DE2165912A1 - Silicate foam material prodn - by treating aqs silicate soln with blowing agent and curing agent - Google Patents

Abstract

Foam material for use in insulations, filling hollow spaces, packages and building materials is produced by treating an aqs. silicate soln., which may contain inorg. or org. additives, with blowing agents and acid-providing curing agents. Product has high porosity and good resistance to solvents and fire. Specif., the blowing agent is butane or CFCl3. The curing agent is carbon dioxide, carbonyl chloride, chloroformic ester, or sulphochloride. The curing agent is added to a sodium silicate soln. with a density of 1.36 (8.6 wt.% Na2O and 25.4 wt.% SiO2) so that gelling is effected in 15 mins. at 25 degrees C.

Description

Process for Making Foams The present invention relates to a process for the production of foams, which is an essentially have a structure consisting of silicates.

It has already been proposed that aqueous silicate solutions possibly contain thickener, beat with air to form a foam and this Then let the foam harden (see e.g. French patent specification 2 055 341).

Such methods have the disadvantage that the intended for solidification foamy material retains or even reduces its volume during hardening. So it is difficult to create complicated shapes, such as undercuts have to be filled in evenly or to carry out such foaming who care to ensure that the foam on the mold walls a certain Exerts pressure, e.g. to create a better bond with the wall material or its through urge to ensure.

A process for the production of foams has now been found, which is characterized in that optionally inorganic and / or Aqueous silicate solutions containing organic admixtures with propellants and acid-releasing hardeners added.

Surprisingly, it has been found that aqueous silicate solutions Can be foamed very well, and that also one with the hardening process in parallel progressive expansion of the silicate that forms can be achieved if one the silicate solution mixed together with a blowing agent and a hardener and If necessary, foam the mixture produced in this way while shaping it and harden it leaves. Particularly suitable hardeners are those substances which are in aqueous media Set free carboxylic acid and / or sulfonic acids and / or mineral acids. Preferred are acid-releasing hardeners that are more than 10% admixture to a 0.5 wt. Na-C14-Alkylsulfonat containing sodium silicate solution with a density of approx. 1.36 (Na2O content approx. SiO2 content approx. 25.4% by weight), this at 25 0C to gel in less than 15 minutes bring.

Aqueous silicate solutions are used for the process according to the invention Solutions of silicates in water or aqueous media into consideration, which both the Can have the character of real as well as colloidal solutions; e.g. ammonium silicates or metal silicates. Preferably alkali silicate solutions, e.g. sodium and / or Potassium silicate solutions into consideration. A very suitable starting material are those so-called water glass solutions that have been on the market for a long time. Here the dissolved silicate does not necessarily need the formula Na2O. To correspond to 3 - 4 SiO2, as it is used as a basis for water glass, for example. The proportions of alkali metal oxide to SiO2, e.g. NagSiO4 to polysilicates of various degrees of polymerization, in which the ratio of alkali metal oxide to SiO2 is less than 1: 1, e.g. 0.1: 1, vary. However, a flowable silicate solution is a prerequisite. The concentration this solutions is upward due to the necessary fluidity of the solutions with about 60 ", although more concentrated solutions, for example, are also limited Kneading units would be processable at elevated temperatures. Down is the Concentration limited by using solutions with less than 5% solids in general only give gels with unsatisfactory strength. Silicate solutions are preferred used with 10 - 50% by weight fixed content.

Inorganic or organic admixtures are to be understood as meaning which can be soluble or insoluble in the silicate solution in gaseous, liquid or solid form, as long as they are compatible, i.e. the silicate solution is not already under the mixing conditions to fail.

Preferred additions are those which keep the silicate solution at room temperature do not fail even after days or months. These admixtures can change the character of fillers can be diluents or special auxiliaries.

Solid inorganic or organic substances can be used as fillers Find use that z. B. as powder, granules, wire, fibers, dumbbells, crystallites, Spirals, rods, pearls, hollow beads, foam parts, fleeces, pieces of fabric, Knitted fabrics, tapes, pieces of film, etc. are present, for example dolomite, chalk, Alumina, asbestos, basic silicas, sand, talc, iron oxide, aluminum oxide and oxide hydrates, alkali silicates, zeolites, mixed silicates, calcium silicates, calcium sulfates, Aluminosilicates, cements, basalt wool or powder, glass fibers, carbon fibers, graphite, Soot, Al, Fe, Cu, Ag powder, molybdenum sulfide, steel wool, bronze or copper mesh, Silicon powder, expanded clay particles, hollow glass spheres, glass powder, lava and pumice particles, Wood shavings, wood flour, cork, cotton, straw, popcorn, coke, filled particles or unfilled, foamed or unfoamed, stretched or unstretched organic Polymers. Examples are from the large number of organic ones that can be considered Polymers some listed, these z. B.

as powder, granules, foam particles, pearls, hollow pearls, foamable but still unfoamed particles, such as fibers, tapes, woven fabrics, fleece, etc. are present can: polystyrene, polyethylene, polypropylene, polyacrylonitrile, polybutadiene, polyisoprene, Polytetrafluoroethylene, aliphatic and aromatic polyesters, melamine or urea Phenolic resins, polyacetal resins, polyepoxides, polyhydantiones, polyureas, polyethers, Polyurethanes, polyimides, polyamides, polysulfones, polycarbonates, of course also any copolymers, provided that they meet the precondition of compatibility meet with the silicate solutions.

Particularly noteworthy fillers are dolomite, chalk, talc, glass in any shape, carbon, polystyrene, polyvinyl chloride, and polyethylene in foamed and unfoamed form, terephthalic acid polyester, polyacrylonitrile, polyamides, polypropylene, Polyurethanes as fibers, non-woven fabrics or foam.

According to a particular embodiment of the method according to the invention can also use the precursors of solid polymers, provided they meet the condition of compatibility meet with the silicate solutions, in solid or liquid form as an admixture or Filler used and during or after the curing process in turn by appropriate Reactions are polymerized or hardened.

For example, styrene, mixtures of styrene and unsaturated z, B. Maleic acid polyesters, diallyl phthalate or methyl methacrylate or solutions of monomers in polymers.

Also suitable in this sense are, for example, melamine, Urea, phenols or other substances such as amines that interact with other reactive components which, such as formaldehyde or certain isocyanates, are compatible with the silicate solutions and can also be added3 if necessary one to harden the Silicate solution additionally running hardening process or polymerization, polycondensation or polyaddition process.

In the context of the method according to the invention, compatible gaseous admixtures to the silicate solutions as more or less voluminous Consider filler. Such gases, to which preferably air, but also Oxygen, Nitrogen, SF6J hydrogen, noble gas, methane, CF4 can include the silicate solutions possibly in a mixture with the other admixtures, without pressure or under overpressure are mixed in. Here is an additional use of foam-forming and Foam stabilizing auxiliaries, as described below, are advantageous.

In this way, according to the invention, foamed moldings can be obtained the admixture of the gases, as well as the other fillers, Thinners or other auxiliaries, i.e. the admixtures, in whole or in part before, during or immediately after the addition of the curing reaction Additions can be made in one or more operations.

In general, the additives referred to as fillers added in such amounts that the content of the reaction mixtures of dissolved Silicate if possible over 5% by weight, preferably between 10 and 50% by weight.

Diluents can be used as further admixtures. Here it can be aqueous or non-aqueous diluents.

A borderline case to fillers is next to their use of polymer solutions e.g. of polystyrene, polyesters, rubber in gasoline, benzene or chloroform or phenol, urea or melamine-formaldehyde precondensates the use of polymer dispersions as diluents in water. Such polymer dispersions come into consideration here, according to conventional Processes are accessible, but with the silicate solutions in double Must be compatible: once they must not precipitate the silicate solution, on the other hand, they must not be precipitated by the silicate solution. This condition is available from many commercially available or known in the art Dispersions of polyurethanes, polyvinyl acetate, polystyrene, polybutadiene, polyacrylates, Polyacrylonitrile, polyethylene, polyvinyl chloride or their copolymers, however, since it is often dependent on the emulsifier, it must be carried out in simple preliminary tests on a case-by-case basis to be checked.

These diluents can be used in such amounts that the silicate content of the mixtures is over 5% by weight, preferably between 10 and 50 wt.

Other diluents, e.g. aqueous formaldehyde solutions or diluents insoluble in the silicate solution, which can also serve as a diluent for the hardener to be added later, be worked, whereby their compatibility is a prerequisite. Such diluents are for example aliphatic and aromatic hydrocarbons such as benzene, Toluene, xylene, styrene, benzine, paraffin oil, paraffin waxes, fatty acid esters, bis (ethoxy) terephthalate, Diethyl carbonate, glycol diacetate, diethyl phthalate, silicones, triethyl phosphate, ethyl benzoate, Butyl acetate, ethyl orthoformate, oleic acid glyceride, chlorinated hydrocarbons such as halomethanes, petroleum cuts, bitumen, etc.

These diluents can also be added as propellants Connections are counted. Suitable propellants are alkanes, alkenes and halogen-substituted ones Alkanes or alkenes or dialkyl ethers. Volatile substances are primarily used for this purpose with boiling points between -25 0C and + 500C possible, preferred with boiling points between -150C and + 400C, preferably in the silicate solution are insoluble. Such substances are e.g. saturated or unsaturated hydrocarbons with 4 - 5 carbon atoms such as isobutylene, butadiene, isoprene, butane, pentane, petroleum ether, halogenated saturated or unsaturated hydrocarbons such as chloromethyl, methylene chloride, Fluorotrichloromethane, difluorodichloromethane, trifluorochloromethane, chloroethane, vinyl chloride, Vinylidene chloride. Trichlorofluoromethane and vinyl chloride have proven to be the most suitable and C4 hydrocarbons such as butane.

The task of these blowing agents is during the hardening process Reaction mixture passing through states of increasing viscosity during hardening or to be converted into a foam during a post-heating process. The propellants are preferred in amounts of 0.1-50 g, based on the reaction mixture 2 - 30 wt., Used.

As a special aid from the group of inorganic or organic In addition to colorants, odorous substances and thickeners such as, for example, auxiliaries are Methyl cellulose, starch, water repellants such as silicone or fluorinated compounds in particular wetting agents, foam stabilizers, pore regulators and emulsifiers with ionic or non-ionic character. Emulsifying agents are particularly important here Substances that the incorporation of the hardener and other admixtures are essential can facilitate. In addition to the non-ionic compounds, the mostly addition products from alkylene oxides such as ethylene oxide to hydrophobic siloxanes, copolymers of ethylene oxide and propylene oxide, fatty acids, fatty alcohols or phenols are preferred here Alkyl sulfonates with 10-18 C atoms in the alkyl radical named with the silicate solutions are well tolerated and have a good emulsifying effect for systems with a continuous water phase and a good foaming effect. These tools are in pure form or preferably in the form of their aqueous solutions or dispersions or also in the diluents or

used dissolved in the hardeners. In the reaction mixture they can be used in Amounts from 0.05 to 40 wt.

Additional amounts of 0.5 to 15% by weight are preferred. In special cases, for example when the desired shaped bodies have a very strongly hydrophilic character These additional amounts can be used as a carrier or as a carrier for these substances be crossed, be exceeded, be passed.

The hardeners correspond to known substance classes. Mixtures can also be used different hardeners can be used to make thickening and hardening times variable to adjust.

Mixtures of hardeners with other alkali silicate solutions also solidify Additives can be used; such as with pyrocarbonic acid esters or carboxylic acid carbonic acid ester anhydrides or other carboxylic acid esters with hardening effect or additives according to the Belgian U.S. Patent 753,761. According to the invention, in principle, all substances can be used as Hardeners are used, which cause an acidic reaction in an aqueous medium by they release CO2, carboxylic acids, sulfonic acids or mineral acids, for example.

Such compounds or mixtures of are preferably used as hardeners Compounds which are used as a 10% by weight admixture to a 0.5% by weight Na-C14-alkyl sulfonate containing sodium silicate solution with a density of approx. 1.36 (Na2O content approx. 8.6% by weight SiO2 content approx. 25.4% by weight) this gels at 25 ° C in less than 15 minutes bring. This test is Easily feasible and is used in experimental Part described.

Particularly suitable hardeners or hardener mixtures are in particular that are liquid at temperatures below 500C, especially those that are too are still liquid below 300C, as these hardeners are particularly easy to use technically permit.

Accordingly, aliphatic, cyclic, araliphatic or aromatic compounds used, for example derived from the following classes of compounds: carboxylic acids and carboxylic acid anhydrides such as methylhexahydrophthalic anhydride, isopropenylsuccinic anhydride, octanecarboxylic anhydride, Oleic acid-acetic acid mixed anhydride, benzoic acid-acetic acid mixed anhydride, carboxylic acid halides, preferably carboxylic acid chlorides of mono- and polycarboxylic acids such as Versatic acid chloride, Oleic acid chloride, benzoic acid chloride, 3-methylbenzoyl chloride, 3-methoxybenzoyl chloride, higher alkyl or alkoxybenzoyl chlorides, diphenylmethanedicarboxylic acid chlorides, s- and as-phthalyl chloride, isophthalyl chloride, terephthalyl chloride, chlorides of the benzene tri and tetracarboxylic acids, as well as alkyl, alkoxy and halogen substitution products of Benzene dicarboxylic acid chlorides, such as chloroisophthalyl chlorides. Chlor ant esters such as e.g. the chorium ant esters of ethanol, butanol and octanol, of ethylene glycol, of glycerine, trimethylolpropane, pentaerythritol, fatty alcohols, cyclohexanol, of phenol, pyrocatechol, hydroxyethoxyphenol, hydroxypropoxyphenol or hydroquinones, of diphenol methane or dimethyl diphenol methane and their Alkoxylation products, of cresol or xylenol and their alkoxylation products, the alkylphenols, for example isopropylphenol. Sulfates, e.g. dimethyl sulfate, Diethyl sulfate, dipropyl sulfate, sulfonic acid halides, especially sulfochlorides such as Eenzenesulfon chloride, tosyl chloride, 3,4-dichlorobenzenesulfochloride, isopropyl or Isooctylbenzenesulfochloride Also suitable are sulfonic acid esters, phosphoric acid esters, Isocyanates such as cyclohexyl isocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Phenyl isocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate. links with easily split off halogen, such as imide chlorides, isocyanide dichrides, e.g. phenyl isocyanide dichloride, Chlorpyrimidines, halotriazines such as 2- (methoxyethoxy) -4,6-dichloro-s-triazine, 2-isopropoxy-4, 6-dichloro-s-triazine.

Are particularly well suited for the present method Acid chlorides, chloroform iron esters and anhydrides such as benzoyl chloride, phthalyl chloride, Phenyl chloroformate, bis-chloroformate of diphenol methane or dimethyl-diphenol methane.

The substances mentioned as hardeners can be used alone or in a mixture with each other or with other substances gelling silicate solutions e.g. with diethyl pyrocarbonate, with isophthalic acid-bis-carbonic acid monoethyl ester anhydride, diethyloxalate, methyl and ethyl esters of (mono, di, tri) chloroacetic acid, 2-oxo-4-methyl-l,) - dioxolone, Vinyl acetate, dimethyl carbonate, dimethyl maleate, glycol diacetate, etc. can be used.

Substangemixtures can also be used in which at least one component, by definition, has a gel time of more than 15 minutes yields, which, however, bring about gel times of less than 15 minutes.

The hardener or hardener mixtures should, based on the reaction mixture Can be used in amounts of 0.01 to 60% by weight, preferably 0.5 to 30% by weight.

It is also easily possible to use the hardening substances alone, i.e. without adding propellant. In this case, there are no foams, but obtained more or less massive masses, the inventive production of Foams are basically done so that one in a discontinuous or continuous mixing device the reaction components described mixed with one another in one or more stages and the resulting mixture mostly outside the mixing device in forms or on suitable documents foam and freeze. This can be between about 0 ° C and 100 ° C, preferred between 25 ° C and 60 ° C, the reaction temperature can either be reached in such a way that that one or more reaction components are preheated before the mixing process or the mixing apparatus itself is heated, or the reaction mixture prepared after heats up after mixing. Combinations of these or others are of course also possible Procedures suitable for adjusting the reaction temperature. Often developed during the reaction itself enough heat so that the original reaction temperature may well increase to values above 100 ° C. after the start of the reaction or foaming can. However, the measure provided according to the invention is achieved by this heat of reaction, which says that the foaming is carried out at temperatures between 0 and 1000C should not be touched, because this measure relates to the initiation of the Foaming. The properties of the resulting foams, e.g. their density in the moist state depends on the details for a given recipe of the mixing process, e.g. shape and number of revolutions of the stirrer, design of the mixing chamber etc. as well as the chosen reaction temperature when initiating the foaming somewhat dependent. It can vary in order of magnitude between 0.05 and 0.95, mostly one obtains densities of the moist, fresh foam between 0.15 and 0.6. The dried ones Foams can have a closed or open-pore character, in most cases they are largely open-pored and have densities between 0.02 and 0.9 It goes without saying also possible, the optionally already inorganic andX or organic admixtures containing silicate solutions initially by an insufficient amount, i.e. probably the condensation the silicates or silicic acid to form higher molecular weight aggregates, but not their final aggregates Crosslinking, i.e. the amount of hardener that sets the material in a more viscous state to be transferred and then later after storage or any application technology Manipulations, if necessary, by adding further quantities of hardener, the hardening to be completed to any extent.

The behavior of the reaction mixtures results in the inventive Process diverse application possibilities and corresponding areas of application, some of which are outlined below as examples. The possibility of that water contained in the hardened mixtures either as a desired component to be left in the foam or the foam by means of a suitable coating or To protect the lamination against water leakage, or the water by means of suitable drying processes, e.g. heating cabinet, hot air, IR heating, ultrasound or high frequency exposure to completely or partially remove, karin the required application technology on a case-by-case basis Goals to be chosen according to.

The reaction mixture containing propellant can be given, for example warm, cold or IR or HF irradiated documents are painted on or after Passing through the mixing device with compressed air or using the airless method be sprayed onto these substrates where it can foam and harden and so on results in a filling or insulating or moisture-resistant coating. One can Press and pour the foaming reaction mixture into cold or heated molds or injection molding and it in these forms, be it relief or solid or hollow forms, optionally by centrifugal casting at room temperature or temperatures up to 2000C, optionally let harden under pressure. The use of reinforcing elements is also important here, be it inorganic and / or organic or

metallic wires, fibers, fleeces, foams, fabrics, scaffolding etc., quite possible. This can be done, for example, using the fiber mat impregnation process or by methods in which, for example by means of a spray device, reaction mixtures and reinforcing fibers are applied together to the mold. the Molded parts that are accessible in this way can be used as components, e.g. in the form of directly or subsequently by lamination with metal, glass, plastic, etc.

produced, optionally foamed, sandwich moldings used the favorable fire behavior in the wet or dry state of Advantage is. However, they can also be used as a hollow body, e.g. as a container for possibly Goods that are to be kept moist or cool are used as filter materials or Exchangers, as catalyst or active ingredient carriers, as decorative elements, furniture components and cavity fillings. They can also be used as highly stressable lubricants and coolants or carriers for it, e.g. used in metal extrusion. Also an application in the field of model and mold making, as well as the production of molds for the metal casting is to be considered.

A preferred mode of operation is the foaming process to go hand in hand with the hardening process, e.g. by placing in a mixing chamber the reaction mixture produces and at the same time the volatile propellant added, such as dichlorodifluoromethane, trichlorofluoromethane, butane, isobutylene, Vinyl chloride, so that with a suitable choice of the mixing temperature that from the mixing chamber exiting reaction mixture foams at the same time by evaporation of the propellant and hardens by the action of the hardener, the resulting foam, which optionally still contains emulsifiers and foam stabilizers and other auxiliaries, fixed will. Furthermore, the initially still thin reaction mixture can be added by entering it possibly pressurized gases such as air, methane, CF4, noble gases, to form a foam, which is brought into the desired shape and cured in this way will. You can also proceed accordingly by first of all, if necessary Foam stabilizers such as wetting agents, foaming agents, emulsifiers and possibly others Silicate solution containing organic or inorganic fillers or diluents converted into a foam by gassing with the gases mentioned and this foam then in a mixing device with the serving as precipitants Hardener mixed and then foamed and allowed to harden.

The foams accessible in this way can be dried or moist, optionally after a compression or tempering process, optionally under Printing, as insulating materials, cavity fillings, packaging materials, building materials with good solvent resistance and favorable fire behavior can be used. They are also available as lightweight building blocks, in the form of sandwiches, e.g. with metal top layers Can be used in house, vehicle and aircraft construction.

The reaction mixtures can also be dispersed in droplet form, e.g. in gasoline or during a free fall or similar

brought to a foaming and hardening, whereby foam pearls are formed.

You can also use the foaming reaction mixtures as long as they are still flowable, organic and / or inorganic, capable of foaming or already foamed particles, e.g. expanded clay, expanded glass, wood, popcorn, cork, hollow beads made of plastics e.g. vinyl chloride polymers, polyethylene, styrene polymers or foam particles made of these or, for example, polysulfone, polyepoxy, polyurethane, Incorporate or incorporate urea-formaldehyde, phenol-formaldehyde, polyimide polymers Let the reaction mixtures foam through beds of these particles, and In this way, produce insulating materials that have a favorable fire behavior distinguish.

If a mixture of optionally inorganic and / or organic Aqueous silicate solutions containing admixtures and the hardeners at a predetermined level Temperature that under these temperatures enabled evaporation or gas formation Propellant, for example a (halogen) hydrocarbon, added at the same time the resulting initially liquid mixture can not only be used for production of uniform foams or other foamed or non-foamed fillers Containing foams can be used, but you can also use it with predetermined Nonwovens, fabrics, grids, structural parts or other permeable structures Foam through from foamed or non-foamed material, so that in this way Composite foams with special properties, e.g. favorable fire behavior can be accessed directly as a construction element in construction, furniture or Driving and aircraft sectors can be used.

The foams which can be produced by the process according to the invention can the soil in crumbs, if necessary with fertilizers and pesticides enriched in order to improve its agrarian consistency. High water-containing foams can be used as a substrate for the propagation of seedlings, cuttings and plants or schmittflowers are used. By spraying the mixtures on impassable or loosely grounded terrain, such as dunes or swamps, a effective consolidation can be achieved, which can be walked on after a short time, or a Protection against erosion offers.

It is also of interest to use the proposed reaction mixtures spray onto an object to be protected in the event of a fire or disaster, where the included Water on the surface of what is to be protected Body cannot run off or evaporate prematurely, so that a particularly effective one Fire, heat or radiation protection is achieved because the hardened mixture, as long as it still contains water, it cannot heat up significantly above 1000C or IR or nuclear radiation absorbed.

Due to the good sprayability, the mixtures can be mixed by using them for example on fabric, other surfaces, grids or even just on walls sprays, effective protective walls and protective layers in mining in the event of an accident or also educate in routine work. Here it is of particular importance that curing can be achieved even in the short term.

The foaming mixtures according to the invention can also be used in the Building construction, civil engineering and road construction to create walls, igloos, seals, for grouting, plastering, grounds, insulating, decorating, as coating, screed and Covering material can be used. Their use as glue or mortar or Casting compound optionally in filled form, with inorganic or organic fillers should also be considered.

As the hardened foams according to the method after drying can have considerable porosity, they are suitable as desiccants, because they can in turn absorb water. However, you can also use them with active ingredients loaded or used as a catalyst carrier or filter and absorbent.

Optionally used or subsequently used in the reaction mixture added auxiliaries such as emulsifiers, detergent raw materials, Dispersants, Wetting agents, fragrances and substances with a hydrophobic effect make the properties possible of the foams in the water-containing or dried state as required.

On the other hand, the foams can be water-based or dried or in the impregnated state, subsequently painted, metallized, coated, laminated, galvanized, vapor-deposited, glued or flocked. The moldings can be in water-containing or dried state are further deformed, for example by sawing, milling, drilling, planing, polishing and other processing methods.

The optionally filled shaped bodies can be subjected to thermal aftertreatment, Oxidation processes, hot pressing, sintering processes or superficial melting or other compression processes continue to be modified in their properties will.

Inorganic and / or organic foamed materials are suitable as molding material or non-foamed materials such as metals, e.g. iron, nickel, stainless steel, lacquered or e.g. Teflonized aluminum, porcelain, glass, plaster, cement, wood, plastics such as PVC, polyethylene, polyurethane, ABS, polycarbonate, etc.

The foams accessible according to the process can be superficial or as long as the structures are largely permeable, for example more open-pored Dealing with foams or porous materials, including by centrifugation, vacuum treatment, Blowing through with air or rinsing with the contained water to remove (if necessary heated) liquids or gases such as methanol, ethanol, acetone, dioxane, Benzene, Chloroform and the like or air, CO2> superheated steam. In an analogous way is also an aftertreatment of the moist or dry moldings by rinsing or impregnation with aqueous or non-aqueous acidic, neutral or basic Liquids or gases e.g. hydrochloric acid, phosphoric acid, formic acid, acetic acid, Ammonia, amines, organic or inorganic salt solutions, paint solutions, solutions of monomers that have yet to be polymerized or that have already been polymerized, dye solutions, Electroplating baths, solutions of catalysts or catalyst precursors, odorous substances to consider.

The previous presentation should not claim to be exhaustive the general application possibilities of production according to the process of moldings, i.e. their mostly already predetermined by the manufacturing process Explain possible uses.

The method according to the invention is explained below by way of example will. The parts given are parts by weight, unless otherwise noted is.

Example 1: In the following, the determination of the gel time, which of the various hardeners or hardener mixtures provided, described, and for some hardener prototypes are given as examples: All substances and devices are tempered to 25 ° C. Then 100 g of sodium silicate solution are added to a mixing beaker (5 cm) (Density 1.36, Na20 content approx. 8.6% by weight, SiO2 content approx. 25.4% by weight) in the previous 0.5 weight g of C14 alkyl sulfonate sodium had been dissolved. ln the solution is enough an L-shaped curved one Glass rod up to the middle of the filling level, the Distance from the wall of the curved leg is approx. 5 mm. The glass rod is 250 IJpM rotated and acts as a stirrer, the mixing bowl is fixed. Now you give into the stirred water glass solution the hardener substance and measures the time from that moment passes until the mixture, which can initially be smoothly stirrable, has solidified. This time will referred to as the gel time.

The following substances which act as hardeners are exemplified The following gel times are determined: Hardener substance: Min. sec. Hardener number Butyric acid chloride 7 1 tetrapropenyl succinic anhydride 21 2 hexahydrophthalic anhydride 30 3 butyl chloroformate 48 4 isooctyl chloroformate 1 18 5 oleic acid chlorici 1 31 6 Benzoyl chloride 2 1 7 2 (Methoxyethoxy) -4, 6-dichloros-triazine 2 21 8 3-Methyl-benzoyl chloride 3 17 9 oleic acid acetic anhydride 4 26 10 phenyl chloroformate 4 27 11 2-chlorobenzoyl chloride 6 24 12 tolylene diisocyanate 9 30 13 benzenesulfonic acid chloride 10 19 14 hexamethylene diisocyanate 12 57 15 dimethyl sulfate 13 55 16 phthalyl chloride, sym. 4 12 17 Hardener substance: Min. Sec. Hardener number isophthalchloride 3 28 18 cresyl chloroformate 3 30 19 5-chloroisophthalyl chloride 10 10 20 diphenolmethane dichloroformate 2 50 21 The im The following substances mentioned have, by definition, a too slow one on their own Gelling effect, however, they can be components of a mixture that is produced by a corresponding content of fast-acting hardener, however, the required gelling speed he brings.

Types of such mixtures are listed by way of example; here is the additional use of gelling substances in the present process are not claimed1 quite possible, provided the necessary gel times can be achieved.

Weight ratio Min. Sec.

p Toluenesulfonic acid chloride / benzoyl chloride 2: 1 4 19 2-isopropyl-4,6-dichloro-s-triazine / ethyl chloroacetate 1: 1 5 54 3, 4-dichlorobenzoyl chloride / butyrochloride 4: 1 6 16 phthalyl chloride / benzoyl chloride 1: 1 1 49 The numbering of the hardener substances made in Example 1 is shown in used in the following examples.

Example 2: Using the example of hardener 7, the production of im Foam produced by hand foaming process under various conditions the following are described: 800 parts of 40some soda waterglass solution, the 4 parts of C14-Al -Kylsulfonat-Sodium in solution, are brought to 45 ° C and in an open Mixing bowl filled. While stirring with a propeller stirrer, one adds in one Adding: 90 parts of benzoyl chloride mixed with 65 parts. Trichlorofluoromethane. Despite The mixture can be stirred well for a few seconds before the elevated temperature it begins to rise in the mixing bowl. The foaming mixture is then poured immediately in a box made of paper; there the mixture begins to rise immediately and after a few seconds continues the rising process, intensified because of the reaction of the hardener 7 sets in a further increase in temperature. After about 4 minutes it is Foam solidifies in the box and can then be removed from the paper. As a result of further reaction, part of the water contained in the foam (approx. 140 Tle.) Pressed out of the foam by itself. The finished moist foam can easily cut into any shape. It has a density of approx. 0.3 and is evenly fine-pored. It dries when standing in moving air or in a circulating cupboard very quickly and then has a density of approx. 0.06. Such foams can be used as Insulating material can be used.

Example 3: The procedure is as in Example 2. However, one uses a DO «-ige potassium silicate solution. There are no differences in the course of the default. The resulting foam has a density of 0.045 in the dry state.

Example 4: The procedure is as in Example 2. Instead of 40-fist Soda water glass solution, however, a 20% solution will be used, in addition only 30 parts of trichlorofluoromethane used. The resulting foam has a density of 0.09 when dry.

Example 5: The procedure is as in Example 2, but one uses 150 parts of the hardener 7. In this case, stir as quickly and briefly as possible so that the mixture does not harden until it has foamed enough. Pours after approx. 5 sec. mixing time in the mold, you get a foam that is moist State has a density of approx. 0.3 and then, if it immediately after hardening, i.e. after approx. 2 - 3 minutes is removed from the mold, approx. 200 teaspoons of water run off leaves, which of course makes the subsequent drying process cheaper.

Example 6: The procedure is as in Example 2, but now not worked at 450C, but at 3000. The foam doesn't rise as much, his Density in the dry state is approx. 0.15.

Example 7: The procedure is as in Example 2, but at approx. 250C, the foam produced has a density of approx. 0.28 in the dry state.

Example 8: The procedure is as in example 2, but one uses only 40 parts hardener 7. The resulting foam has a dry density of 0.07 State.

Example 9: The procedure is as in Example 2, but one uses only 10 parts trichlorofluoromethane. The resulting foam has dried in Condition a density of approx. Ob55.

Example 10: The procedure is analogous to Example 2, but one uses as an additive to the silicate solution instead of the C14-alkylsulphonate sodium now 20 parts. of an adduct of 10 moles of Athylenoxic with isooctyl phenol. The dried one Foam has a density of approx.

Example 11: The procedure is analogous to Example 2, in the sodium silicate solution however, an additional 200 teaspoons of chalk powder are stirred in. The resulting After drying, foam has a density of approx. 0.1. You can also use the Use chalk talc powder, quartz powder, short glass fiber, silicon powder or kaolin.

The mixtures formed in Example 2-11 can after stirring can also be filled into a mold in which there are expanded clay particles, fibers or styrene foam particles are located. Since the freshly made mixture is still very thin, it penetrates it the filling of the mold and wets the filled particles. When frothing the foam particles in the mold become fibers or other solids distributed in the resulting foam, creating a combined foam body.

The freshly made mixture can also be used before foaming into one that is too narrow for the volume of the foam produced and for sicfl Fill the mold in which then foamed the mixture and fills in and depicts all the elements of the form under pressure. This creates foam bodies, which have a largely closed surface layer. The achievable here The density of the resulting foam body depends on the degree of filling the mold with the freshly prepared reaction mixture.

In principle, examples 2-11 can also be used analogously with the others Hardeners 1 - 20 can be carried out. Other propellants can also be used Find. This involves working in open vessels by hand with low-boiling ones However, there are naturally limits to blowing agents and fast-reacting hardeners. If you want to reduce too much activity of a hardener, next is recommended Reducing the reaction temperature, diluting the hardener with one of e.g. described diluent.

Example 12: The procedure is as in Example 2. However, one uses instead of hardener 7 a mixture of ethyl chloroformate (not in example 1 listed) and chloroform in a weight ratio of 30:60. The resulting foam has a density of approx. 0.15 after drying.

The foams according to the process can be better processed in a continuous manner working apparatus: This apparatus continuously mixes a metered one Stream of silicate solution (the optionally inorganic and / or organic additions may contain) with further added components e.g. hardeners, blowing agents, Diluents and carries that at the respective desired temperature manufactured Mixture, optionally filled into molds or applied to tapes can be, or is sprayed. The construction of such a mixing apparatus is not subject to any restrictions, in principle such devices are made from polyurethane foam technology well known.

In the following examples a mixing apparatus is used which consists of an approx. 40 ml mixing chamber in which there is an approx. 1000 UpX rotating propeller is located. At the head of the mixing chamber, if necessary preheated silicate solution and, via a separate feed, hardener and blowing agent and diluent (if used) metered in. The mixture of the reaction components is forced through the mixing chamber provided with a temperature measuring device and is homogenized and discharged through a nozzle. This nozzle consists of an outlet pipe the length of which can be varied as required. The exit mixture can be converted into Discharge forms or on running belts and there the foaming process in front of you let go. The foams produced on a moving belt are cut in such a way that that rectangular plates are formed. These plates are in the circulating air cabinet or dried in a high-frequency oven, trimmed again on cutting devices and used to determine the density. The sheet goods obtained can be used as insulating material with high heat resistance and favorable fire behavior can be used. Removed the still moist foams by extraction with water or acids, for example HC1 or the organic substance by treatment with suitable solvents largely, after drying, insulating materials are obtained that are completely non-flammable are to be classified. One can also get the organic matter through thermal Aftercare remove from the foams by distilling, subliming or oxidizing, whereby a complete incombustibility can be achieved.

The following are foams which can be produced on the apparatus described in the form of recipe information tabella.risch listed as an example: Example 13: In all of the tests listed in the table below, a 58 ", filler-free Soda waterglass solution containing 0.5% by weight of Na-C14-alkylsulfonate at 1600 parts / minute dosed.

Hardener thinner propellant mixture dry. Foam No. / Part / Min. Name / Part / Min. Name / Part / Min. ° C gr / cm3 4/100 A / 60 18 0.09 2 / 50.3 / 100 H / 200 A / 80 25 0.1 1 / 20.20 / 50 K / 70 B / 100 15 0.11 4/10, 5/90 I / 200 B / 100 15 0.08 6/50, 8/100 B / 50 30 0.17 18/100, 9/20 D / 50 50 0.1 19/120 C / 30 35 0.08 16/60 K / 100 D / 40 55 0.1 17/70 C / 60 30 0.06 11/80 D / 80 40 0.05 11/120 C / 20, D / 80 30 0.04 9/80, 13/30 D / 50 50 0.09 11/40 D / 20 45 0.2 1/8, 17/40 A / 50 10 0.1 16/40, 3/15 C / 50 18 0.09 16/80 C / 50 27 0.11 14/130 D / 60 50 0.1 14/120, P / 12 D / 20 45 0.2 14/120, R / 30 D / 80 45 0.05 12/100, Q / 20 D / 60 45 0.08 Hardener thinner propellant Mix trookn. Foam No. / Part / Min. Name / Part / Min. Name / Part / Min. ° C gr / cm3 9/80, 7/40, 3/20 C / 20, D / 60 40 0.05 7/190 D / 60 45 0.05 7/190 D / 40 45 0.09 7/190 D / 20 45 0.13 7/190 D / 10 45 0.26 7/190 D / 5 45 0.55 7/300 D / 60 40 0.18 7/150 D / 60 40 0.09 7/75 D / 60 40 0.07 7/35 D / 60 40 0.06 In the table from example 13 the following abbreviations were used for hardeners> thinners and propellants used: Additional gelling substances: P = diethyloxalate Q = ethyl formate R = diethyl pyrocarbonate. Diluent: H = chloroform I = petroleum ether (Bp from 400C) K = trichlorethylene propellant: A = vinyl chloride B = butane C = dichlorodifluoromethane D = trichlorofluoromethane.

Example 14: The procedure is analogous to Example 13. 1600 parts of the Na-C14-alkylsulfonate-containing sodium silicate solution according to Example 13 (preheated to 450C), 160 parts of hardener 9 and 60 parts of propellant D are passed through the Mixing apparatus given. The outflowing mixture is due to its own pressure a slowly rotating inflated half-shell made of rubber blanket sprayed. On this Half-shell foams the mixture and hardens. This way you can make an igloo or build a hollow body of any wall thickness. Appropriately, a Wall thickness of approx. 40 cm selected. After about 60 minutes the smell is gone after Benzoyl chloride almost completely disappeared. After 3 hours it is placed in the half-shell cut a doorway and the rubber skin. after venting through the opening removed. It is a self-supporting foam igloo, which after a few Days has dried out in dry weather and e.g. by a bitumen coating can be protected against the effects of the weather. The igloo made in this way is not flammable.

Example 15: You work analogously to Example 2, but use instead of hardener 7 Now 150 parts of hardener 16 and 85 parts of trichlorofluoromethane. The emerging Foam hardens much more slowly and is somewhat larger-pored. After about 10 minutes can be demolded. The dried foam has a density of approx. Ovo8.

Example 16: The procedure is analogous to Example 2, but used as Hardener 6o parts. Hardener 17. A fine-pored foam that rises very well is obtained, which when dry has a density of approx. 0.04. Is used in this experiment Only half the amount of trichlorofluoromethane, the resulting fine-pored foam has a density of 0.09 when dry. Phthaloyl chloride (hardener 17) is due its low vapor pressure as well as trimellitic acid trichloride for the procedural Production of foams very suitable.

Example 17: 800 parts of approx. 38% sodium waterglass solution, the 1% by weight sodium alkyl sulfonate contains, are made with a mixture of 65 tlen. Trichlorofluoromethane, 20 tsp. Benzoyl chloride and 100 parts. 3,4-dichlorobenzene-sulfonic acid chloride stirred well. The mixture is poured into a loaf pan, in which it is about twice its volume foams up. The soft foam produced in this way is heated to approx. 120 ° C. Pseiz closet brought to where it is about four times its original volume foams while hardening.

Example 18: 800 parts of the waterglass solution used in Example 1 are brought to 450C and quickly with a solution of 50 Tlen. Chloroform ethyl ester in 50 tlen. Trichlorofluoromethane stirred. Ethyl chloroformate causes under the conditions of Example 1 cure within 50 seconds. The thin one foamy reaction mixture is poured into a box form, in which it foams and hardens. The resulting foam has a density when dry of 0.11.

Claims (10)

Patent claims: 1) Process for the production of foams, characterized in that that one optionally containing inorganic and / or organic admixtures aqueous silicate solutions mixed with blowing agents and acid-releasing hardeners. 2) Method according to claim 1, characterized in that as a hardener Substances are used which in an aqueous medium CO2> carboxylic acids, sulfonic acids or release mineral acids. 3) Method according to one of claims 1 to 2, characterized in that that as hardeners, carboxylic acid anhydrides, carboxylic acid chlorides, chloroformic acid esters or sulfochlorides are used. 4) Method according to one of claims 1 to), characterized in that that as a hardener such acid-releasing compounds or mixtures of compounds are used, as a 10 wt .-% - admixture to a 0.5 wt .- Na-C14-alkyl sulfonate containing sodium silicate solution with a density of 1.36 (Na2O content about 8.6% by weight, SiO2 content around 25.4% by weight of this to gel in less than 15 minutes at 25 ° C brings. 5) Method according to one of claims 1 to 4, characterized in that that as blowing agents alkanes, alkenes, halogen-substituted alkanes, halogen-substituted Alkenes and dialkyl ethers are used. 6) Method according to one of claims 1 to 5, characterized in that that the propellants used are those whose boiling point is between -25 and + 500C. 7) Method according to one of claims 1 to 6, characterized in that that butane and / or fluorotrichloromethane is used as propellant. 8) Water-containing foams produced by a method according to one of claims 1 to 7. 9) Largely anhydrous foams with a density between 0.04 and 0.6 produced by a method according to one of claims 1 to 7. 10) Process for the production of foams, characterized in that that in addition to propellants, mixtures of aqueous rings, optionally inorganic and / or Silicate solutions containing organic admixtures and acid-releasing substances be used.