EP0000579B1 - Process for the preparation of inorganic-organic synthetic resins - Google Patents

Process for the preparation of inorganic-organic synthetic resins Download PDF

Info

Publication number
EP0000579B1
EP0000579B1 EP78100504A EP78100504A EP0000579B1 EP 0000579 B1 EP0000579 B1 EP 0000579B1 EP 78100504 A EP78100504 A EP 78100504A EP 78100504 A EP78100504 A EP 78100504A EP 0000579 B1 EP0000579 B1 EP 0000579B1
Authority
EP
European Patent Office
Prior art keywords
sec
weight
polyisocyanate
inorganic
aqueous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100504A
Other languages
German (de)
French (fr)
Other versions
EP0000579A1 (en
Inventor
Hans-Joachim Dr. Scholl
Dieter Dr. Dieterich
Peter Dr. Markusch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0000579A1 publication Critical patent/EP0000579A1/en
Application granted granted Critical
Publication of EP0000579B1 publication Critical patent/EP0000579B1/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/775—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • 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 2 325 909 and 2 310 559.
  • plastics can be produced which, due to the inorganic components, have above all improved fire resistance compared to purely organic substances and which, depending on the composition and reaction conditions, can be foamed or unfoamed, 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.
  • the plastics resulting from a W / 0 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.
  • 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.
  • the process according to the invention can be carried out continuously or preferably batchwise.
  • the stable primary dispersion is first prepared from polyisocyanate, aqueous alkali silicate solution or aqueous silica sol and optionally further additives (components d) and / or e)) such as activators, emulsifiers and blowing agents and then component c) is added.
  • component c component c
  • 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, and mixing with component c) takes place continuously in a downstream mixing head.
  • the individual components are mixed, for example, in the order that first spatially and temporally from components a) and b), optionally with the addition of all or part of components d) and / or e), a dispersion with the aid of a Mixing unit is produced and this dispersion in a spatially and temporally thereafter arranged mixing / aggregate component c), optionally with the addition of all or part of component d) and / or e) is added.
  • Starting components (component a) to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those as mentioned in DE-A-2 647 482, pages 5-6.
  • distillation residues obtained in the industrial production of isocyanate groups optionally dissolved in one or more of the above. called polyisocyanates to use. It is also possible to use any mixtures of the aforementioned polyisocyanates.
  • polyisocyanates e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers
  • TDI polyisocyanates
  • polyphenylpolymethylene 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 polyisocyanates ("modified polyisocyanates").
  • polyisocyanates containing ionic groups for example sulfonated polyisocyanates (DE-A-2 227 111, 2 359 614, 2 359 615), polyisocyanates containing carboxylate groups (DE - A - 2 359 613).
  • nonionic-hydrophilic polyisocyanates as described in DE-A-2 325 909, furthermore polyisocyanates containing polar groups according to DE-A-2 359 608 and phenolic OH groups containing polyisocyanates, as described in US Pat DE - A - 2 359 616.
  • 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 have between 5000 and 5000 000 mPa s / 25 ° C, an NCO content of 28-33 weight percent and a functionality> 2.
  • aqueous alkali silicate solutions or alkaline stabilized aqueous silica sols with an inorganic solid content of 20-80% by weight are also used as starting components (component b). preferably 30-70 wt .-%, used.
  • Aqueous solutions of alkali silicates are to be understood as meaning the solutions of sodium and / or potassium silicate in water which are usually referred to as “water glasses”.
  • Raw technical solutions which are e.g. Calcium silicate, magnesium silicate, borates and aluminates can be used.
  • the molar ratio Me 2 0 / S'0 2 (Me alkali metal, eg Na, K.) Is not critical and can fluctuate 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 minor role because water does not interfere or because it can be easily removed by drying, then only alkaline sodium silicate, of which 20-35% by weight can be used, can be safely used. Have% solutions made. Preferably, however, 32-54% by weight silicate solutions are used which only have the viscosity of less than 50,000 mPas required for problem-free processing if they are sufficiently alkaline. Ammonium silicate solutions, for example solutions of guanidinium silicate, can also be used, but these are less preferred. It can be real or colloidal solutions.
  • concentration mainly depends on the desired 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 produced.
  • silicate solutions with a 30-35% by weight content are preferred for the production of open-pore lightweight 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 of 30-35% content are preferred.
  • alkali 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.
  • Component c) can also be identical to component b) in some cases.
  • component c) are water, an aqueous alkali silicate solution or an aqueous suspension of fillers which have a solids content of between 20 and 80% by weight and at least 50% by weight of a particle size of less than 50 microns (preferably 50% by weight below 10 microns) to understand.
  • Inert mineral fillers or also hydraulic mineral binders are preferably suitable as fillers. 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. Are the particles 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.
  • 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.
  • a mixing device e.g. a screw within this feed line
  • hydraulic binders especially cement
  • the use of hydraulic binders, especially 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 mPa s 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 mPas is preferably not exceeded. A good and very intimate mixture 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 selected if non-spherical fillers are also used, e.g. Asbestos, talc, clays or special iron oxides.
  • isocyanate catalysts (component d) are also often used, e.g. those as described in DE-A-2 647 482, pages 13-15.
  • the catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of polyisocyanate.
  • customary additives can also be used, including the substances mentioned below: surface-active additives such as emulsifiers and foam stabilizers, reaction retarders, cell regulators of the type known per se, pigments, dyes, flame retardants of the type known per se, and further Stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances (see, for example, DE - A - 2 647 482, pages 15-16), volatile organic substances as blowing agents.
  • surface-active additives such as emulsifiers and foam stabilizers, reaction retarders, cell regulators of the type known per se, pigments, dyes, flame retardants of the type known per se, and further Stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances (see, for example, DE - A - 2 647 482, pages 15-16), volatile organic substances as blowing agents.
  • 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.
  • Suspensions as component c) which are prepared with the addition of 0.05 to 20% by weight, based on filler, of one or more of the additives listed under 1), 2) and 3) are particularly preferred.
  • 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 component c) used.
  • the batch process is preferably used when the following fillers component e) are used as aqueous suspensions with component c) (since they partially spontaneously gel aqueous alkali silicates): calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, chalk, lime, dolomite, calcium sulfate , Gypsum and anhydride.
  • fillers (component e) in a suspension as component c) which allow the use of both the batch and the continuous process (those which do not or only slowly gel aqueous alkali silicates) are e.g. 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.
  • 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 hardening, can lead to disruptions in the structure of the inorganic-organic plastic, because inorganic substances, introduced by conventional mixing techniques, can initiate segregation processes and thus the production prevent technically usable inorganic-organic plastics.
  • plastics that can be produced 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, railway 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 pieces, etc. You can get decorative panels such as those used as facade elements.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Description

Anorganisch-organische Kunststoffe auf Basis von Polyisocyanaten und wäßrigen Alkalisilikatlösungen sind bekannt; vergl. z.B. 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 2 325 909 und 2 310 559.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 2 325 909 and 2 310 559.

Auf diese Weise lassen sich Kunststoffe herstellen, die aufgrund der anorganischen Anteile gegenüber rein organischen Stoffen vor allem verbesserte Brandwidrigkeit aufweisen und die je nach Zusammensetzung und Reaktionsbedingungen geschäumt oder ungeschäumt, hart oder weich, spröde oder flexibel sein können. Durch die große Variabilität der Eigenschaften bieten diese anorganisch-organischen Kunststoffe ein breites Spektrum von Anwendungsmöglichkeiten.In this way, plastics can be produced which, due to the inorganic components, have above all improved fire resistance compared to purely organic substances and which, depending on the composition and reaction conditions, can be foamed or unfoamed, 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.

Diesen Kombinationskunststoffen ist gemeinsam, daß zu ihrer Herstellung die organische und die anorganische Phase miteinander vermischt werden müssen. Hierbei entstehen Dispersionen vom Typ W/O (Wasser in 01) oder O/W (01- in-Wasser).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 01) or O / W (01 in water).

Die aus einer Dispersion vom Typ W/0 hervorgegangenen Kunststoffe sind besonders interessant. Sie weisen, auch unter Feuchteinwirkung, hohe mechanische Festigkeiten auf, weil die gehärtete kohärente organische Phase die ebenfalls gehärtete wäßrige anorganische inkohärente Phase umhüllt und damit fixiert. Von der perfekten kohärenten organischen Phase dieser Kunststoffe hängt aber auch, bedingt durch die eingeschlossene Wassermenge, die verbesserte Brandwidrigkeit derartiger Systeme ab.The plastics resulting from a W / 0 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.

Man hat versucht, zur Herstellung der beschriebenen Kunststoffe die Reaktionskomponenten in einer diskontinuierlich oder kontinuierlich arbeitenden Mischvorrichtung einstufig oder in mehreren Stufen miteinander zu vermischen und die entstandene Dispersion anschließend erstarren zu lassen.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.

Man erhält auf diese Weise indessen in der Regel Produkte, die mit zunehmendem Anteil an anorganischer Komponente in steigendem Maße ihre mechanische Festigkeit verlieren und im Extremfall sogar sandartigen Charakter und Hohlräume aufweisen. Gerade diese Produkte mit hohen anorganischen Anteilen sind jedoch aus wirtschaftlichen Gründen und wegen ihrer erhöhten Brandwidgrigkeit besonders interessant.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.

Der Erfindung liegt die Aufgabe zugrunde, die oben beschriebenen Nachteile zu vermeiden und anorganisch-organische Kunststoffe, auch bei hohen Mengen an anorganischen Anteilen, problemlos herzustellen.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.

Diese Aufgabe wird mit dem erfindungsgemäßen Verfahren gelöst. Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung anorganisch-organischer Kunststoffe hoher Festigkeit, Elastizität, Wärmeformbeständigkeit und Schwerentflammbarkeit bestehend aus einem als kolloids Xerosol vorliegenden Polymer-Polykieselsäuregel-Verbundmaterial durch Vermischen von

  • a) einem organischen Polyisocyanat,
  • b) einer wäßrigen Alkalisilikatlösung oder einem wäßrigen Kieselsol mit Gehalten an anorganischem Feststoff von 20-80 Gewichtsprozent,
  • c) Wasser, einer wäßrigen Alkalisilikatlösung und/oder einer wäßrigen Suspension von Füllstoffen mit einem Feststoffgehalt zwischen 20 und 80 Gewichtsprozent wobie die Füllstoffe zu mindestens 50 Gewichtsprozent, eine Teilchengröße von kleiner als 50 Mikron aufweisen, und gegebenenfalls zusätzlich,
  • d) Isocyanat-Katalysatoren und/oder e) weiteren üblichen Zusatzmitteln
und Ausreagierenlassen des so erhaltenen Gemischs, dadurch gekennzeichnet, daß die Vermischung in der Weise vorgenommen wird, daß zunächst die Komponente a) und b), gegebenenfalls unter Zusatz der ganzen Menge oder eines Teils der Komponente d) und/oder e) zu einer stabilen Primärdispersion umgesetzt und anschließend Komponente c), gegebenenfalls unter Zusatz der ganzen Menge oder eines Teils der Komponente d) und/oder e) unter Ausbildung einer Enddispersion zugegeben wird, wobei die Enddispersion vor Beginn des Aushärtens bei Raumtemperatur einen Viskositätsbereich von 600-6000 mPa s aufweist und aus 50-90 Gewichtsprozent anorganisch-wäßriger Phase und 10-50 Gewichtsprozent organischer Phase besteht.This object is achieved with the method according to the invention. The present invention 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 alkali silicate solution or an aqueous silica sol with an inorganic solid content of 20-80 percent by weight,
  • c) water, an aqueous alkali silicate solution and / or an aqueous suspension of fillers with a solids content of between 20 and 80 percent by weight, the fillers having at least 50 percent by weight, a particle size of less than 50 microns, and optionally additionally,
  • d) isocyanate catalysts and / or e) other customary additives
and allowing the mixture thus obtained to react, characterized in that the mixing is carried out in such a way that first component a) and b), optionally with the addition of all or part of component d) and / or e) to a stable one Primary dispersion implemented and then component c), optionally with the addition of all or part of component d) and / or e) is added to form a final dispersion, the final dispersion before the start of curing at room temperature a viscosity range of 600-6000 mPa s has and consists of 50-90 weight percent inorganic-aqueous phase and 10-50 weight percent organic phase.

Das erfindungsgemäße Verfahren kann kontinuierlich oder vorzugsweise diskontinuierlich durchgeführt werden. Nach der diskontinuierlichen Arbeitsweise wird zuerst die stabile Primärdispersion aus Polyisocyanat, wäßriger Alkalisilikatlösung oder wäßrigem Kieselsol und gegebenenfalls weiteren Zusatzmitteln (Komponenten d) und/oder e)) wie Aktivatoren, Emulgatoren und Treibmitteln hergestellt und dann die Zugabe der Komponente c) vorgenommen. Nach der kontinuierlichen Arbeitsweise wird entsprechend der diskontinuierlichen Arbeitsweise durch eine spezielle maschinelle Anordnung vorab die Primärdispersion in einer Vorkammer erzeugt, die Vermischung mit der Komponente c) erfolgt kontinuierlich in einem nachgelagerten Mischkopf.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 alkali silicate solution or aqueous silica sol and optionally further additives (components d) and / or e)) such as activators, emulsifiers and blowing agents and then 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, and mixing with component c) takes place continuously in a downstream mixing head.

Erfindungsgemäß wird eine Vermischung der einzelnen Komponenten z.B. in der Reihenfolge vorgenommen, daß räumlich und zeitlich zuerst aus den Komponenten a) und b), gegebenenfalls unter Zusatz der ganzen Menge oder eines Teils der Komponentel d) und/oder e) eine Dispersion mit Hilfe eines Mischaggregats hergestellt wird und zu dieser Dispersion in einem räumlich und zeitlich danach angeordneten Misch/aggregat die Komponente c), gegebenenfalls unter Zusatz der ganzen Menge oder eines Teils der Komponente d) und/oder e) zugegeben wird.According to the invention, the individual components are mixed, for example, in the order that first spatially and temporally from components a) and b), optionally with the addition of all or part of components d) and / or e), a dispersion with the aid of a Mixing unit is produced and this dispersion in a spatially and temporally thereafter arranged mixing / aggregate component c), optionally with the addition of all or part of component d) and / or e) is added.

Als erfindungsgemäß einzusetzende Ausgangskomponenten (Komponente a) kommen aliphatische, cycloaliphatische, araliphatische, aromatische und heterocyclische Polyisocyanate in Betracht, wie sie z.B. von W. Siefken in Justus Liebigs Annalen der Chemie, 562, Seiten 75 bis 136, beschrieben werden, beispielsweise solche, wie sie in der DE - A - 2 647 482, Seiten 5-6, genannt werden.Starting components (component a) to be used according to the invention are aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates, such as those e.g. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example those as mentioned in DE-A-2 647 482, pages 5-6.

Es ist auch möglich, die bei der technischen Isocyanatherstellung anfallenden Isocyanatgruppen aufweisenden Destillationsrückstände, gegebenenfalls gelöst in einem oder mehreren der vorge-. nannten Polyisocyanate, einzusetzen. Ferner ist es möglich, beliebige Mischungen der vorgenannten Polyisocyanate zu verwenden.It is also possible to have the distillation residues obtained in the industrial production of isocyanate groups, optionally dissolved in one or more of the above. called polyisocyanates to use. It is also possible to use any mixtures of the aforementioned polyisocyanates.

Besonders bevorzugt werden in der Regel die technisch leicht zugänglichen Polyisocyanate, z.B. das 2,4- und 2,6-Toluylendiisocyanat sowie beliebige Gemische dieser Isomeren ("TDI"), Polyphenylpolymethylen-polyisocyanate, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung hergestellt werden ("rohes MDI") und Carbodiimidgruppen, Urethangruppen, Allophanatgruppen, Isocyanuratgruppen, Harnstoffgruppen oder Biuretgruppen aufweisenden Polyisocyanate ("modifizierte Polyisocyanate").The technically easily accessible polyisocyanates, e.g. 2,4- and 2,6-tolylene diisocyanate as well as any mixtures of these isomers ("TDI"), polyphenylpolymethylene 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 polyisocyanates ("modified polyisocyanates").

Erfindungsgemäß besonders bevorzugt sind ionische Gruppen aufweisende Polyisocyanate, wie sie in der DE - A - 2 227 147 beschrieben werden, beispielsweise sulfonierte Polyisocyanate (DE - A - 2 227 111, 2 359 614, 2 359 615), Carboxylatgruppen aufweisende Polyisocyanate (DE - A - 2 359 613). Erfindungsgemäß bevorzugt sind auch nicht ionisch-hydrophile Polyisocyanate, wie sie in der DE - A - 2 325 909 beschrieben werden, ferner polare Gruppen aufweisende Polyisocyanate gemäß der DE - A - 2 359 608 und phenolische OH-Gruppen aufweisende Polyisocyanate, wie sie in der DE - A - 2 359 616 genannt werden.According to the invention, particular preference is given to polyisocyanates containing ionic groups, as described in DE-A-2 227 147, for example sulfonated polyisocyanates (DE-A-2 227 111, 2 359 614, 2 359 615), polyisocyanates containing carboxylate groups (DE - A - 2 359 613). Also preferred according to the invention are nonionic-hydrophilic polyisocyanates, as described in DE-A-2 325 909, furthermore polyisocyanates containing polar groups according to DE-A-2 359 608 and phenolic OH groups containing polyisocyanates, as described in US Pat DE - A - 2 359 616.

Die obengenannten, besonders bevorzugten Polyisocyanate werden vorzugsweise aus Polyphenyl-polymethylen-polyisocyanaten, wie sie durch Anilin-Formaldehyd-Kondensation und anschließende Phosgenierung hergestellt werden ('rohes MDI') sowie aus den daraus durch Abdestillation von Zweikernprodukten erhältlichen Destillationsrückständen, die im allgemeinen eine Viskosität zwischen 5000 und 5000 000 mPa s/25°C, einem NCO-Gehalt von 28-33 Gewichtsprozent sowie eine Funktionalität >2 aufweisen, hergestellt.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 have between 5000 and 5000 000 mPa s / 25 ° C, an NCO content of 28-33 weight percent and a functionality> 2.

Erfindungsgemäß werden ferner als Ausgangskomponenten (Komponente b) wäßrige Alkalisilikatlösungen oder alkalisch stabilisierte wäßrige Kieselsole mit einem Gehalt an anorganischem Feststoff von 20-80 Gew.-%. vorzugsweise 30-70 Gew.-%, eingesetzt.According to the invention, aqueous alkali silicate solutions or alkaline stabilized aqueous silica sols with an inorganic solid content of 20-80% by weight are also used as starting components (component b). preferably 30-70 wt .-%, used.

Unter wäßrigen Lösungen von Alkalisilikaten sind die üblicherweise als "Wasserglas" bezeichneten Lösungen von Natrium- und/oder Kaliumsilikat in Wasser zu verstehen. Es können auch rohe technische Lösungen, welche zusätzlich z.B. Calciumsilikat, Magnesiumsilikat, Borate und Aluminate erhalten können, Verwendung finden.Aqueous solutions of alkali silicates are to be understood as meaning the solutions of sodium and / or potassium silicate in water which are usually referred to as “water glasses”. Raw technical solutions, which are e.g. Calcium silicate, magnesium silicate, borates and aluminates can be used.

Das molare Verhältnis Me20/S'02 (Me = Alkalimetall, z.B. Na,K.) ist nicht kritisch und kann in den üblichen Grenzen schwanken; vorzugsweise beträgt es 1:1,6 bis 1:3,3. Spielt der Wassergehalt des durch Umsetzung mit dem Polyisocyanat zunächst erhaltenen Kunststoffs eine untergeordnete Rolle, weil Wasser nicht stört oder weil es leicht durch Trocknen entfernt werden kann, so kann unbedenklich nur schwash alkalisches Natriumsilikat eingesetzt werden, von welchem sich z.B. 20-35 Gew.-%ige Lösungen herstellen lassen. Vorzugsweise werden indessen 32-54 Gew.-%ige Silikatlösungen eingesetzt, die nur bei hinreichender Alkalität die für eine problemlose Verarbeitung erforderliche Viskosität von unter 50 000 mPa s aufweisen. Auch Ammoniumsilikatlösungen, z.B. Lösungen von Guanidiniumsilikat, können verwendet werden, allerdings sind diese weniger bevorzugt. Es kann sich um echte oder auch um kolloide Lösungen handeln.The molar ratio Me 2 0 / S'0 2 (Me = alkali metal, eg Na, K.) Is not critical and can fluctuate 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 minor role because water does not interfere or because it can be easily removed by drying, then only alkaline sodium silicate, of which 20-35% by weight can be used, can be safely used. Have% solutions made. Preferably, however, 32-54% by weight silicate solutions are used which only have the viscosity of less than 50,000 mPas required for problem-free processing if they are sufficiently alkaline. Ammonium silicate solutions, for example solutions of guanidinium silicate, can also be used, but these are less preferred. It can be real or colloidal solutions.

Die Wahl der Konzentration hängt vor allem vom gewünschten Endprodukt ab. Kompakte oder geschlossenzellige Materialien werden vorzugsweise mit konzentrierten Silikatlösungen hergestellt, die erforderlichenfalls durch Zusatz von Alkalihydroxid auf niedrige Viskosität eingestellt werden. Auf diese Weise lassen sich 40-70 Gew.-%ige Lösungen herstellen. Andererseits werden zur Herstellung offenporiger Leichtschaumstoffe Silikatlösungen mit 30-35 Gew.-%igem Gehalt bevorzugt, um niedrige Viskositäten, ausreichend lange Reaktionszeiten und niedere Raumgewichte zu erzielen. Auch bei Einsatz feinteiliger anorganischer Füllstoffe in größeren Mengen sind Silikatlösungen von 30-35%igem Gahalt bevorzugt.The choice of concentration mainly depends on the desired 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 produced. On the other hand, silicate solutions with a 30-35% by weight content are preferred for the production of open-pore lightweight 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 of 30-35% content are preferred.

Weitere ausführliche Angaben über erfindungsgemäß brauchbare Alkalisilikatlösungen findet man bei James G. Vail 'Soluble Silicates, their properties and uses', Reinhold Publishing Corporation, New York 1952.Further detailed information on alkali 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.

Die Komponente c) kann auch in einigen Fällen mit der Komponente b) identisch werden.Component c) can also be identical to component b) in some cases.

Als Komponente c) sind Wasser, eine wäßrige Alkalisilikatlösung oder eine wäßrige Suspension von Füllstoffen, die einen Feststoffgehalt zwischen 20 und 80 Gew.-% und zu mindestens 50 Gew.-% eine Teilchengröße von unter 50 Mikron (yorzugsweise 50 Gew.-% unter 10 Mikron) aufweisen, zu verstehen. Vorzugsweise kommen hier inerte mineralische Füllstoffe oder auch hydraulische mineralische Bindemittel als Füllstoffe in Frage. Sofern die trockenen Füllstoffe bereits die erfindungsgemäßen Kriterien hinsichtlich der Teilchengröße erfüllen (mindestens 50 Gew.-% kleiner als 50 Mikron), können sie unmittelbar mit Wasser zu einer Suspension angerührt werden. Sind die Teilchen gröber, so kann auch eine wäßrige Grobsuspension der Füllstoffe durch bekannte Verfahren der Naßmahlung in einer erfindungsgemäß brauchbare Feinsuspension übergeführt werden.As component c) are water, an aqueous alkali silicate solution or an aqueous suspension of fillers which have a solids content of between 20 and 80% by weight and at least 50% by weight of a particle size of less than 50 microns (preferably 50% by weight below 10 microns) to understand. Inert mineral fillers or also hydraulic mineral binders are preferably suitable as fillers. 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. Are the particles 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.

Besonders bevorzugte wäßrige Suspensionen sind solche, welche sedimentationsstabil sind und ein viskoses zügiges Fließverhalten zeigen, wie es beispeilsweise von Papierstreichmassen bekannt ist. Zur Herstellung solcher Füllstoffsuspensionen bedient man sich daher vorteilhaft der zur Herstellung solcher Streichmassen bekannten Methoden.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.

Erfindungsgemäß bevorzugte stabilisierte Suspensionen sind solche, welche innerhalb von einem Tag nicht nennenswert sedimentieren und ein zügiges viskoses Fließverhalten zeigen. Im Rahmen vorliegender Erfindung gelten wäßrige Füllstoff-Suspensionen dann als 'stabilisiert', wenn die dispergierten Füllstoffe durch eine oder mehrere der nachfolgend aufgeführten Maßnahmen oder durch Mitverwendung von später im einzelnen genannten Dispergierhilfsmitteln oder Dispersionsstabilisatoren oder Verdickungsmitteln überwiegend agglomeratfrei als Einzelteilchen dispergiert sind:

  • 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.
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 deemed to be 'stabilized' if the dispersed fillers are dispersed as individual particles predominantly agglomerate-free by one or more of the measures listed below or by the use of dispersing aids or dispersion stabilizers or thickening agents mentioned later in detail:
  • 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, for example, 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.

Selbstverständlich kann die Füllstoff-Suspension auch unmittelbar vor der Zumischung hergestellt werden, z.B. indem in eine Zuleitung zum Mischraum, in dem die Vermischung des Polyisocyanats mit wäßrigem Alkalisilikat stattfindet, trockene Füllstoffe und Wasser eindosiert werden und durch eine Mischvorrichtung, z.B. eine Schnecke innerhalb dieser Zuleitung die wäßrige Füllstoff-Suspension in situ erzeugt wird.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.

Die Verwendung hydraulischer Bindemittel, insbesondere Zement, erfordert im allgemeinen die Suspendierung im Wasser oder wäßrigem Alkalisilikat unmittelbar vor der Verarbeitung mit der Isocyanatkomponente, damit der Abbindeprozeß und ein gegebenenfalls durch Zement verursachter Gelierungsprozeß zweckmäßigerweise im fertigen Kunststoff stattfindet.The use of hydraulic binders, especially 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.

Die eingesetzten Füllstoffsuspensionen weisen vorzugsweise eine Viskosität über 100 mPa s auf, um eine für die Verarbeitung günstiges rheologisches Verhalten zu gewährleisten. Sie sollen andererseits gut fließfähig sein und keinesfalls krümelige Konsistenz aufweisen. Vorzugsweise wird eine Viskosität von 10.000 mPa s nicht überschritten. Eine gute und sehr innige Vermischung mit dem Polyisocyanat in üblichen Verarbeitungsapparaturen sollte gewährleistet sein. Andererseits sollte der Gehalt der wäßrigen Suspension an Füllstoffen möglichst hoch sein, um nicht mehr Wasser als unumgänglich in den Kunststoff einzubringen. In Abhängigkeit von der Teilchengröße und der Gestalt der Füllstoffteilchen beträgt die Füllstoffkonzentration zwischen 20 und 80%. Bevorzugt ist ein Gehalt von 30-70%. Niedere Konzentrationen müssen im allgemeinen dann gewählt werden, wenn nichtkugelige Füllstoffe mitverwendet werden, wie z.B. Asbest, Talk, Tone oder spezielle Eisenoxide.The filler suspensions used preferably have a viscosity above 100 mPa s 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 mPas is preferably not exceeded. A good and very intimate mixture 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 selected if non-spherical fillers are also used, e.g. Asbestos, talc, clays or special iron oxides.

Erfindungsgemäß werden ferner oft Isocyanat-Katalysatoren (Komponente d)) mitverwendet, z.B. solche, wie sie in der DE - A - 2 647 482, Seiten 13-15, beschrieben werden.According to the invention, isocyanate catalysts (component d)) are also often used, e.g. those as described in DE-A-2 647 482, pages 13-15.

Weitere Vertreter von erfindungsgemäß zu verwendenden Katalysatoren sowie Einzelheiten über die Wirkungsweise der Katalysatoren sind im Kunststoff-Handbuch, Band VII, herausgegeben von Vieweg und Höchtlen, Carl-Hanser-Verlag, München, 1966, z.B. auf den S.96 bis 102, beschrieben.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.

Die Katalysatoren werden in der Regel in einer Menge zwischen etwa 0,001 und 10 Gew.-%, bezogen auf die Menge an Poiyisocyanat, eingesetzt.The catalysts are generally used in an amount between about 0.001 and 10% by weight, based on the amount of polyisocyanate.

Erfindungsgemäß können auch weitere übliche Zusatzmittel (Komponente e)) mitverwendet werden, zu denen die nachfolgend genannten Substanzen zählen: Oberflächenaktive Zusatzstoffe wie Emulgatoren und Schaumstabilisatoren, Reaktionsverzögerer, Zellregler der an sich bekannten Art, Pigmente, Farbstoffe, Flammschutzmittel der an sich bekannten Art, ferner Stabilisatoren gegen Alterungs- und Witterungseinflüsse, Weichmacher und fungistatisch und bakteriostatisch wirkende Substanzen (vergl. hierzu z.B. DE - A - 2 647 482, Seiten 15-16), leicht flüchtige organische Substanzen als Treibmittel. Als organische Treibmittel kommen z.B. Aceton, Äthylacetat, halogensubstituierte Alkane wie Methylenchlorid, Chloroform, Äthyliden-chlorid, Vinylidenchlorid, Monofluortrichlormethan, Chlordifluormethan, Dichlordifluormethan, ferner Butan, Hexan, Heptan oder Diäthyläther in Frage. Eine Treibwirkung kann auch durch Zusatz von bei Temperaturen über Raumtemperatur unter Abspaltung von Gasen, beispielsweise von Stickstoff, sich zersetzenden Verbindungen, z.B. Azoverbindungen wie Azoisobuttersäurenitril, erzielt werden.According to the invention, other customary additives (component e)) can also be used, including the substances mentioned below: surface-active additives such as emulsifiers and foam stabilizers, reaction retarders, cell regulators of the type known per se, pigments, dyes, flame retardants of the type known per se, and further Stabilizers against aging and weather influences, plasticizers and fungistatic and bacteriostatic substances (see, for example, DE - A - 2 647 482, pages 15-16), volatile organic substances 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.

Auch das in den Komponenten b) und c) enthaltene Wasser kann die Funktion des Treibmittels übernehmen. Ferner können feine Metallpulver, z.B. Calcium, Magnesium, Aluminium oder Zink durch Wasserstoffentwicklung mit ausreichend alkalischem Wasserglas als Treibmittel dienen, wobei sie gleichzeitig eine härtende und verstärkende Wirkung ausüben.
Ferner gegebenenfalls folgende Zusatzmittel:

  • 1) Dispergierhilfsmittel und Dispersionsstabilisatoren, wie Salze der Phosphorsäure, Pyrophosphorsäure, Metaphosphorsäure, Polyphosphorsäure, phosphorigen Säure, Oligokieselsäure, Polykieselsäure, Salze von organischen hochmolekularen Polysäuren, wie z.B. Poly (meth) acrylsäuren, copolymeren Poly (meth) acrylsäuren, Polymaleinsäuren, copolymeren Polymaleinsäuren, wasserlösliche Derivate der Zellulose, Stärke, Alginsäuren sowie Pflanzengummen. Auch die üblichen oberflächenaktiven Verbindungen, wie Emulgatoren, Netzmittel und Tenside kommen in Betracht.
  • 2) Verdickungsmittel, wie Zellulosederivate, Polyacrylamid, Alginate, Pflanzengummen, wasserlösliche Polymere, z.B. Polyäthylenoxid.
  • 3) Hoch- und niedermolekulare Di- oder Polyalkohole oder Di- bzw. Polyamine.
The water contained in components b) and c) can also act as a blowing agent. Furthermore, fine metal powders, for example calcium, magnesium, aluminum or zinc, can be used as blowing agents by developing hydrogen with sufficient alkaline water glass, while at the same time having a hardening and strengthening effect.
Furthermore, if necessary, the following additives:
  • 1) Dispersing aids and dispersion stabilizers, such as salts of phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, phosphorous acid, oligosilicic acid, polysilicic acid, salts of organic high molecular weight polyacids, such as, for example, poly (meth) acrylic acids, copolymeric poly (meth) acrylic acids, polymaleic acids, polymaleic acids water-soluble derivatives of cellulose, starch, alginic acids and plant gums. The usual surface-active compounds, such as emulsifiers, wetting agents and surfactants, are also suitable.
  • 2) Thickeners, such as cellulose derivatives, polyacrylamide, alginates, plant gums, water-soluble polymers, for example polyethylene oxide.
  • 3) High and low molecular weight di- or polyalcohols or di- or polyamines.

Besonders bevorzugt werden Suspensionen als Komponente c) die unter Zusatz von 0,05 bis 20 Gew.-%, bezogen auf Füllstoff, von einer oder mehreren der unter 1), 2) und 3) aufgeführten Zusatzmitteln hergestellt sind.Suspensions as component c) which are prepared with the addition of 0.05 to 20% by weight, based on filler, of one or more of the additives listed under 1), 2) and 3) are particularly preferred.

Weitere Beispiele von gegebenenfalls erfindungsgemäß mitzuverwendenden oberflächenaktiven Zusatzstoffen und Schaumstabilisatoren sowie Zellreglern, Reaktionsverzögerern, Stabilisatoren, flammhemmende Substanzen, Weichmachern, Farbstoffen sowie fungistatisch und bakteriostatisch wirksamen Substanzen sowie Einzelheiten über Verwendungs- und Wirkungsweise dieser Zusatzmittel sind im Kunststoff-Handbuch, Band VII, herausgegeben von Vieweg und Höchtlen, Carl-Hanser-Verlag, München 1966, z.B. auf den S. 103 bis 113, beschrieben.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 fungistatic and bacteriostatic substances, as well as details on the use and mode of action of these additives are published in the plastics manual, Volume VII, by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on pages 103 to 113.

Die Vermischung der Reaktionskomponenten erfolgt vorzugsweise bei Raumtemperatur.The mixing of the reaction components is preferably carried out at room temperature.

Die Wahl des Mischverfahrens hängt weitgehend von der Art der verwendeten Komponente c) ab. Nach dem diskontinuierlichen Verfahren wird dann vorzugsweise gearbeitet, wenn mit der Komponente c) folgende Füllstoffe komponente e) als wäßrige Suspensionen eingesetzt werden (da sie wäßrige Alkalisilikate z.T. spontan gelieren): Calciumhydroxid, Magnesiumhydroxid, Calciumcarbonat, Magnesiumcarbonat, Kreide, Kalk, Dolomit, Calciumsulfat, Gips und Anhydrid. Beispiele für Füllstoffe (Komponente e) in einer Suspension als Komponente c), die die Anwendung sowohl des diskontinuierlichen als auch des kontinuierlichen Verfahrens erlauben (solche, die wäßrige Alkalisilikate nicht oder nur langsam gelieren) sind z.B. Eisenoxide, Aluminiumoxide, Quarzmehl, Tone, Asbest, Gläser in Pulverform, Silikatmineralien und Wasserzemente wie Rotbandzement, schnellbindender Zement oder Tonerdeschmelzzement.The choice of the mixing process largely depends on the type of component c) used. The batch process is preferably used when the following fillers component e) are used as aqueous suspensions with component c) (since they partially spontaneously gel aqueous alkali silicates): calcium hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, chalk, lime, dolomite, calcium sulfate , Gypsum and anhydride. Examples of fillers (component e) in a suspension as component c) which allow the use of both the batch and the continuous process (those which do not or only slowly gel aqueous alkali silicates) are e.g. 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.

Zur Deutung der technischen Vorteile gemäß der Erfindung wird angenommen, daß die nach dem erfindungsgemäßen Verfahren zwischenzeitlich hergestellte Primärdispersion außerordentlich stabil ist und auch weitere Zusätze diesen stabilen Zustand über die Reaktions- und Aushärtungszeit hinaus nicht gefährden.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.

Nach dem bisherigen Stand der Technik erhält man hingegen in der Regel Dispersionen; die bei zunehmend höherem Anteil an anorganischen Komponenten unter Veränderung der W/O-Phasenstruktur instabile Dispergierungszustände durchlaufen, die nach Aushärtung Störungen im Aufbau des anorganisch-organischen Kunststoffs ergeben können, denn anorganische Substanzen können, nach herkömmlichen Mischtechniken eingebracht, Entmischungsvorgänge einleiten und dadurch die Herstellung technisch brauchbarer anorganisch-organischer Kunststoffe verhindern.According to the prior art, however, 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 hardening, can lead to disruptions in the structure of the inorganic-organic plastic, because inorganic substances, introduced by conventional mixing techniques, can initiate segregation processes and thus the production prevent technically usable inorganic-organic plastics.

Die erfindungsgemäß herstellbaren Kunststoffe einschließlich Schaumstoffe eröffnen neue Möglichkeiten im Hoch- und Tiefbau sowie bei der Herstellung von Fertigteilen und Elementen.The plastics that can be produced 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.

Beispielhaft seien als Anwendungsmöglichkeiten die Herstellung von Wandelelementen im Fertigbau, verlorene Schalungen, Rolladenkästen, Fensterbänken, Eisenbahn- und U-Bahn-Schwellen, Bordsteinen, Treppen, die Ausschäumung von Fugen sowie die Hinterschäumung von Kermikfliesen genannt.Examples of possible applications include the manufacture of convertible elements in prefabricated buildings, lost formwork, roller shutter boxes, window sills, railway and subway sleepers, curbs, stairs, the foaming of joints and the back-foaming of ceramic tiles.

Vorteilhaft läßt sich der Schaumbeton auch zum Binden von Kies, Marmorstücken usw. einsetzen. Man kann so dekorative Platten erhalten, wie sie beispielsweise als Fassadenelemente Verwendung finden.The foam concrete can also be used advantageously to bind gravel, marble pieces, etc. You can get decorative panels such as those used as facade elements.

Die Erfindung wird nachstehend and Hand von Beispielen näher erläutert:The invention is explained in more detail below with the aid of examples:

BEISPIELEEXAMPLES (%-Angaben sind, falls nicht anders vermerkt, Gew.-%-Angaben).(Unless otherwise noted,% figures are percentages by weight).

Ausgangsmaterialien:

  • (1) Komponenten a)
    • A3: Von rohem Phosgenierungsprodukt eines Anilin/Formaldehyd-Kondensats wird soviel Diisocyanato-diphenylmethan abdestilliert, daß der Destillationsrückstand bei 25°C eine Viskosität von 400 mPas aufweist. (2-Kernanteil: 45,1 Gew.-%, 3-Kernanteil:, 22,3 Gew.-%, Anteil an höherkernigen Polyisocyanaten: 32,6 Gew.-%) NCO-Gehalt: 30-31 Gew.-%.
    • A,: Mit gasförmigem Schwefeltrioxid sulfoniertes A3 (Schwefelgehalt: 0.96%, NCO-Gehalt: 30,5%, Viskosität bei 25°C: 24000 mPas, Herstellung s. DT-OS 2 227 1 1 1
    • AZ: Entsprechend mit Chlorsulfonsäure sulfoniertes A3 (Schwefelgehalt: 0.9%, NCO-Gehalt: 30,2% Viskosität bei 20°C: 2000 mPas).
  • (2) Komponenten b)
    • B1: Natriumwasserglas, 44% Feststoff, Molgewichtverhältnis Na2O: SiO2 = 1:2
    • B2: Natriumwasserglas, 48,6% Feststoff, Molgewichtverhältnis Na2O:SiO2 = 1:2
  • (3) Komponenten c)
    • C1: In 1000 g einer 54%igen Natriumsilikatlösung mit einem SiO2/Na2O-Verhältnis von 2,0 werden bei Raumtemperatur 1000 g eines Filterschlamms des Typs Eisenoxidschwarz 320 der Firma Bayer AG mit einem Feststoffgehalt von 62% unter einer vorherrschenden Teilchengröße von 0,2µ (das Pigment beseitzt Kugelform) eingerührt. Die entstandene sedimentationsstabile Suspension hat folgende Zusammensetzung:
      • 31 Gew.-% Eisenoxid
      • 27 Gew.-% Natriumsilikat
      • 42 Gew.-% Wasser
    • C2: In 2,5 kg Wasser, 100 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 µ; Weißkalkhydrat der Firma Arminia-Hydroka) suspendiert. Feststoffgehalt: 47%
  • (4) Komponenten e)
    • E1: Auf Äthylendiamin gestarteter Polypropylentetraalkohol OH-Zahl: 630
    • E2: Auf n-Butanol gestartteter Polyäthylenoxid-monoalkohol OH-Zahl: 49,2
Starting materials:
  • (1) Components a)
    • A 3 : So much diisocyanatodiphenylmethane is distilled off from the crude phosgenation product of an aniline / formaldehyde condensate that the distillation residue at 25 ° C. has a viscosity of 400 mPas. (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,: A 3 sulfonated with gaseous sulfur trioxide (sulfur content: 0.96%, NCO content: 30.5%, viscosity at 25 ° C: 24000 mPas, production see DT-OS 2 227 1 1 1
    • A Z : A 3 correspondingly sulfonated with chlorosulfonic acid (sulfur content: 0.9%, NCO content: 30.2% viscosity at 20 ° C: 2000 mPas).
  • (2) components b)
    • B 1 : sodium water glass, 44% solids, molar weight ratio Na 2 O: SiO 2 = 1: 2
    • B 2 : sodium water glass, 48.6% solids, molar weight ratio Na 2 O: SiO 2 = 1: 2
  • (3) components c)
    • C 1 : 1000 g of a filter sludge of the type iron oxide black 320 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 O ratio of 2.0 at room temperature of 0.2µ (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
    • C 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% strength aqueous iron (III) chloride solution, 2 , 5 kg of white lime hydrate (particle size: 80% <30 μ; white lime hydrate from Arminia-Hydroka) suspended. Solids content: 47%
  • (4) Components e)
    • E 1 : Polypropylene tetraalcohol started on ethylenediamine OH number: 630
    • E2: Polyethylene oxide monoalcohol started on n-butanol OH number: 49.2

In den nachfolgenden Beispielen bedeuten

  • tR = Rührzeit (Mischzeit der Mischungen)
  • tL = Liegezeit, Zeitraum von Beginn des Mischens bis zum Beginn des Aufschäumens
  • tA = Abbindezeit, Zeitraum von Beginn des Mischens bis zur Erhärtung.
Mean in the examples below
  • t R = stirring time (mixing time of the mixtures)
  • t L = lying time, period from the start of mixing to the start of foaming
  • t A = setting time, period from the start of mixing to hardening.

BEISPIEL 1EXAMPLE 1

Figure imgb0001
Figure imgb0001

Mischung I und II wurden 10 sec. mit einem Schnellrührer vorgemischt, Mischung III wurde anschließend innerhalb von 10 sec. unter Rühren zugegeben. Nach tR = 30 sec. Gesamtmischzeit wurde das Reaktionsgemisch in ein Papierpäckchen ausgegossen, begann nach tL = 40 sec. aufzuschäumen und war nach tA = 58 sec. erstarrt. Man erhielt einen harten anorganisch-organischen Schwerschaum mit den Werten:

  • Rohdichte [kg/m3]: 152
  • Druckfestigkeit [MPa]: 0,77
Mixtures I and II were premixed for 10 seconds with a high-speed stirrer, and mixture III was then added over the course of 10 seconds with stirring. 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

Vergleichsbeispiel 1 a)Comparative Example 1 a)

Gemäß Beispiel 1 wurden Mischungen II und III vorgemischt und schnell innerhalb von 5 sec. in Mischung I eingeruhrt. Nach tR = 30 sec. Mischzeit wurde das Gemisch in ein Papierpäckchen ausgegossen begann nach tL = 44 sec. aufzuschäumen und war nach tA = 68 sec. unter Ausbildung eines Hohlraums erstarrt. Man erhielt einen sandigen, inhomogenen, hohlraumhaltigen Kunststoff ohne vergleichbare Druckfestigkeit.According to Example 1, mixtures II and III were premixed and rapidly mixed into mixture I within 5 seconds. After t R = 30 sec. Mixing time, the mixture was poured into a paper packet and started to foam up after t L = 44 sec. And solidified after t A = 68 sec. To form a cavity. A sandy, inhomogeneous, void-containing plastic was obtained without comparable pressure resistance.

BEISPIEL 2EXAMPLE 2

Figure imgb0002
Figure imgb0002

Die Verschäumung wurde gemäß Beispiel 1 durchgeführt. Man erhielt einen harten anorganisch-organischen Schwerschaum mit den Werten:

  • tR: 30 sec., tL: 37 sec., tA: 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:
  • t R : 30 sec., t L : 37 sec., t A : 54 sec.
  • Bulk density [kg / m 3 ]: 241
  • Compressive strength [MPa]: 0.3

Vergleichsbeispiel 2a)Comparative Example 2a)

Vermischte man die Mischungen I, II und III aus Beispiel 2 gleichzeitig, so erhielt man innerhalb von 30 sec. Rührzeit ein hochviskoses, nicht gießbares Reaktionsgemisch ohne Aufschäumtendenz.If mixtures 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.

Vergleichsbeispiel 2b)Comparative Example 2b)

Vermischte man die Mischungen I, II und III aus Beispiel 2 gleichzeitig mit der Maßgabe, daß der Aktivator Triäthylamin aus Mischung III von 8 g auf 6 g reduziert wurde, so entstand nach tR = 20 sec. ein gießfähiges Reaktionsgemisch, daß nach tL = 36 sec. aufschäumte und nach tA = 72 sec. erstarrte. Man erhielt ein sandiges, inhomogenes, wenig festes Produkt mit Hohlräumen.Mixed to the mixtures I, was II and III of Example 2 g is reduced simultaneously with the proviso that the activator g of triethylamine of Mixture 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.

BEISPIEL 3EXAMPLE 3

Figure imgb0003
Figure imgb0003

Die Verschäumung wurde gemäß Beispiel 1 durchgeführt. Man erhielt einen harten Schwerschaum mit den Werten:

  • tR: 30 sec., tL: 35 sec., tA: 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.
  • Bulk density [kg / m 3 ]: 213
  • Compressive strength [MPa]: 0.48

BEISPIEL 4EXAMPLE 4

Figure imgb0004
Figure imgb0004

Die Verschäumung erfolgte gemäß Beispiel 1. Man erhielt einen harten Schwerschaum mit den Werten:

  • tR: 30 sec., tL: 36 sec., tA: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 : 30 sec., t L : 36 sec., t A : 52 sec.
  • Bulk density [kg / m 3 ]: 406
  • Compressive strength [MPa]: 1.37

BEISPIEL 5EXAMPLE 5

Polyisocyanat A, wurde durch Polyisocyanat A2 ersetzt. Die Verschäumung erfolgte ansonsten mit den Komponenten aus Beispiel 4 gemäß Beispiel 1.

  • tR: 30 sec., tL: 37 sec., tA: 67 sec.
  • Rohdichte [kg/m3]: 242
  • Druckfestigkeit [MPa]: 0,42
Polyisocyanate A, 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

BEISPIEL 6EXAMPLE 6

Beispiel 5 wurde mit 75 g Trichlorfluormethan wiederholt.

  • tR: 30 sec., tL: 34 sec, TA: 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

BEISPIEL 7EXAMPLE 7

Figure imgb0005
Figure imgb0005

Die Verschäumung erfolgte gemäß Beispiel 1

  • tR: 30 sec., tL: 34 sec., tA: 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 ]: 273
  • Compressive strength [MPa]: 1.02

Vergleichsbeispiel 7a)Comparative Example 7a)

Vermischte man die Mischungen aus Beispiel 7 gleichzeitig, so erhielt man nach 30 sec. Rührzeit ein hochviskoses, nicht gießbares Reaktionsgemisch ohne Aufschäumtendenz.If the mixtures from Example 7 were mixed at the same time, a highly viscous, non-pourable reaction mixture without foaming tendency was obtained after 30 seconds of stirring.

BEISPIEL 8EXAMPLE 8

Figure imgb0006
Figure imgb0006

Die Verschäumung erfolgte gemäß Beispiel 1.

  • tR: 30 sec., tL: 38 sec., tA: 52 sec.
  • Rohdichte [kg/m3): 370
  • Druckfestigkeit [MPa]: 1,21
Foaming was carried out according to Example 1.
  • t R : 30 sec., t L : 38 sec., t A : 52 sec.
  • Bulk density [kg / m 3 ): 370
  • Compressive strength [MPa]: 1.21

Vergleichsbeispiel 8a)Comparative Example 8a)

Vermischte man die Mischungen aus Beispiel 8 gleichzeitig, so erhielt man nach tR = 20 sec. Rührzeit ein gießfähiges Reaktionsgemisch, das nach tL = 32 sec. und nach tA = 70 sec. erstarrte. Das Produkt wies Hohlräume auf und war sandig, inhomogen und wenig fest.If the mixtures from Example 8 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.

BEISPIEL 9EXAMPLE 9

Figure imgb0007
Figure imgb0007

Die Verschäumung erfolgte gemäß Beispiel 1. Man erhielt einen harten Schwerschaum mit den Werten:

  • tR: 30 sec., tL: 37 sec., tA: 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

Vergleichsbeispiel 9a)Comparative Example 9a)

Versuchte man die Komponenten aus Beispiel 9 gleichzeitig zu vermischen, so trat schlagartig Gelierung des Reaktionsgemisches ein.If one tried to mix the components from Example 9 at the same time, the reaction mixture suddenly gelled.

BEISPIEL 10EXAMPLE 10

Figure imgb0008
Figure imgb0008

Mischung I wurde 5 sec. mit einem Schnellrührer vorgemischt und anschließend 10 sec. mit Mischung II zur Primärdispersion verrührt. Nach 15 sec. Gesamtrührzeit wurde Komponente c) eingerührt. Nach tR = 30 sec. wurde das Reaktionsgemisch in ein Papierpäckchen gegossen, begann nach tL = 36 sec. aufzuschäumen und war nach tA = 130 sec. erstarrt. Man erhielt einen zäh-elastischen anorganisch-organischen Leichtschaum mit einer Rohdichte von 78 kg/m3.Mixture I was premixed for 5 seconds with a high-speed stirrer and then mixed with mixture II for 10 seconds to form the primary dispersion. After a total stirring time of 15 seconds, component c) 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 .

Vergleichsbeispiel 10a)Comparative Example 10a)

Vermischte man die Komponenten gemäß Beispiel 10 gleichzeitig, so erhielt man nach 30 sec. Rührzeit ein Raktionsgemisch, das nach tL = 32 sec. aufschäumte und nach tA = 75 sec. erstarrte. Man erhielt einen Schaum mit stark gestörter Zellstruktur.If the components according to Example 10 were mixed simultaneously, a raction mixture was obtained after 30 seconds of stirring, which foamed after t L = 32 seconds and solidified after t A = 75 seconds. A foam with a strongly disturbed cell structure was obtained.

BEISPIEL 11EXAMPLE 11

Figure imgb0009
Figure imgb0009

Die Vermischung und Verschäumung erfolgte gemäß Beispiel 10. Man erhielt einen zäh-elastischen Leichtschaum mit den Werten:

  • tR: 30 sec., tL: 90 sec.
  • Rohdichte kg/m3: 70
Mixing and foaming were carried out in accordance with Example 10. A tough, elastic light foam was obtained with the values:
  • t R : 30 sec., t L : 90 sec.
  • Gross density kg / m 3 : 70

Vergleichsbeispiel 11 a)Comparative Example 11 a)

Vermischte man die Komponenten gemäß Beispiel 11 gleichzeitig, so erhielt man nach tR = 30 sec Rührzeit ein Reaktionsgemisch, das nach 35 sec. aufschäumte und während des Aufschäumens kollabierte.If the components according to Example 11 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 (6)

1. Process for the preparation of inorganic/organic plastics which have a high strength, elasticity and heat distortion point and very low inflammability and consist of a polymer/polysilicic acid composite material present as a colloidal xerosol, by mixing
a) an organic polyisocyanate,
b) an aqueous alkali metal silicate solution or an aqueous silica sol, containing 20-80 per cent by weight of inorganic solids,
c) water, an aqueous alkali metal silicate solution and/or an aqueous suspension of fillers with a solids content between 20 and 80 per cent by weight, at least 50 per cent by weight of the fillers having a particle size of less then 50 microns, and optionally also
d) isocyanate catalysts and/or e) other customary additives, and allowing the mixture thus obtained to react, characterised in that mixing is carried out in a manner such that components a) and b), optionally with the addition of all or some of components d) and/or e), are reacted to form a stable primary dispersion and component c), optionally with the addition of all or some of components d) and/or e), is then added to form a final dispersion, the final dispersion having a viscosity range of 600-6,000 mPas at room temperature before the start of hardening and consisting of an inorganic aqueous phase to the extent of 50-90 per cent by weight and an organic phase to the extent of 10-50 per cent by weight.
2. Process according to Claim 1, characterised in that sodium silicate with a molar ratio of Na,O:S'02 in the range from 1:1.6 to 3.3 is used as the alkali metal silicate.
3. Process according to Claims 1-2, characterised in that products obtained by phosgenation of the aniline/formaldehyde condensation products are employed as the organic polyisocyanates.
4. Process according to Claims 1-3, characterised in that a polyisocyanate which contains ionic groups is used as the polyisocyanate.
5. Process according to Claim 4, characterised in that the polyisocyanate containing ionic groups is a polyisocyanate containing sulphonic acid groups and/or sulphonate groups.
6. Process according to Claims 1 and 2, characterised in that a prepolymer which contains nonionic hydrophilic groups and has isocyanate end groups is employed as the polyisocyanate.
EP78100504A 1977-08-02 1978-07-26 Process for the preparation of inorganic-organic synthetic resins Expired EP0000579B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772734691 DE2734691A1 (en) 1977-08-02 1977-08-02 PROCESS FOR THE PRODUCTION OF INORGANIC-ORGANIC PLASTICS
DE2734691 1977-08-02

Publications (2)

Publication Number Publication Date
EP0000579A1 EP0000579A1 (en) 1979-02-07
EP0000579B1 true EP0000579B1 (en) 1980-10-29

Family

ID=6015397

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100504A Expired EP0000579B1 (en) 1977-08-02 1978-07-26 Process for the preparation of inorganic-organic synthetic resins

Country Status (5)

Country Link
US (1) US4276404A (en)
EP (1) EP0000579B1 (en)
JP (1) JPS5428398A (en)
DE (2) DE2734691A1 (en)
IT (1) IT1105389B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0016262A1 (en) * 1979-03-06 1980-10-01 Bergwerksverband GmbH Process for consolidating and sealing geological and heaped rock and earth formations
EP0099531A2 (en) * 1982-07-23 1984-02-01 BASF Aktiengesellschaft Stable water-glass solutions, process for preparing them, their use in producing organosilicate foam plastics, and process for preraring these organosilicate foams
US4669919A (en) * 1984-06-06 1987-06-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Process for consolidation and sealing coal and/or rock, soil and brick formations in mining, tunnelling and construction
DE3625278A1 (en) * 1986-07-25 1988-01-28 Kvt Kunststoff METHOD FOR PRODUCING INORGANIC-ORGANIC FOAMS
US4827005A (en) * 1984-06-06 1989-05-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Organomineral products, a process for their manufacture and their use
WO2001058975A1 (en) 2000-02-08 2001-08-16 Fosroc International Limited Compositions for the manufacture of organo-mineral products, products obtained therefrom and their use

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE31946E (en) * 1979-03-06 1985-07-16 Bergwerksverband Gmbh Process for consolidating and sealing off geological and artificially deposited rock and earth formations
US4518718A (en) * 1984-05-18 1985-05-21 The United States Of America As Represented By The United States Department Of Energy Rigid zeolite containing polyurethane foams
ATE377061T1 (en) * 2003-05-15 2007-11-15 Huntsman Int Llc POLYISOCYANATE-BASED ADHESIVE COMPOSITION FOR USE IN SANDWICH PANELS
US20060166834A1 (en) * 2004-02-10 2006-07-27 Halliburton Energy Services, Inc. Subterranean treatment fluids comprising substantially hydrated cement particulates
BE1018111A3 (en) * 2008-04-29 2010-05-04 Maras Monique Georgette H METHOD FOR OBTAINING A FIRE-RESISTANT FOAM

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3826769A (en) * 1969-07-14 1974-07-30 Minnesota Mining & Mfg Self-emulsified polyurethanes prepared by direct sulfonation of isocyanate
DE2310559C3 (en) * 1973-03-02 1975-09-11 Bayer Ag, 5090 Leverkusen Foam concrete, a process for its manufacture and its use for the manufacture of building elements
US4097423A (en) * 1972-06-03 1978-06-27 Bayer Aktiengesellschaft Inorganic-organic compositions
US4057519A (en) * 1974-09-05 1977-11-08 H. H. Robertson Company Sodium silicate extended polyurethane foam
DE2512170C3 (en) * 1975-03-20 1981-06-11 Bayer Ag, 5090 Leverkusen Process for the production of optionally foam-shaped, hard inorganic-organic composite material
DE2524191C3 (en) * 1975-05-31 1980-04-03 Bayer Ag, 5090 Leverkusen Process for the production of hole-filled lightweight foams containing hydrophobic urea groups
DE2734690A1 (en) * 1977-08-02 1979-02-08 Bayer Ag PROCESS FOR THE PRODUCTION OF INORGANIC-ORGANIC PLASTICS

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0016262A1 (en) * 1979-03-06 1980-10-01 Bergwerksverband GmbH Process for consolidating and sealing geological and heaped rock and earth formations
EP0099531A2 (en) * 1982-07-23 1984-02-01 BASF Aktiengesellschaft Stable water-glass solutions, process for preparing them, their use in producing organosilicate foam plastics, and process for preraring these organosilicate foams
EP0099531A3 (en) * 1982-07-23 1986-12-10 Basf Aktiengesellschaft Stable water-glass solutions, process for preparing them, their use in producing organosilicate foam plastics, and process for preraring these organosilicate foams
US4669919A (en) * 1984-06-06 1987-06-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Process for consolidation and sealing coal and/or rock, soil and brick formations in mining, tunnelling and construction
US4827005A (en) * 1984-06-06 1989-05-02 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Organomineral products, a process for their manufacture and their use
US4871829A (en) * 1984-06-06 1989-10-03 Kvt Kunststoffverfahrenstechnik Gmbh & Co. Organomineral products, a process for their manufacture and their use
DE3625278A1 (en) * 1986-07-25 1988-01-28 Kvt Kunststoff METHOD FOR PRODUCING INORGANIC-ORGANIC FOAMS
WO2001058975A1 (en) 2000-02-08 2001-08-16 Fosroc International Limited Compositions for the manufacture of organo-mineral products, products obtained therefrom and their use

Also Published As

Publication number Publication date
DE2734691A1 (en) 1979-02-08
US4276404A (en) 1981-06-30
EP0000579A1 (en) 1979-02-07
IT1105389B (en) 1985-10-28
JPS5519929B2 (en) 1980-05-29
IT7850543A0 (en) 1978-07-31
DE2860257D1 (en) 1981-01-29
JPS5428398A (en) 1979-03-02

Similar Documents

Publication Publication Date Title
EP0179775B1 (en) Light ceramic material for building, method to manufacture such material and utilization thereof
DE2631090C3 (en) Sufficient binder
DE2359611A1 (en) COMPOSITES
DE102005005259B4 (en) Mineral insulating element and method for its production
DE2808101A1 (en) PLASTER PREPARATION
DE2333317B2 (en) RAW DIMENSIONS FOR THE MANUFACTURING OF POROESE BUILDING MATERIALS AND THE METHOD FOR THEIR MANUFACTURING
EP0000579B1 (en) Process for the preparation of inorganic-organic synthetic resins
DE3004346A1 (en) METHOD FOR PRODUCING VAPOR-HARDENED LIGHTWEIGHT GAS CONCRETE WITH HYDROPHOBIC PROPERTIES
DE10005707A1 (en) Powdery composition based on water-soluble polymers
DE2559255C2 (en) Process for the production of inorganic-organic plastics
WO2009133046A1 (en) Elastic inorganic-organic hybrid foam
DE60105603T3 (en) PREPARATION OF A COLLOIDAL SILICATE DISPERSION
DE3008755A1 (en) INORGANIC ELASTIC FOAM AND METHOD FOR THE PRODUCTION THEREOF
DE3134682C2 (en) Process for the production of a porous mass
DE2323488A1 (en) PROCESS FOR MANUFACTURING FOAM OR COMPACT MATERIALS
EP0001992B1 (en) Foamable magnesia cement mixture, its utilisation and method for the preparation of porous shaped bodies
DE3243573C2 (en) Water-based plaster mixture based on gypsum and other additives
CH684480A5 (en) Sound-insulating foam body.
WO2018103794A1 (en) Method for producing a component from aerated concrete and same
EP0000580B1 (en) Process for the preparation of inorganic-organic plastics
DE2752897A1 (en) ANHYDRITE-BASED FOAM CONCRETE
DE102005005258B4 (en) Mineral insulating element and method for its production
DE4325829C1 (en) Process for preparing calcium hydroxide-rich binders for concretes, mortars, plasters, renders, screeds or slurries and use of the binders thus prepared
DE3221463A1 (en) Process for producing a light building material
DE3227079A1 (en) Rigid foam material and process for its manufacture

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed
AK Designated contracting states

Designated state(s): BE DE FR GB

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Designated state(s): BE DE FR GB

REF Corresponds to:

Ref document number: 2860257

Country of ref document: DE

Date of ref document: 19810129

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19890617

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19890726

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19890728

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19890731

Year of fee payment: 12

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19900726

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19900731

BERE Be: lapsed

Owner name: BAYER A.G.

Effective date: 19900731

GBPC Gb: european patent ceased through non-payment of renewal fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19910329

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19910403

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT