DE2520079C2 - Inorganic-organic plastics and a process for their production - Google Patents

Description

2. Inorganic-organic plastics according to claim 1, obtainable by reacting a mixture of

20-80 percent by weight, based on the total mixture, aqueous silica sol,
10-80 percent by weight, based on the total mixture, of organic polyisocyanate, with the exception of non-ionic hydrophilic polyisocyanate prepolymers,
is 10-70 percent by weight, based on the total mixture, of water-binding aggregates.

3. Inorganic-organic plastics according to claim 1 and 2, characterized in that ias in the Aqueous silica sol contained in the reaction mixture has a silica content of 20-60 percent by weight.

4. A method for producing an inorganic-organic plastic according to claim 1, in particular of a foam, by reacting an organic polyisocyanate with aqueous Kieseiso! and water-binding additives, and optionally additives, which is characterized in that one Reaction mixture consisting of

25 2-95 percent by weight, based on the total mixture, aqueous silica sol,

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

non-ionic hydrophilic polyisocyanate prepolymers,
0-93 percent by weight, based on the total mixture, water-binding additives,

30 used.

5. The method according to claim 4, characterized in that the contained in the reaction mixture aqueous silica sol has a silica content of 20-60% by weight.

6. The method according to claim 4 and 5, characterized in that a propellant is also used.

7. The method according to claim 4-6, characterized in that one accelerates the isocyanate reaction Activator also used.

8. The method according to claim 4-7. characterized in that a foam stabilizing agent and / or an emulsifying aid is also used.

9. The method according to claim 4-8, characterized in that one organic, fire-retardant additives used.

10. The method according to claim 4-9, characterized in that a polymeric substance is mitverwen

det.

II. Process according to Claims 4-10, characterized in that inert inorganic, particulate and / or fibrous material is also used.

12. The method according to claim 4-11, characterized in that one inert organic, particulate and / or fibrous material is also used.

13. The method according to claim 4-12, characterized in that one compounds with opposite isocyanate reactive hydrogen atoms are also used.

14. The method according to claim 4, characterized in that the polyisocyanate is an ion group containing Polyisocyanate used.

15. The method according to claim 4, characterized in that the polyisocyanate containing ion groups

Nat is a polyisocyanate containing sulfonic acid and / or sulfonate groups.

16. The method according to claim 4, characterized in that water cement is used as the water-binding filler, synthetic anhydrite, gypsum or quick lime are used.

17. The method according to claim 6, characterized in that a halogenated hydrocarbon with a boiling point below 100 ⁰ C is used as the blowing agent.

18. The method according to claim 7, characterized in that a tertiary amine is used as the activator.

It is already known that insulating materials are obtained using mineral grains and synthetic resins can be. Also a process for the production of synthetic concrete from porous mineral materials and foamable mixtures are state of the art (DE-AS 12 39 229).

In these cases, the mineral material is always cemented or glued through the plastic. The so produced Plastic concrete materials, however, have the disadvantage of inhomogeneity, which is mechanically different highly stressable areas? Furthermore, there are often considerable amounts of expensive, organic plastic is required, which also has a negative effect on the fire behavior.

The leaning of concrete materials commonly used for building purposes with organic, porous Plastics are just as well known as the process of adding propellants or gases to concrete mixtures to be generated in situ in order to obtain porous materials with a reduced bulk density.

Disadvantages of these largely inorganic materials are the relatively high brittleness compared to organic foams form poor thermal insulation and the relatively long setting times. s

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

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

It is also known cement masses made of water cement, a silica filler and an organic To produce a compound with a plurality of isocyanate groups (DE-OS 19 24 468). Main disadvantages of this porous cement masses are the still quite long setting time of 5-6 hours and the not very good thermal insulation. A main area of application for these materials is screed coverings.

It has also been proposed to produce foams from isocvanates and alkali silicates (DE-OS 17 70 384). According to this procedure, foams which have the disadvantages are generally obtained have a high water content and have too little mechanical strength in relation to their bulk density.

Heat-resistant foams can be made from foamable or already cellular thermoplastics obtained in the presence of aqueous alkali metal silicate solutions (DE-AS 14 94 955). Cons of this Process are the necessary heat supply to the thermoplastics for foaming bring the problem of hardening of the alkali silicate solutions as well as the water content of the resulting composite material.

It is also known (DE-OS 22 27 147), inorganic-organic plastics from aqueous silicate solutions and prepolymers containing ionic groups, e.g. B. ionic groups containing polyisocyanates to produce. The silicates present in aqueous solution have to undergo a hardening process. This hardening stage is avoided in the process according to the invention.

While according to this DE-OS inorganic-organic plastics by reaction of an aqueous silicate solution with z. B. a terminal isocyanate prepolymet ionomer can be obtained, these aqueous solutions of alkali silicates can be both real and colloidal solutions, but in no case do they represent silica sols as used according to the invention. In contrast to the aqueous alkali silicate solutions contain z. B. silica sols almost no cations.

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

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

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

2-95 percent by weight, based on the total mixture, aqueous silica sol, preferably with one

Content of 20-60 percent by weight silica,
5-98 percent by weight, based on the total mixture, excluding organic polyisocyanate

non-ionic hydrophilic polyisocyanate prepolymers,
0-93 percent by weight, based on the total mixture, of water-binding additives.

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

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

20-80 percent by weight, based on the total mixture, silica sol, preferably with a content of

20-60 percent by weight silica,
10-80 percent by weight, based on the total mixture, of organic polyisocyanate, with the exception of non-ionic hydrophilic polyisocyanate prepolymers,

10-70 percent by weight, based on the total mixture, of water-binding additives.

The invention also relates to a method for producing an inorganic-organic plastic, especially foam, by reacting an organic polyisocyanate with aqueous silica sol and water-binding additives, and optionally additives, which consists of a reaction mixture consisting of

2-95 percent by weight, based on the total mixture, aqueous silica sol, preferably with one

Content of 20-60 percent by weight silica,
5-98 percent by weight, based on the total mixture, excluding organic polyisocyanate

non-ionic hydrophilic polyisocyanate prepolymers,
0-93 percent by weight, based on the total mixture, water-binding additives,

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

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

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

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

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

Silica sol is to be understood as meaning aqueous, colloidal silica solutions which, depending on the type, have a bluish opalescence to have a milky, cloudy appearance. They contain ultra-crosslinked, spherical particles made of high-purity amorphous silica. The η silica particles hydroxylated on the surface generally have none internal porosity. The size of the particles is in the submicroscopic, colloidal range and can be 7-200 nm but it is preferably 10-50 nm. In individual cases, the diameter of the particles can also be down to 2 nm, but there are also agglomerates with a particle diameter > 200 μ possible. The silica content is generally between 20 and 60 percent by weight, preferably between 25 and 40.

Commercially available silica sols can contain a trace of sodium or other alkali metal ions or an acid, to stabilize the colloidal system. The pH value is usually 3 to 12. Colloid silicas are either by peptizing a silica hydrogel or by gradual destabilization made of alkali silicates. For further literature see: Kirk-Othmer; Encyclopedia of "Technical Technology, Volume 18 (1969), pages 61-72. R. K. Her; The Colloid Chemistry of Silica and Silicates, Cornel! University Press, New York, 1955. J. G. Vail; Soluble Silicates, Vol. I and II, Reinhold, New York, 1952.

In addition to the silica sols mentioned, it is also possible to use aqueous solutions of alkali metal silicates which generally have a solids content of 20-60 percent by weight. As aqueous solutions from alkali silicates come the well-known solutions commonly referred to as "water glass" Sodium and / or potassium silicate in water, as described, for example, in DE-OS 22 27 147 will.

As organic polyisocyanates to be used according to the invention, aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates come into consideration, as they are, for. B. by W. Siefksn in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, are described, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, l. ^ - dodecane diisocyanate, cyclobutane-l ^ -diisocyanate, cyclohexane-1,3-and-1,4-diisocyanate and any mixtures of these isomers, 1-isocyanato-3 _r 3,5-trimethyl-5-isocyanatomethyl-cyclohexane (DE-AS 12 02 785), 2, 4- and 2,6-hexahydr-toluylene diisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, perhydro-2,4'- and / or ^ / i'-diphenylmethane diisocyanate , 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-toliylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-lJ-diisocyanate , Triphenylmethane-4,4 ', 4 "-triisocyanate, polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and, for example, in British patents 8 74 430 u nd 8 48 671 are described, perchlorinated aryl polyisocyanates, as they are, for. B. in DE-AS1157 601, cart jdiimidgruppen containing polyisocyanates, as described in DE-PS 10 92 007, diisocyanates as described in US-PS 34 92 330 neither, polyisocyanates containing allophanate groups, such as them z. B. in GB-PS 9 94 890, dsr BE-PS 7 61626 and the published Dutch patent application 71 02 524 are described, isocyanurate-containing polyisocyanates, as they are, for. B. in DE-PS 10 22 789.12 22 067 and 10 27 394 and in DE-OS 19 29 034 and 20 04 048, urethane-containing polyisocyanates, such as are described, for. B. in BE-PS 7 52 261 or in the American patent 33 54 164 are described, acylated urea group-containing polyisocyanates according to DE-PS 12 30 778, biuret group-containing polyisocyanates such. B. in DE-PS1101394, in GB-PS 8 89 050 and in FR-PS 70 17 514, polyisocyanates produced by Telomerisationsreakliionen, such as are described, for. B. in BE-PS 7 23 640 are described, ester groups containing polyisocyanates, such as are used, for. B. in GB-PS 9 65 474 and 10 72 956, in US-PS 35 67 763 and in DE-PS 12 31 688 mentioned, reaction products of the above isocyanates with acetals according to DE-PS 10 72 385.

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

The technically easily accessible polyisocyanates, eg. B. the 2,4- and 2,6-Toluy-

Lene diisocyanate and any mixtures of these isomers (»TDI«), polyphenyl-polymethylene-polyisocyanates,

as they are produced by aniline-formaldehyde condensation and subsequent phosgenation (»crude

MDI «) and carbodiimide groups. Urethane groups, allophanate groups, isocyanurate groups, urea groups

60 or polyisocyanates containing biuret groups ("modified polyisocyanates").

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

65 I I

- N ^e - —S®— - P * ~ —COO ⁶ --SOf - O —SO?

o ^e o ^e

- SO? - P - P

Il \ Il \

O OH O R

Polyisocyanates containing sulfonic acid and / or sulfonate groups are very particularly preferred.

Such isocyanates are prepared according to a separate, older proposal that one liquid Multi-component mixtures of aromatic polyisocyanates which have an NCO content of 10-42% by weight and have a viscosity of 50-10,000 cP at 25 ° C, with 0.1 to 10 wt .-% sulfur trioxide or an equivalent Amount of oleum, sulfuric acid or chlorosulfonic acid mixed at -20 to + 200 ° C and allowed to react leaves and the sulfonation products obtained in this way, optionally wholly or partially with a basic compound neutralized (DE-PS 22 27 111).

According to the invention, polyisocyanate prepolymers containing nonionic-hydrophilic groups are not used into consideration.

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

Portland cement, quick-setting cement, blast furnace Portland cement, low-fired cement, sulphate-resistant cement, wall cement, natural cement, lime cement, Gypsum cement, pozzolan cement and calcium sulphate cement are used.

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

The filler materials can be organic or inorganic, preferably fibrous or particulate or be any mixture thereof, e.g. B. sand, aluminum oxide, aluminum silicates, magnesium oxide and others particulate refractory materials, metal fibers, asbestos, glass fibers, rock wool or mineral fibers, aluminum silicate, Calcium silicate fibers and other fibrous refractory materials, sawdust or wood flour, coke and other organic or carbonaceous particles, paper pulp, cotton waste, cotton, jute, sisal, Hemp, flax, rayon or synthetic fibers, e.g. B. polyester, polyamiu- and acrylonitrile fibers and other organic fibrous materials.

According to the invention, highly volatile inorganic and / or organic substances are often used as blowing agents used. As organic blowing agents such. B. acetone, ethyl acetate, methanol, ethanol, halogen-substituted Alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, Chlorodifluoromethane, dichlorodifluoromethane, also butane, hexane, heptane or diethyl ether are possible. A blowing effect can also be achieved by adding at temperatures above room temperature with elimination of Gases such as nitrogen, decomposing compounds, e.g. B. azo compounds such as azoisobutyronitrile, be achieved. Further examples of propellants and details on the use of Propellants are in the Kunststoff-Handbuch, Volume VII, published by Viewg and Höchtlen, Carl-i'anser-Verlag, Munich 1966, z. B. on pages 108 and 109, 453 to 455 and 507 to 510 described. However can the water contained in the mixture also takes on the function of the propellant. Furthermore, fine Metal powder, e.g. B. calcium, magnesium, aluminum or zinc due to the evolution of hydrogen with sufficient Alkaline water glass serve as a propellant, while at the same time having a hardening and strengthening effect exercise.

According to the invention, catalysts are also often used. Catalysts to be used are also available those of the type known per se in question, e.g. B. tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethyl-morpholine, N-cocomorpholine, Ν, Ν, Ν'Ν'-tetramethyl-ethylenediamine, 1,4-diaza-bicycio (2,2,2) -octane, N-methyl-N'-dimethylaminoethylpiperazine, Ν, Ν-dimethylbenzylamine, bis- (N, N-diethylaminoäthyO-adipate, N, N-diethylbenzylamine, pentamethyldiethylenetriamine, Ν, Ν-dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-1,3-butanediamine, N.N-dimethyl-jS-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole and in particular also hexahydrotriazine derivatives.

Tertiary amines containing hydrogen atoms active towards isocyanate groups are e.g. B. triethanolamine, Triisopropanolamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, Ν, Ν-dimethyl-ethanolamine, as well as their reaction products with alkylene oxides, such as propylene oxide and / or ethylene oxide.

As catalysts, there are also silaamines with carbon-silicon bonds, such as those used, for. B. in DE-PS 12 29 290 are described in question, e.g. B. Σ ^^ ΤπΐηβΟ ^ Ι ^ -βΠαηιΟΓρΙιοΙϊη, 1,3-diethylaminomethyl-tetramethyl-disiloxane.

Nitrogen-containing bases such as tetraalkylammonium hydroxides and alkali metal hydroxides can also be used as catalysts such as sodium hydroxide, alkali phenolates such as sodium phenolate or alkali alcoholates such as sodium methylate into consideration. Hexahydrotriazines can also be used as catalysts.

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

The preferred organic tin compounds are tin (II) salts of carboxylic acids such as tin (II) acelate, Tin and D-octoate, tin (II) ethylhexoate and tin (II) laurate and the dialkyltin salts of carboxylic acids, such as z. B. dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin maleate or dioctyl tin diacetate into consideration.

Further representatives of catalysts to be used according to the invention and details of the mode of action of the catalysts are in the Kunststoff-Handbuch, Volume VI, edited by Viewg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, z. B. on pages 96-102 described.

The catalysts are usually in an amount between about 0.001 and 10 wt .-%, based on the Amount of isocyanate used.

According to the invention, surface-active additives (emulsifiers and foam stabilizers) can also be used will. As emulsifiers z. B. the sodium salts of castor oil sulfonates, sodium salts sulfonated paraffins or of fatty acids or salts of fatty acids with amines such as oleic diethylamine or stearic acid diethanolamine in question. Also alkali or ammonium salts of sulfonic acids such as from Dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or of fatty acids such as ricinoleic acid or polymeric fatty acids can be used as surface-active additives.

Water-soluble polyether siloxanes are particularly suitable as foam stabilizers. These connections are generally constructed in such a way that a copolymer of ethylene oxide and propylene oxide with a polydimethylsiloxane radical connected is. Such foam stabilizers are z. B. in US Pat. No. 2,764,565.

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

Further examples of surface-active additives which can optionally be used according to the invention and foam stabilizers as well as cell regulators, reaction retarders, stabilizers, flame retardant substances, Plasticizers, dyes and fillers as well as fungistatic and bacteriostatic substances as well as details about the use and mode of action of these additives can be found in the plastics manual, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser-Verlag, Munich 1966, z. B. on described on pages 103 to 113.

According to the invention, starting components which are preferably also to be used are also compounds with at least two isocyanate-reactive hydrogen atoms with a molecular weight in

usually from 62-10,000. This includes amino groups, thiol groups or carboxyl groups containing compounds, preferably polyhydroxy compounds, in particular two to eight hydroxyl | group-containing compounds, especially those with a molecular weight of 400 to 10,000, preferably 1,000 up to 6000, e.g. B. at least two, usually 2 to 8, but preferably 2 to 4 hydroxyl groups Polyesters, polyethers, polythioethers, polyacetals, polycarbonates, polyester amides, such as those used for the production of homogeneous and cellular polyurethanes are known per se. These connections are usually in an amount of up to 1-30% by weight, based on the mixture of polyisocyanate, silica sol and water-binding agent

Aggregate, also used. |

The polyester containing hydroxyl groups in question are, for. B. conversion products of &

polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dibasic carboxylic acids. Instead of the free polycarboxylic acids, the corresponding Polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures of these can be used to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic ^ aromatic and / or heterocyclic nature and optionally, z. B. by Halogen atoms, substituted and / or unsaturated. Examples include: succinic acid, adipic acid, Suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, Tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, Fumaric acid, dimeric and trimeric fatty acids such as oleic acid, optionally mixed with monomeric fatty acids, Dimethyl terephthalate, bis-glycol terephthalate. Come as polyhydric alcohols

z. B. ethylene glycol, propylene glycol (1,2) and - (1,3), butylene glycol (1,4) and - (2,3), hexanediol (1,6), octanediol (1,8), Neopentyl glycol, cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane), 2-methyl-1,3-propanediol, Glycerin, trimethylolpropane, hexanetriol (1,2,6), butanetriol (1,2,4), trimethylolethane, pentaerythritol, quinite, Mannitol and sorbitol, methyl glycoside, also diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols, Dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols are possible. The polyester may have a proportion of terminal carboxyl groups. Also polyesters made from lactones, e.g. B. ^ Caprolactone or hydroxycarboxylic acids, e.g. B. ω-hydroxycaproic acid can be used. According to the invention can also the above-mentioned low molecular weight polyols are used. Low molecular weight amines such as alkylene

diamine are possible.

The polyethers which can be considered according to the invention, at least two, usually two to eight, preferably two to three, hydroxyl groups are those of the type known per se and are, for. B. by polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, e.g. B. in the presence of BF ₃ , or by adding these epoxides, optionally in a mixture or in succession, to starting components with reactive hydrogen atoms such as alcohols or amines, eg. B. water, ethylene glycol, propylene glycol (1,3) or - (1,2), trimethylolpropane, 4,4'-

Dihydroxydiphenylpropane, aniline, ammonia, ethanolamine, ethylenediamine are produced. Also sucrose polyether, how they z. B. in DE-AS 11 76 358 and 10 64 938, come according to the invention in Question. In many cases those polyethers are preferred which predominantly (up to 90% by weight, based on all OH groups in the polyether) have primary OH groups. Also modified with vinyl polymers Polyethers, such as those used, for. B. by polymerization of styrene, acrylonitrile in the presence of polyethers (US-PS 33 83 351, 3304273, 3523093, 3110695, DE-PS 1152 536) are also suitable, as are those containing OH groups Polybutadienes.

Among the polythioethers are in particular the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols

'_;; iingcl 'leads. Depending on the co-components, the products are polythio mixed ethers, polythioi; ethereal esters, polythioether ester amides.

Ίί As polyacetals come z. B. from glycols such as diethylene glycol, triethylene glycol, 4,4'-dioxäthoxy-

£ diphcny Idimcthylmethan, I lexanediol and formaldehyde preparable compounds in question. Also through poly According to the invention, suitable polyacetals can be produced by mcrization of cyclic acetals.

·. Polycarbonates containing hydroxyl groups are those of the type known per se, which

; τ. B. by reacting diols such as? Ropanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene \\ glycol, Triäthylcnßiykol, tetraethylene glycol with diaryl carbonates, z. B. diphenyl carbonate or phosgene, her- '. can be asked.
'' - [ The polyester amides and polyamides include e.g. B. those of polyvalent saturated and unsaturated

Carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, di-; amines, polyamines and their mixtures, predominantly linear condensates.
■ ', Also polyhydroxyl compounds already containing urethane or urea groups, and optionally

; modified natural polyols such as castor oil, carbohydrates, starch can be used. Also accumulation pro-

duktc of alkylene oxides to phenolformaldehyde resins or even with urea-formaldehyde resins are inventions''' dungsgemüß cinsetzbar.

'Representatives of these compounds to be used according to the invention are, for. B. in High Polymers, Vol. XVI,

% "Polyurethanes, Chemistry and Technology," written by Saunders-Frisch, Interscience Publishers, New York, $ London, Volume i, 1962, lines 32-42 and pages 44-54 and Volume H, 1964, lines 5-6 and 198-199, as well as in I Kunststorr-Handbuch, Volume VU, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, z. B. on pages 45 [* to 71 described.

f < The production of the inorganic-organic plastics according to the invention is generally carried out in such a way that one

§ in a batchwise or continuous mixing apparatus, the Reaktionskom- ^ i-described components in one stage or in multiple stages are mixed together and the resulting mixture mostly% outside the mixing apparatus in molds or on a suitable medium optionally lather and allowed to solidify%. Are in this case can be between about 0 and 200 ⁰ C, preferably 50 to 160 ⁰ C, lying Reaktionstempera-! Fj door either achieved so that it preheats one or more reaction components before the mixing process or heating the mixing apparatus itself or the manufactured Reaction mixture heats up after mixing. Of course, combinations of these or other procedures for turning i \ make the reaction temperature suitable. In most cases, sufficiently developed during the reaction itself I heat so that the reaction temperature after the start of the reaction to values above 100 ⁰ C M can increase ^1.

When mixing the components, the general procedure is that the water-binding aggregate

I] material first the polyisocyanate or the silica sol or both the polyisocyanate and the silica sol p is added. However, the water-binding aggregate can also be added to the mixture subsequently without any disadvantage SS isocyanate and silica sol are added or vice versa.

I i iilfsstofic such. B. propellants, catalysts, stabilizers, emulsifiers, flame retardants! and inert

i Fillers can be added to the various reactants. Preferably, however, the driving § added medium to the isocyanate and the catalyst to the silica sol.

The mixing of the reaction components is carried out preferably at room temperature, but the processing temperature may also be quite -20 ⁰ C to + 8O ⁰ C.

The quantitative ratio of the three reaction components polyisocyanate, silica sol and the water-binding one Aggregate peat has already been mentioned. It can vary within wide limits, e.g. B. between 5: 2: 93 weight parts and 5: 95: 0 parts by weight and 98: 2: 0 parts by weight. Materials with optimal usage characteristics, in particular high strength, elasticity, heat resistance and good fire-resistant properties, is obtained when the proportion of silica sol is between 20 and 80% by weight, based on the total mixture, organic polyisocyanate between 10 and 80% by weight, based on the total mixture, and water-binding Additives between 10 and 70 wt .-%, based on the total mixture, is. This Range is therefore preferred.

From the standpoint of both superior properties and high economic efficiency Mixtures of

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

10-50% by weight based on the total mixture, organic polyisocyanate, with the exception of nonionic hydrophilic polyisocyanate prepolymers, 20-70% by weight, based on the total mixture, of water-binding additives

especially preferred.

From the stated proportions it can be seen that for the production of inorganic-organic Plastics made from polyisocyanate, silica sol and water-binding filler, the quantitative ratio is not critical is. This is particularly advantageous for continuous production, since precise dosing is not taken into account needs to be. Robust conveyor systems such as gear pumps or screws can be used.

The properties of the inorganic-organic plastics according to the invention, in particular the foams, e.g. B. their density is for a given recipe of the details of the mixing process, z. B. Shape and number of revolutions of the stirrer, design of the mixing chamber us *, and the selected reaction temperature when initiating the foaming somewhat dependent. Ka density can vary between approximately 10 and 200 kg / m ³ . However, foamed materials with bulk densities between 20 and 800 kg / m ³ are preferred.

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

but mostly it is largely open-pored and has compressive strengths between 0.1 and 150 kp / cm ^{2 at densities between 20 and 800 kg / m 1} .

Foamable reaction mixtures can also be poured into cold or heated molds and in these molds, be it relief or solid or hollow shapes, at room temperatures or temperatures up to 200 ° C, if necessary, let harden under pressure.

When using this foam molding technique, molded parts with compacted F ^ aniizonen and completely pore-free, smooth surfaces obtained. Here is the use of reinforcing elements, be it inorganic and / or organic or metallic wires, fibers, fleeces, foams, fabrics, Scaffolding, etc. quite possible. The molded parts accessible in this way can be used directly as components or ζ. Β in ίο Form of sandwich molded parts produced directly or subsequently by lamination with metal, glass, plastic, etc. be used.

In addition to their favorable fire behavior, these materials are characterized by the fact that they are subsequently applied organic or inorganic masses, e.g. B. paints, plaster of paris, putty or sand masses, excellent be liable.

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

The compressive strengths achieved according to the invention on porous materials are to a large extent dependent on the mixing ratio of the starting components and the resulting density, e.g. B. densities between 200 and 600 ig / m ³ and compressive strengths of 10 to 100 kp / cm ² when using a mixture of approximately equal parts of polyisocyanate, silica sol and water-binding filler while using about 5 wt .-% (based on the total amount) of a low-boiling propellant reached.

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

During production, these advantages allow short mold downtimes and thus quick manufacturing cycles reach.

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

The machinability of a foamed material according to the invention offers considerable advantages. So leave it excellent sawing, screwing, nageta, drilling and milling, for example, and is therefore versatile Possible applications.

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

The materials according to the invention open up new possibilities in building construction and civil engineering, as well as in production of prefabricated parts and elements.

Examples of possible applications are the production of wall elements in prefabricated buildings, lost Formwork, roller shutter boxes, window sills, railway · and subway thresholds, curbs, stairs, the Foaming of joints and back foaming of ceramic tiles called.

The compositions according to the invention can also advantageously be used to bind gravel and pieces of marble etc. insert. Decorative panels can be obtained such as those used, for example, as facade elements Find.

Examples

50 output connections

A) polyisocyanate component

Pl: Polyphenyl-polymethylene-polyisocyanate, obtained by aniline-formaldehyde condensation and subsequent Phosgenation. Viscosity at 25 ° C 400 cP, NCO content: 31% by weight (2-core content: 45, 1% by weight, 3-core fraction: 22.3% by weight, proportion of higher-core polyisocyanates 32.6% by weight).

P 2: sulfonated polyphenyl-polymethylene-polyisocyanate (P1) obtained by aniline-formaldehyde condensation and subsequent phosgenation and sulfonation with gaseous sulfur trioxide (sulfur content: 0.98% by weight, NCO content: 30.2% by weight, viscosity at 25 ° C.: 1200 cP).

60 B) Silicate component

S 1: Sodium water glass (44% solids, molar weight ratio Na ₂ O / SiO ₂ = 1: 2) (Henkel)
S 2: silica sol,

65 Bayer silica sol 100

SiOj content ³ ) approx. 30%

Na ₂ O content ^b ) approx. 0.15%

PH value

density

Viscosity')

spec. Surface ¹¹ )

Particle size

ionogenicity

colour

odor

approx. 9.0 1.20 g / cmr 2-3 cp approx. 100 nr / g 25-30 πΐμ anionic milky cloudy odorless

^b )
^c )
^d )
■■ ·)

Determined by drying the brine at 110 ^° C.

Determined by titration. Determined with the Haake falling ball viscometer.

BET value, determined according to Brunauer, Emrnett, Teller.

Solid stone content, which is composed of silica and basic aluminum chloride

S3: silica sol,

Bayer silica sol
SiOj content ³ )
Na ₂ O content ^b )
PH value

density

Viscosity ⁰ )

spec. Surface " ¹ )

Particle size

ionogenicity

colour

odor

200 approx. 30% approx. 0.15% approx. 9.0 UO g / cm ³ 3-4 cp 140-180 nr / g 15-20 ma anionic transparent odorless

Determined by drying the brine at 11 ° C.

Determined by titration. Determined with the Haake falling ball viscometer.

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

Solid content, which is composed of silica and basic aluminum chloride.

S 4: silica sol,

Bayer silica sol

SiOj content ")

Na ₂ O content ^b )

PH value

density

Viscosity')

spec. Surface ")

Particle size

ionogenicity

colour

odor

200E

approx 30%

approx. 0.15%

approx. 9.0

UO g / cm ³

approx. 4 cp

approx. 200 m ² / g

12-15 πΐμ

anionic

slightly opalescent

gemchlos

Determined by drying the brine at 110 ^° C.

Determined by titration. Determined with the Haake falling ball viscometer.

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

l'cslstolTgchalt, which is composed of silica and basic aluminum chloride

10 15th 20th 25th 30th 35 40 45 50

55

S 5: silica sol,

Bayer silica sol 200S Health and safety content ") approx30% ^e ) Na ₂ O content ^b ) - PH value approx. 3.4 density 1.20 g / cm ³ Viscosity ¹ ) 2-3 cp spec. Surface ") Particle size

60 65

Ionicity cationic

Color slightly cloudy

Odorless

₅ ^a ) Determined by drying the brine at 110 ^° C.

^b ) Determined by titration.

^c ) Determined with the Haake falling ball viscometer.

^d ) BET value, determined according to Brunauer, Eminett, Teller.

^c ) Solids content, which is composed of silica and basic aluminum chloride

C) additives

Z 1: emulsifier, 50% strength aqueous solution of the Na salt of a sulfochlorinated paraffin mixture _{Ci 0 -Ci 4} .
Z 2: 33 '/ ₃ % aqueous solution of di-ammonium hydrogen phosphate, (NH ^ HPO ,,.

is Z 3: catalyst consisting of 75% by weight Ν, Ν-dimethylaminoethanol and 25% by weight diazabicyclooctane. Z 4: stabilizer, polyether polysiloxane.
Z 5: chlorinated paraffin

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

Example 1-8

The examples are summarized in the table below Component I and Component II were used for mixed well and then mixed together in a paper cup using a high-speed mixer. in the If Z2 (di-ammonium hydrogen phosphate solution) was also used, this was used as component III separately and added directly after combining the other two components.

It means:

t _R - stirring time (mixing time of the mixture of component I and component II and, if applicable, component III.

t _L = lay time, period from the start of mixing to the start of foaming.
t _A = setting time, the period from the start of mixing to the end of the foaming process (in general, this is also the point in time at which hardening begins).

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

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

IC

P2 Lime ¹ ) Component 1 Triethyl
amine Kataly
sator
Z3 Example l-u emul
gator
Zl Compo
element 3 in
(lake) (sec) Yes
(sec) space
weight
kp / m ¹ pressure
strength
(kp / cm ² ) Table 1 200 100 Trichloro
fluorine-
methane 3 _ _ Compo
nent
Z2 example 200 100 _ 5 - Component 2 - 5 20th 65 140 284 44.8 200 100 - - 2 Silicate-
Comp.
S3 - 5 20th 50 120 297 46.8 1 200 100 - 3 - 100 0.2 5 25th 50 140 324 19.5 2 200 100 - 2 - 100 - 5 20th 53 no 338 43.1 3 175 100 5 3 - 100 - 8th 20th 60 120 386 69.1 4th 175 100 - 2 - 100 0.2 5 20th 47 80 390 63.0 5 175 100 - 2 _ 100 0.2 - 20th 85 125 438 57.0 6th - 100 5 20th 60 135 356 50.6 7th 100 8th 100

') Quick lime, CaO.

Example 9-18

The examples are summarized in the table below. The foams were produced according to Example 1-8, the lower-viscosity component in each case being added to the higher-viscosity component. The abbreviations correspond to those in Examples 1-8, all quantities are in g.

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

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

12th

P2 Z 5 Component I. Sl Example 9-18 component 2 Triäthyi- cement ¹ ) (lake) Il 1.4 space pressure cn / \ amine (sec) (sec) weight strength NJ Table 2 Trichlor cement ¹ ) KuIk ² ) Zl kg / m ³ kp / enr O example 170 20th lluor- 50 5 O
^ J 170 20th methun 50 S3 4th 20th 150 20th 10 50 0.2 C. 20th 22nd 40 292 29.9 150 20th 15th 75 0.2 "J 20th 33 58 291 18.4 200 20th 15th 75 100 0.2 3 15th 22nd 35 265 24.2 9 150 20th 20th 100 100 0.2 4th 15th 24 37 236 18.7 10 200 20th 10 100 100 0.2 15th 30th 45 293 26.2 200 20th 20th 100 75 0.2 ^ 15th 18th 20th 262 31.1 12th 200 20th 30th 100 75 0.2 2 20th 35 52 128 6.6 13th 200 20th 30 100 100 50 0.2 2 100 15th 35 60 277 25.7 14th ') Fast binding cr cement 25th 50 0.2 15th 33 53 157 11.7 15th ² ) quick lime, CuO. 25-100 50 0.2 18th 28 189 15.3 16 "Fondu Lafurge". 50 17th 50 18th

Example 19

To a mixture consisting of 150 parts by weight of cement (PZ 350 F according to DIN 1164), 150 parts by weight of building sand (washed Rhine sand, 0-3 mm) and 175 parts by weight of water became a mixture of 100 parts by weight Silicate component S 3 and 50 parts by weight of polyisocyanate component P2 and the total mixture Intensive mixing for 2 minutes using a high-speed mixer. The pourable mass was in a layer thickness poured from 20 mm, began to solidify 10 minutes later and the test specimen could after 35 minutes Retaining the contours are demolded. The obtained inorganic-organic composite was 3 hours accessible after manufacture.

Example 20

A mixture of 100 parts by weight of polyisocyanate P 1 and 100 parts by weight of cement was added within

Stir in 200 parts by weight of silicate component S 3 for 2 minutes. A trowelable compound was obtained, which in a Layer thickness of 20 mm was spread. The mass began to solidify 20 minutes later and could Can be removed from the mold 1 hour after the start of mixing while retaining the contours. Another hour after that was the

Inorganic-organic composite plastic can be walked on.

Example 21

To a mixture consisting of 250 parts by weight of silicate component S3, 50 parts by weight of water and 40 parts by weight of cement were added to 30 parts by weight of polyisocyanate P2 and the entire mixture for 1 minute by means of mixed with a high speed stirrer. A pourable mass was obtained which was poured out in a layer thickness of 20 mm began to solidify 1 hour later and was accessible after 3 hours.

Example 22

A mixture consisting of 200 parts by weight of silicate component S 3 and 400 parts by weight of building sand was added successively 100 parts by weight of polyisocyanate P2 and 3.5 parts by weight of triethylamine and the total mixture Mix thoroughly for 5 minutes using a high-speed stirrer and spread out in a 20 mm layer. Within In the next 30 minutes, the mass began to set with an increase in volume of approx. 5% and was 3 hours later solidified into a rock-hard, yet elastic, porous, inorganic-organic composite.

Example 23 35

To a mixture of 100 parts by weight of polyisocyanate P2 and 100 parts by weight of cement according to Example 30

100 parts by weight of silicate component S2 were added and the total mixture was mixed well for 1 min. Man received a plasterable mass which was spread in a 20 mm layer thickness, 50 rviin. after manufacture began to set and after a further 2 hours to a walkable inorganic-organic composite

40 was hardened.

14th

Claims (1)

Patent claims: I. Inorganic-organic plastics, obtainable by reacting a mixture of S 2-95 percent by weight, based on the total mixture, aqueous silica sol, 5-98 percent by weight, based on the total mixture, excluding organic polyisocyanate non-ionic hydrophilic polyisocyanate prepolymers,
0-93 percent by weight, based on the total mixture, of water-binding additives.