 111).
  • A ₂ : Correspondingly A ₃ sulfonated with chlorosulfonic acid (sulfur content: 0.9%, NCO content: 30.2% viscosity at 20 ° C: 2000 cP).
• b) silicate component
  • B ₁ : sodium water glass, 44% solids, molecular weight ratio _. Na ₂ 0: Si0 ₂ = 1: 2
  • B ₂ : sodium water glass, 48.6% solids, molar weight ratio Na ₂ 0: SiO ₂ = 1: 2
• c) polyether
  • C ₂ : Polyethylene oxide monoalcohol started on n-butanol OH number: 49.2
  • C ₁ : Polypropylene tetraalcohol started on ethylenediamine OH number: 63o
• d) suspensions
  • D ₁ : 1000 g of a filter sludge of the iron oxide black 32o type from Bayer AG with a solids content of 62% below a prevailing particle size are in 1000 g of a 54% sodium silicate solution with an SiO ₂ / Na ₂ 0 ratio of 2.0 at room temperature of 0.2 _/ u (the pigment eliminates spherical shape). The resulting sedimentation-stable suspension has the following composition:
    31% by weight iron oxide
    27% by weight sodium silicate
    42% by weight of water
  • D ₂ : In 2.5 kg of water, 100 g of a 30% strength aqueous solution of a high molecular weight di-potassium salt of a maleic acid Styrene copolymer with carboxylate and sulfonate groups and 209 g of 30% aqueous iron (III) chloride solution, 2.5 kg of white lime hydrate (particle size: 80% <30 _/ u; white lime hydrate from Arminia-Hydroka) were suspended. Solids content: 47%

example 1

• Rohdichte [kg/m³] : 152
• Druckfestigkeit [MPa] : 0,77

Components I and II were premixed with a high-speed stirrer for 10 seconds, component III was then added with stirring within 10 seconds. After t _{R =} 30 sec. Total mixing time, the reaction mixture was poured out into a paper packet, began to foam up after t _L = 40 sec. And had solidified after t _A = 58 sec. A hard inorganic-organic heavy foam was obtained with the values:

• Bulk density [kg / m ³ ]: 152
• Compressive strength [MPa]: 0.77

Comparative Example 1a)

• tR : 30 sec., t_L : 43 sec., t_A : 60 sec. Rohdichte [kg/m³] . 223

According to Example 1, components II and III were premixed. The mixture was slowly stirred into component I within 20 seconds. A hard inorganic-organic heavy foam was obtained with the values:

• tR: 30 sec., t _L : 43 sec., t _A : 60 sec. Gross density [kg / m ³ ]. 223

Comparative Example 1b)

According to Example 1, components II and III were premixed and quickly stirred into component I within 5 seconds. After t _R = 30 sec. Mixing time, the mixture was poured into a paper packet and began to foam up after t _L = 44 sec. And was solidified after t _A = 68 sec. To form a cavity. A sandy, inhomogeneous, void-containing plastic was obtained without comparable pressure resistance.

Example 2

• tR : 30 sec., t_L : 37 sec., t_A : 54 sec. Rohdichte [kg/m³] : 241
• Druckfestigkeit [MPa] : 0,3

The foaming was carried out according to Example 1. A hard inorganic-organic heavy foam was obtained with the values:

• tR: 30 sec., t _L : 37 sec., t _A : 54 sec. Gross density [kg / m ³ ]: 241
• Compressive strength [MPa]: 0.3

Comparative Example 2a)

If components I, II and III from Example 2 were mixed simultaneously, a highly viscous, non-pourable reaction mixture without foaming tendency was obtained within 30 seconds of stirring.

Comparative Example 2b)

Mixed the components I, was II and III of Example 2 g is reduced simultaneously with the proviso that the activator g of triethylamine of component III from 8 to 6, so emerged after t _R = sec 20th a pourable reaction mixture that after t _L = Foamed for 36 seconds and solidified after t _A = 72 seconds. A sandy, inhomogeneous, low-strength product with cavities was obtained.

Comparative Example 2c)

• t_R : 30 sec., t_L : 34 sec., t_A : 56 sec.
• Rohdichte [kg/m³] : ₂₆₈
• Druckfestigkeit /MPa/ : 0,41

Components II and III from comparative example 2b) above were premixed and then slowly stirred into component I within 20 seconds. A hard inorganic-organic heavy foam was obtained with the values:

• t _R : 30 sec., t _L : 34 sec., t _A : 56 sec.
• Bulk density [kg / m ³ ]: ₂₆₈
• Compressive strength / MPa /: 0.41

Example 3

• t_R : 30 sec., t_L : 35 sec., t_A : 50 sec.
• Rohdichte [kg/m³] . 213
• Druckfestigkeit [MPa] : 0,48

The foaming was carried out according to Example 1. A hard foam was obtained with the values:

• t _R : 30 sec., t _L : 35 sec., t _A : 50 sec.
• Gross density [kg / m ³ ]. 213
• Compressive strength [MPa]: 0.48

Example 4

• t_R : 3o sec., t_L : 36 sec., t_A : 52 sec.
• Rohdichte [kg/m³] : 406
• Druckfestigkeit [MPa] 1,37

The foaming was carried out according to Example 1. A hard heavy foam with the values:

• t _R : 3o sec., t _L : 36 sec., t _A : 52 sec.
• Bulk density [kg / m ³ ]: 406
• Compressive strength [MPa] 1.37

Example 5

• t_R : 30 sec., t_L : 37 sec., t_A : 67 sec.
• Rohdichte [kg/m³] : 242
• Druckfestigkeit [MPa] 0,42

Polyisocyanate A ₁ was replaced by polyisocyanate A ₂ . The foaming was otherwise carried out using the components from Example 4 according to Example 1.

• t _R : 30 sec., t _L : 37 sec., t _A : 67 sec.
• Bulk density [kg / m ³ ]: 242
• Compressive strength [MPa] 0.42

Example 6

• t_R : 30 sec., t_L : 34 sec, T_A : 52 sec.
• Rohdichte [kg/m³] : 383
• Druckfestigkeit [MPa] : 1,09

Example 5 was repeated with 75 g of trichlorofluoromethane.

• t _R : 30 sec., t _L : 34 sec, T _A : 52 sec.
• Bulk density [kg / m ³ ]: 383
• Compressive strength [MPa]: 1.09

Example 7

• _{tR : 30 sec.}, t_L : _{32 sec}., t_A : 49 sec.
• Rohdichte [kg-m³] : 395
• Druckfestigkeit [MPa] : 0,80

Components II and III were premixed and then slowly stirred into component I within 20 seconds. A hard foam was obtained with the values:

• _{tR: 30 sec.} , t _L : _{32 sec} ., t _A : 49 sec.
• Bulk density [kg-m ³ ]: 395
• Compressive strength [MPa]: 0.80

Comparative Example 7a)

Components II and III were premixed in accordance with Example 5 and subsequently quickly stirred into component I within 5 seconds. After 20 seconds of stirring, a highly viscous, non-pourable reaction mixture was obtained which did not foam. The solidified product was sandy and crumbly.

Example 8

• t_R : 30 sec., t_L : 34 sec., t_A : 46 sec.
• Rohdichte [kg/m³] : 27₃
• Druckfestigkeit [MPa] : 1,02

Foaming was carried out according to Example 1

• t _R : 30 sec., t _L : 34 sec., t _A : 46 sec.
• Bulk density [kg / m ³ ]: 27 ₃
• Compressive strength [MPa]: 1.02

Comparative Example 8a)

• t_R : 30 sec., t_L : 33 sec., t_A : 40 sec.
• Rohdichte [kg/m³] : 28₀
• Druckfestigkeit [MPa] : 1,17

Components II and III were premixed and then slowly stirred into component I within 20 seconds.

• t _R : 30 sec., t _L : 33 sec., t _A : 40 sec.
• Bulk density [kg / m ³ ]: 28 ₀
• Compressive strength [MPa]: 1.17

Comparative Example 8b)

If the components from Example 8 were mixed at the same time, a highly viscous, non-pourable reaction mixture without foaming tendency was obtained after 30 seconds of stirring.

Example 9

• tR : 30 sec., t_L : 38 sec., t_A : 52 sec.
• Rohdichte [kg/m³] : ₃₇₀
• Druckfestigkeit [MPa] : 1,21

Foaming was carried out according to Example 1.

• tR: 30 sec., t _L : 38 sec., t _A : 52 sec.
• Bulk density [kg / m ³ ]: ₃₇₀
• Compressive strength [MPa]: 1.21

Comparative Example 9a)

If the components from Example 9 were mixed simultaneously, a pourable reaction mixture was obtained after t _R = 20 sec. Stirring time and solidified after t _L = 32 sec. And after t _A = 70 sec. The product had voids and was sandy, inhomogeneous and not very solid.

Example 10

• t_R : 30 sec., t_L: 37 sec., t_A : 51 sec.
• Raumgewicht [kg/m³] : 245

The foaming was carried out according to Example 1. A hard heavy foam with the values:

• t _R : 30 sec., t _L : 37 sec., t _A : 51 sec.
• Density [kg / m ³ ]: 245

Comparative Example 10a)

If one tried to mix the components from Example 10 at the same time, the reaction mixture suddenly gelled.

Example 11

Component I was premixed for 5 seconds with a high-speed stirrer and then for 10 seconds with component II to the primary dispersion stirred. After a total stirring time of 15 seconds, component III was stirred in. After t _R = 30 sec. The reaction mixture was poured into a paper packet, started to foam after t _L = 36 sec. And had solidified after t _A = 130 sec. A tough, elastic, inorganic-organic lightweight foam with a bulk density of 78 _kg / m ^{3 was obtained} .

Comparative Example 11a)

If the components according to Example 11 were mixed simultaneously, a reaction mixture was obtained after 30 seconds of stirring, which foamed after t _L = 32 seconds and solidified after t _A = 75 seconds. A very disturbed foam with a large cavity was obtained.

Example 12

• t_R : 30 sec., t_L : 36 sec., t_A : 90 sec.
• Rohdichte [kg/m³] :70

Foaming was carried out according to Example 11. A tough, elastic light foam was obtained with the values:

• t _R : 30 sec., t _L : 36 sec., t _A : 90 sec.
• Bulk density [kg / m ³ ]: 70

Comparative Example 12a)

If the components according to Example 12 were mixed simultaneously, a reaction mixture was obtained after t _R = 30 sec. Stirring time, which foamed after 35 sec. And collapsed during the foaming.

Claims (8)

1. Process for the production of inorganic-organic plastics of high strength, elasticity, heat resistance and flame resistance consisting of a polymer-polysilicic acid gel composite material present as a colloidal xerosol by mixing a) an organic polyisocyanate ' b) an aqueous basic solution and / or an aqueous basic suspension with an inorganic solid content of 20-80% by weight, preferably 30-70% by weight, c) contains a flowable inorganic compound, and optionally d) catalysts and other additives
and allowing the resulting mixture to react. characterized in that the mixing is carried out in such a way that component a) and b), if appropriate with the addition of all or part of component d), is first converted to a stable primary suspension and then component c), if appropriate with addition all or part of component d) is added to form a final dispersion. 2. The method according to claim 1, characterized in that aqueous alkali silicate solutions or aqueous silica sols are used as the aqueous, basic solution or suspension. 3. The method according to claim 1 and 2, characterized in that sodium silicate with an Na ₂ O: SiO ₂ molar ratio in the range of 1: 1.6 to 3.3 is used as the alkali silicate. 4. The method according to claim 1-3, characterized in that phosgenation products of aniline / formaldehyde condensation are used as organic polyisocyanates. 5. The method according to claim 1-4, characterized in that a polyisocyanate having ion groups is used as the polyisocyanate. 6. The method according to claim 5, characterized in that the ion group-containing polyisocyanate is a sulfonic acid and / or sulfonate group-containing polyisocyanate. 7. The method according to claim 1-3, characterized in that a prepolymer containing terminal isocyanate groups containing non-ionic hydrophilic groups is used as the polyisocyanate. 8. Inorganic-organic plastics obtainable according to claim 1 from 50-90 wt .-% inorganic aqueous phase and 10-50 wt .-% organic phase.