EP0000580A1 - Process for the preparation of inorganic-organic plastics - Google Patents

Abstract

Process for the preparation of inorganic-organic plastics of high strength, elasticity, heat resistance and flame resistance consisting of a polymer-polysilica 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 an inorganic solid of 20-80% by weight, preferably $ 30-70% by weight, c) an organic compound which contains at least one hydrogen atom which is reactive towards isocyanate and at least one nonionic-hydrophilic group, and d) optionally catalysts and others 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), first with the addition of all or part of component d), are converted to a stable primary dispersion and then knockout component c), optionally with the addition of all or part of component d), with formation of a final dispersion.

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, 2 359 608, 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 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 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 / 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.

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.

• a) einem organischen Polyisocyanat
• b) einer wäßrigen Silikatlösung
• c) einer organischen Komponente

so vorgenommen, daß zunächst die Anteile b) und c) vorgemischt oder aber a), b) und c) gleichzeitig vermischt werden.For example, according to DT-OS 2 359 606 the mixing of

• a) an organic polyisocyanate
• b) an aqueous silicate solution
• c) an organic component

in such a way that portions b) and c) are premixed or a), b) and c) are mixed simultaneously.

In this way, however, products are often obtained which, with an increasing proportion of organic component, can increasingly have faults which, in extreme cases, prevent the controlled build-up of an inorganic-organic plastic.

The invention has for its object to avoid the disadvantages described above and to produce inorganic-organic plastics, even with high amounts of organic components, without any problems.

This object is achieved with the method according to the invention.

• 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 organischen Verbindung, die mindestens ein gegenüber Isocyanat reaktionsfähiges Wasserstoffatom sowie mindestens eine nichtionisch-hydrophile Gruppe enthält, und
• d) gegebenenfalls Katalysatoren und weiteren Zusatzmitteln und Ausreagierenlassen des so erhaltenen Gemischs,

dadurch 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.The present invention thus relates to a process for the preparation 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) an organic compound which contains at least one hydrogen atom which is reactive toward isocyanate and at least one nonionic-hydrophilic group, and
• d) optionally 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 converted into 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.

According to the invention, it is preferred that the final dispersion has a viscosity range of 100-4000 cP before the start of curing at room temperature and consists of 10-50% by weight of inorganic aqueous phase and 90-50% 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 consisting of polyisocyanate, aqueous basic solution or suspension and, if appropriate, further additives such as activators, emulsifiers and blowing agents prepared and then the addition of the organic compound (component c)) made. 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 the mixing with the organic compound (component c)) takes place continuously in a downstream mixing head.

The discontinuous variant is recommended when using such organic 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).

Often desired, longer mixing times can be achieved by the discontinuous process in that the activator required for curing is only added after the stable primary dispersion has been prepared.

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

According to the invention, the individual components are mixed, for example, in the order that a spatial and temporal dispersion is first prepared from components a) and b), optionally with the addition of all or part of component d), using a mixing unit and component c) for this dispersion in a spatially and temporally arranged mixing unit, optionally with the addition of all or part of component d).

• 1)Es werden zwei Rührwerksmischköpfe 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 ggf. 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 zweites 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 possibly d)] being metered in at the first static mixer and after passing through the first mixing section in the second static mixer with component c) [ and possibly d)] are mixed.
• 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.

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 ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, 1-isocyanto-3,3,5 trimethyl-5-isocyantomethylcyclohexane (DT-AS 1 202 785, US Pat. No. 3,401,190), 2,4- and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or - 1,4-phenylene diisocyanate, perhydro-2,4'- and / or -4,4'-diphenylmethane 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, triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanates such as they are obtained by aniline-formaldehyde condensation and subsequent phosgenation and are described, for example, in GB-PS 874 430 and 848 671, m- and p-isocyanatophenylsulfonyl-isocyanates according to US Pat. No. 3,454,606, perchlorinated aryl polyisocyanates, as described, for example, in the DT-AS 1,157,601 (U.S. Patent 3,227,138), carbodiimide group-containing polyisocyanates as described in DT Patent 1,092,007 (U.S. Patent 3,152,162), diisocyanates as described in U.S. Patent 3,492 330 polyisocyanates containing allophanate groups, such as are described, for example, in British Patent 994 890, BE-PS 761 626 and published Dutch patent application 7 102 524, polyisocyanates containing isocyanurate groups, such as those described in US Pat. No. 3,001,973 , described 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 are described in US Pat. No. 3,394 1-64, acylated urea group-containing polyisocyanates according to polyisocyanates according to DT-PS 1 230 778, biuret group-containing polyisocyanates, as described, for example, in US Pat described 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, as described, for example, in US Pat. No. 3,654,106, Polyisocyanates containing ester groups, as are mentioned, for example, in British Pat. Nos. 965,474 and 1,072,956, in US Pat. No. 3,567,763 and in DT Pat. No. 1,231,688, reaction products of the above-mentioned isocyanates with acetals according to the 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-tclylene 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, Polyisocyanates containing urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups ("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), Car polyisocyanates containing boxylate 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 polyphenyl polymethylene polyisocyanates of how they are produced by aniline-formaldehyde condensation and subse- _ß end phosgenation ( "crude MDI") and from the obtainable therefrom by distilling off of two-core products distillation residues in generally have a viscosity between 50 and 50,000 P / 25 ° C, an NCO content of 28-33 weight percent and a functionality> 2.

According to the invention, basic components (component b)) are furthermore aqueous basic solutions or suspensions with an inorganic solid content 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 also used 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 glasses”. Raw technical solutions can also be used, which can additionally contain, for example, calcium silicate, magnesium silicate, borates and aluminates. Preferably, however, 32-54% by weight sodium silicate solutions are used, with a molar ratio Na ₂ 0 / Si0 ₂ of 1: 1.6 to 1: 3.3.

Component c) is to be understood as meaning (preferably liquid at room temperature) organic compounds which, in addition to at least one isocyanate-reactive hydrogen atom, have at least one nonionic-hydrophilic group.

The nonionic-hydrophilic groups are primarily hydrophilic polyether groups.

Polyether groups which are composed of ethylene oxide and / or propylene oxide are preferred.

Suitable organic compounds which, in addition to a hydrogen atom which is reactive toward isocyanate, have at least one nonionic-hydrophilic group are, in particular, polyethers which are made up of alcohols with a functionality of 1-3 and ethylene oxide and / or propylene oxide and have terminal OH groups .

The hydrophilic center can also be introduced into the organic compound by incorporating a glycol such as tri- and tetraethylene glycol.

Of course, according to the invention, polyether groups produced differently can also have organic compounds are used, provided they contain - in addition to at least one reactive H atom - hydrophilic groups, for example monofunctional polyethers based on monoalcohols and ethylene oxide. The proportion of ethylene oxide in the polyether should preferably be at least 10% by weight.

Nonionic-hydrophilic compounds suitable according to the invention are furthermore polycarbonates based on ethylene glycol, propylene glycol, tetraethylene glycol. Formose can also be used here, as it is e.g. in DT-OS 2 639 084, 2 639 083, 2 714 084, 2 714 104, 2 721 186 and 2 721 093.

Furthermore, compounds are also suitable which have a hydrophilic polyester segment, e.g. Contain tr-ethylene glycol or diethylene glycol and succinic acid or oxalic acid. Such segments can be destroyed in the course of the further reaction with water glass, the organic component becoming hydrophobic with hardening of the inorganic component.

Polyethers which are composed of amines with a functionality of 1-4 and ethylene oxide and / or propylene oxide and have terminal OH groups are also particularly suitable for the batch process.

According to the invention, volatile organic substances are optionally used as blowing agents. Examples of suitable organic blowing agents are acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether. A blowing effect can also be achieved by adding at temperatures above room temperature with elimination of Gases, for example nitrogen, decomposing compounds, for example 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 often also 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-ethylmorpholine, 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-3-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, as described, for example, in the German patent, also come as catalysts Document 1 229 290 are described, in question, for example, 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 can also be used (Emulsifiers and foam stabilizers) can also be used. Suitable emulsifiers are, for example, the sodium salts of castor oil sulfonates, sodium salts of sulfonated paraffins or also of fatty acids or salts of fatty acids with amines such as oleic acid diethylamine or stearic acid diethanolamine. 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-readable 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 which may be used according to the invention sensors and cell regulators, reaction retarders, stabilizers; Flame retardant substances, plasticizers, dyes and fillers as well as fungistatic and bacteriostatic substances as well as details on the use and mode of action of these additives are in the plastic manual, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, e.g. on the p 103 to 113. The reaction components are preferably mixed at room temperature.

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 organic components and changing the W / O phase structure, undergo unstable dispersion states which, after hardening, can result in disturbances in the structure of the inorganic-organic plastic.

This is because organic substances, introduced using conventional mixing techniques, can initiate separation 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 process products find the application known for organic-inorganic plastics, e.g. as sound and heat insulation materials, as building material, as concrete and joint sealing compounds.

Examples

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

• a) Polyisocyanatkomponente
  • A₁: 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.-%.
  • A₂: Mit gasförmigem Schwefeltrioxid sulfoniertes A₁ (Schwefelgehalt: 0,96 %, NCO-Gehalt: 30,5 %, Viskosität bei 25°C: 24000 cP, Herstellung s. DT-OS 2 227 111).
  • A ₃: Entsprechend mit Chlorsulfonsäure sulfoniertes A₁ (Schwefelgehalt: 0,9 %, NCO-Gehalt: 30,2 % Viskosität bei 20°C: 2000 cP).
• b) Silikatkomponente
  • B₁: Natriumwasserglas, 44 % Feststoff, Molgewichtverhältnis Na₂0: SiO₂ = 1:2
  • B₂: Natriumwasserglas, 51 % Feststoff, Molgewichtsverhältnis Na₂0 : SiO₂ = 1:2
  • B₃: Natriumwasserglas, 48,6 % Feststoff, Molgewichtverhältnis Na₂O : SiO₂ = 1:2
• c) Polyäther
  • C₁: Auf n-Butanol gestarteter Polyäthylenoxid-monoalkohol OH-Zahl: 49,2
  • C₂: Auf Glycerin gestarteter Polyäthylenoxid-Polypropylenoxidtrialkohol. OH-Zahl: 56
  • C₃: Auf Saccharose/TMp/H₂O/gestarteter Polypropylenalkohol OH-Zahl: 380
  • C₄: Auf Äthylendiamin gestarteter Polypropylentetraalkohol. OH-Zahl: 630
  • C₅: 2,5 Gew.-Teile C₁ + 7,5 Gew.-Teile C₄
  • C₆: 5 Gew.-Teile C₁ + 10 Gew.-Teile C₄
• d) Formose (hergestellt gemäß DT-OS 2 721 186)
  D₁: 14,5 % H₂O; Säurezahl 9,7; OH-Zahl 724
• e) Suspension
  Herstellung einer Kreidesuspension
  E₁: 240 g einer Kreide (spez. Gewicht: 2,7, 90 % der Teilchen < 2µ, Omyalite 90 der Fa. Omya GmbH) wurden in 80 g Wasser und 5 g einer 30 %igen wäßrigen Lösung eines hochmolekularen Di-Kaliumsalzes eines Maleinsäure-Styrol-Copolymerisats mit Carboxylat und Sulfonatgruppen suspendiert. Feststoffgehalt: 75 %.

Starting materials:

• a) polyisocyanate component
  • A ₁ : Sufficient diisocyanatodiphenylmethane is distilled off from the crude phosgenation product of an aniline / formaldehyde condensate so 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 ₂ : A ₁ 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 ₃ : Correspondingly A ₁ 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, molar weight ratio Na ₂ 0: SiO ₂ = 1: 2
  • B ₂ : sodium water glass, 51% solids, molar weight ratio Na ₂ 0: SiO ₂ = 1: 2
  • B ₃ : sodium water glass, 48.6% solids, molar weight ratio Na ₂ O: SiO ₂ = 1: 2
• c) polyether
  • C ₁ : Polyethylene oxide monoalcohol started on n-butanol OH number: 49.2
  • C ₂ : Polyethylene oxide-polypropylene oxide trial alcohol started on glycerin. OH number: 56
  • C ₃ : on sucrose / TMp / H ₂ O / started polypropylene alcohol OH number: 380
  • C ₄ : Polypropylene tetra alcohol started on ethylenediamine. OH number: 630
  • C ₅ : 2.5 parts by weight of C ₁ + 7.5 parts by weight of C ₄
  • C ₆ : 5 parts by weight of C ₁ + 10 parts by weight of C ₄
• d) Formose (manufactured in accordance with DT-OS 2 721 186)
  D ₁ : 14.5% H ₂ O; Acid number 9.7; OH number 724
• e) suspension
  Production of a chalk suspension
  E ₁ : 240 g of a chalk (specific weight: 2.7, 90% of the particles <2μ, Omyalite 90 from Omya GmbH) were in 80 g of water and 5 g of a 30% aqueous solution of a high molecular weight di-potassium salt a maleic acid-styrene copolymer with carboxylate and sulfonate groups suspended. Solids content: 75%.

example 1

Komponente II und III wurden vorgemischt. Komponente I wurde 10 sek. zur Erzielung der Primärdispersion mit einem Schnellrührer vermischt, die Mischung Komponente (II + III) wurde anschließend innerhalb von 5 sek. unter Rühren zugegeben. Nach 20 sek. Gesamtmischzeit wurde das Reaktionsgemisch in ein Papierpäckchen ausgegossen, begann nach 30 sek. aufzuschäumen und war nach 85 sek. erstarrt. Man erhielt einen Zäh-elastischen anorganisch-organischen Leicht-Schaumstoff mit einer Rohdichte von 48 kg/m und einer Druckfestigkeit von 0,07 [MPa].

Components II and III were premixed. Component I was 10 sec. mixed to achieve the primary dispersion with a high-speed stirrer, the mixture component (II + III) was then within 5 seconds. added with stirring. After 20 seconds Total mixing time, the reaction mixture was poured into a paper packet, started after 30 seconds. to foam up and was after 85 sec. stiffens. A tough-elastic, inorganic-organic lightweight foam with a bulk density of 48 kg / m and a compressive strength of 0.07 [MPa] was obtained.

Comparative example

A conventional, simultaneous mixing of the three components according to Example 1 leads to a foam which is not practical, with foam disorders and defoamed, wet floor zone.

These segregation phenomena in the area of the soil zone are obviously caused by insufficient mixing of the individual components.

Example 2

Die Verschäumung erfolgte gemäß Beispiel 1. Der Aufschäumprozeß setzte nach 28 sek. ein, nach 75 sek. war das Reaktionsgemisch erstarrt.

Foaming was carried out according to Example 1. The foaming process continued after 28 seconds. on, after 75 sec. the reaction mixture had solidified.

Bulk density [kg / m ³ ]: 34

Compressive strength [MPa]: 0.06

• t_R = Rührzeit, Mischzeit der Mischung aus Komponente I, Komponente II und Komponente III
• t_L = Liegezeit, Zeitraum von Beginn des Mischens bis zum Beginn des Aufschäumens
• t_A = Abbindezeit, Zeitraum von Beginn des Mischens bis zur Erhärtung.

In the following examples mean:

• t _R = stirring time, mixing time of the mixture of component I, component II and component III
• 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.

Example 3

Example 2 was repeated with an additional 3 g of polyether C ₃ in component II. A light foam was obtained with the following data:.

t _R : 20 sec., t _{L 3rd} : 33 sec., T _A : 85 sec.

Bulk density [kg / m ³ ]: 2 ₉

Compressive strength [MPa]: 0.04

Example 4

Die Verschäumung erfolgte gemäß Beispiel 1. Man erhielt einen Leichtschaum mit den Daten:

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

t _R : 20 sec .; t _{L 3rd} : 40 sec .; t _A : 105 sec.

Bulk density [kg / m ³ ]: 42

Compressive strength / MPa /: 0.07

Example 5

Foaming was carried out according to Example 1.

t _R : 20 sec .; t _{L 3rd} : 29 sec .; t _A : 105 sec .; Bulk density [kg / m ³ ]: 50

Compressive strength [MPa]: 0.09

Example 6

Die Verschäumung erfolgte gemäß Beispiel 1.

Foaming was carried out according to Example 1.

t _R : 20 sec .; t _{L 3rd} : 42 sec .; t _A : 90 sec .;

Bulk density [kg / m ³ ]: 61

Compressive strength [MPa]: 0.12

Example 7

Foaming was carried out according to Example 1. A tough, elastic, inorganic-organic lightweight foam was obtained with the values: t _R : 20 sec .; t _L : 34 sec .; t _A : 140 sec .;

Conventional, simultaneous mixing of the 3 components leads to inhomogeneous, non-foamable reaction mixtures.

Further inorganic-organic foams produced according to Example 7 are listed in Table 1.

It means:

Example 12

Komponente II und III wurden vermischt. Komponente I wurde 10 sek. zur Erzielung der Primärrdispersion mit einem Schnellrührer vermischt, die Mischung Komponente (II + III) wurde anschließend innerhalb von 5 sek. unter Rühren zugegeben. Nach 20 sek. Gesamtmischzeit wurde das Reaktionsgemisch in ein Papierpäckchen ausgegossen, begann nach 37 sek. aufzuschäumen und war nach 40 sek, erstarrt. Man erhielt einen zäh-elastischen anorganisch-organischen Leicht-Schaumstoff mit einer Rohdichte von 48 kg/m³ und einer Druckfestigkeit von 0,09 [MPa].

Components II and III were mixed. Component I was 10 sec. mixed to achieve the primary dispersion with a high-speed stirrer, the mixture component (II + III) was then within 5 seconds. added with stirring. After 20 seconds Total mixing time, the reaction mixture was poured into a paper packet, started after 37 seconds. to foam up and was frozen after 40 seconds. A tough, elastic, inorganic-organic lightweight foam with a bulk density of 48 kg / m ³ and a compressive strength of 0.09 [MPa] was obtained.

Further inorganic-organic foams produced according to Example 12 are listed in Table 2:

Example 18

Komponente II und III wurden vorgemischt. Komponente I wurde 10 sek. zur Erzielung der Primärdispersion mit einem Schnellrührer vermischt, die Mischung Komponente (II + III) wurde anschließend innerhalb von 5 sek. unter Rühren zugegeben. Nach 20 sek. Gesamtmischzeit wurde das Reaktionsgemisch in ein Papierpäckchen ausgegossen, begann nach 34 sek.. aufzuschäumen und war nach 90 sek. erstarrt. Man erhielt einen zäh-elastischen anorganisch-organischen Leicht-Schaumstoff mit einer Rohdichte von 47 kg/m und einer Druckfestigkeit von 0,10 [MPa].

Components II and III were premixed. Component I was 10 sec. mixed to achieve the primary dispersion with a high-speed stirrer, the mixture component (II + III) was then within 5 seconds. added with stirring. After 20 seconds Total mixing time, the reaction mixture was poured into a paper packet, started to foam after 34 seconds and was after 90 seconds. stiffens. A tough, elastic, inorganic-organic lightweight foam was obtained with a bulk density of 47 kg / m and a compressive strength of 0.10 [MPa].

+) Unsaturated polyester resin from Bayer AG

Example 19

Components I and II were 5 sec. mixed with a high-speed stirrer to achieve the primary dispersion. Component III was subsequently within 5 seconds. added with stirring. After 20 seconds Total mixing time, the reaction mixture was poured out into a paper packet. A hard foam was obtained with the values:

t _R ^{: 2} 0, t _L : 30, t _A : 53

Bulk density [kg / m ³ ]: 212

Compressive strength [MPa]: 0.60

A conventional, simultaneous mixing of all three components leads within 20 seconds. to an inhomogeneous, highly viscous, non-foamable reaction mixture.

Example 20

According to Example 19, components I + II were premixed with a high-speed stirrer, component III was then within 5 seconds. added with stirring. After 30 seconds intensive mixing, the reaction mixture was poured into a wooden box mold of approx. 55 dm ³ , started after 48 sec. to foam up and was after 70 sec. stiffens. A hard inorganic-organic foam with a bulk density of 169 kg / m and a compressive strength of 0.57 [MPa] was obtained.

Example 21

Die Verschäumung erfolgte gemäß Beispiel 19.

Foaming was carried out according to Example 19.

t _R : 20 sec .: t _L : 30 sec .; t _A : 50 sec.

Bulk density [kg / m ³ ]: 225

Compressive strength [MPa]: 0.58

Example 22

Foaming was carried out according to Example 19.

t _R : 20 sec .; t _L : 29 sec .; t _A : 55 sec.

Bulk density [kg / m ³ ]: 229

Compressive strength [MPa]: 0.42

Example 23

Die Verschäumung erfolgte gemäß Beispiel 19.

Foaming was carried out according to Example 19.

t _R : 20 sec .; t _L : 31 sec .; t _A : 65 sec .;

Bulk density [kg / m ³ ]: 166

Compressive strength [MPa]: 0.37

Example 24

In a first stirrer, a dispersion of water glass (50% solids content) and polyisocyanate A _{1 is} prepared, which is then mixed with a mixture M of the following composition in a second stirrer:

The product flows are set to the following values: water glass 8000 g / min, polyisocyanate 8040 g / min., 4920 g / min. the mixture M. Both mixing units have stirrers in a 300 ml mixing chamber at 3000 rpm. The promotion takes place via standard gear pumps.

A uniformly fine-cell foam with a bulk density of 14 kg / m ^{3 is obtained} , which can be produced continuously without difficulty at heights of up to 80 cm and a width of 100 cm.

Example 25 (comparative example)

With product flows of the same size as in Example 24, all components are simultaneously entered into a single mixing head. The foam that is now created is clearly heterogeneous and shows strong flow disturbances on the floor and on the sides posts that reach up to a height of approx. 60% of the block height. The malfunctions cannot be eliminated by increasing the stirrer speed up to 6000 rpm; Likewise, adding more stabilizer does not bring any noticeable improvement, but instead leads to rapidly shrinking foams.

Example 26

With product streams of the same size as in Example 24, a dispersion of water glass and isocyanate is first produced in a mixing unit as in Example 24, which is fed to a static mixer and mixed with the mixture M there. An equally good foam is obtained as in Example 24.

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 _X erosol 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) an organic compound which contains at least one hydrogen atom which is reactive toward isocyanate and at least one nonionic-hydrophilic group, and d) optionally 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) are added first, optionally with the addition of all or part of component d), converted to a stable primary dispersion and then component c), optionally with the addition of 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 1-5, characterized in that ^ß the ionic polyisocyanate is a sulfonic acid and / or sulfonate polyisocyanate. 7. The method according to claim 1-3; characterized in that a prepolymer containing terminal isocyanate groups and non-ionically hydrophilic groups is used as the polyisocyanate. 8. Inorganic-organic plastics obtainable according to claim 1 from 10-50 wt .-% inorganic aqueous phase and 90-50 wt .-% organic phase.