Hard inorganic foam

Abstract

The present invention relates to a rigid inorganic foam comprising at least one cured mineral binder, at least one surfactant, and at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine, wherein the polymer contains anionic groups. The present invention also relates to a method for producing the rigid inorganic foam and its use as an article or in a system for thermal insulation, sound insulation, lightweight construction, and / or passive fire protection.

Description

Technical Field

[0001] The present invention relates to rigid inorganic foams (rigid inorganic foams). The rigid inorganic foam of the present invention comprises at least one cured mineral binder (cured mineral binder), at least one surfactant and / or particles, and at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine, wherein the polymer contains anionic groups. The present invention also relates to a method for producing a rigid inorganic foam and its use as an article for thermal insulation, sound insulation, lightweight construction and / or passive fire protection or in a system.

Background Art

[0002] Inorganic foam materials find numerous applications in the construction industry. For example, it is used as a material for thermal insulation systems. A particular advantage of inorganic foam materials is their low flammability, especially when compared to organic materials commonly used in thermal insulation systems such as XPS or PIR. Another advantage is that inorganic foams are lightweight and can thus be easily incorporated into buildings, for example facades or roofs.

[0003] However, the mechanical stability of inorganic foam materials, especially cement-based foam materials, is usually low. Low mechanical stability makes it difficult to install thermal insulation systems containing inorganic foams.

[0004] WO 2019 / 038105 pamphlet discloses an inorganic hybrid foam comprising a mineral binder, at least one polymer derived from an ethylenically unsaturated monomer or derived from a combination of a polyisocyanate and a polyol and / or a polyamine, at least one surfactant, at least one thickener, and water. These foams are reported to have increased compressive strength and better adhesion to concrete. However, the polymers obtained especially from the combination of a polyisocyanate and a polyol and / or a polyamine are only disclosed in very general terms in WO 2019 / 038105 pamphlet.

[0005] It is particularly desirable to further increase the compressive strength of the inorganic foams disclosed in WO 2019 / 038105 pamphlet. This would facilitate the use of such inorganic foams for building insulation systems and other purposes in the construction industry.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0006] An object of the present invention is to provide an inorganic foam with increased mechanical strength. In particular, the inorganic foam of the present invention should have high compressive strength. The inorganic foam of the present invention can preferably be used for insulation and / or sound insulation, lightweight structures and / or passive fire protection. Another object of the present invention is to provide a system applicable to an insulation system, and / or a sound insulation system, and / or a passive fire protection system, particularly for buildings, preferably facades, floors and / or roofs.

MEANS FOR SOLVING THE PROBLEMS

[0007] These objects are achieved by the subject matter claimed in the independent claims.

[0008] Surprisingly, it has been found that the compressive strength of the inorganic form can be increased by including certain specific polymers obtained from combinations of polyisocyanates with polyols and / or polyamines, including those containing anionic groups. Furthermore, it has been found that the compressive strength of the inorganic form can be further increased by additionally using certain polymer blends consisting of polyvinyl alcohol and further polymers based on vinyl esters, (meth)acrylate esters, vinyl aromatic compounds, vinyl halides and / or olefins.

[0009] Another advantage of the rigid inorganic forms of the present invention is that they can be formulated using superplasticizers for small amounts of cement. Such superplasticizers are particularly advantageous since, in the case of cement-based inorganic forms, they are known to delay the hydration of the cement which can lead to the collapse of the form before hardening occurs. Polymers obtained from combinations of polyisocyanates with polyols and / or polyamines, including those containing anionic groups, can act as plasticizers for mineral binders, particularly cement, and thus reduce the need for additional superplasticizers.

[0010] Polymers obtained from combinations of polyisocyanates with polyols and / or polyamines, including those containing anionic groups, result in the formation of rigid inorganic forms having a closed-cell structure. This is beneficial since, in a closed-cell structure, the compressive strength of the form is generally also higher compared to an open-cell structure of the same density. Furthermore, in a closed-cell form structure, the thermal insulation properties are generally improved.

[0011] The rigid inorganic forms of the present invention have one or more of the following advantages: (i) Low density, (ii) Closed-cell form structure, (iii) Increased mechanical strength, particularly compressive strength, impact resistance and / or flexural strength, (iv) Low water absorption, (v) Quick drying characteristics after wetting, (vi) Non-combustibility, (vii) Low thermal conductivity, (viii) High sound insulation characteristics.

[0012] A further aspect of the present invention is the subject matter of the independent claims. Preferred embodiments of the present invention are the subject matter of the dependent claims.

Mode for Carrying Out the Invention

[0013] In a first aspect, the present invention is a) at least one cured mineral binder, b) at least one surfactant S and / or particles N, c) at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine in a rigid inorganic foam comprising, characterized in that at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine contains anionic groups.

[0014] In this context, the term "rigid inorganic foam" relates to a material composed of gas bubbles encapsulated within a hard inorganic matrix. The gas bubbles can be in the form of pores and / or cells. The content of gas bubbles encapsulated within the inorganic matrix can vary in the range of 20 to 99% by volume, preferably 20 to 98% by volume, particularly 50 to 95% by volume, relative to the total volume of the rigid inorganic foam. In other words, the term "rigid inorganic foam" relates to inorganic materials with high porosity. The rigid inorganic foam can contain gas bubbles in the form of an interconnected network (open cell foam) or in an isolated form (closed cell foam) or as a mixture of interconnected cells and isolated cells. In this context, closed cell foam is preferred. The gas can be any gas, but is preferably air. The hard inorganic matrix is essentially dry. The rigid inorganic foam of the present invention essentially contains no water. By essentially containing no water is meant that in each case the amount of water is less than 5% by weight, preferably less than 1% by weight, particularly less than 0.5% by weight, relative to the total weight of the rigid inorganic foam. Otherwise, the water adsorbed on the surface of the essentially dry rigid inorganic foam is not included in this definition. The hard inorganic matrix contains at least one cured mineral binder. The inorganic matrix can contain other organic and / or inorganic materials. The inorganic matrix preferably consists of at least 51% by weight, preferably at least 70% by weight, more preferably at least 80% by weight of inorganic materials, relative to the total dry weight of the inorganic matrix in each case. Of course, the inorganic matrix further contains at least the surfactant S and / or the particles N, and a polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine. Therefore, the total content of inorganic materials in the inorganic matrix is less than 100% by weight relative to the total dry weight of the inorganic matrix. The term "rigid" or "hard" can be related to a specific compressive strength of the inorganic foam. Preferably, the rigid inorganic foam of the present invention has a compressive strength of at least 10 kPa, more preferably at least 50 kPa, even more preferably at least 100 kPa. The compressive strength can be measured at 10% compression according to the standard DIN EN 826.The porosity of the rigid inorganic foam or porous inorganic material can be measured by mercury porosimetry in accordance with Standard ISO 15901-1:2016. However, in many cases, it is more convenient to consider the dry density of the porous material. In this regard, high porosity is associated with low density. In other words, the lower the density, the higher the porosity of the rigid inorganic foam. Overall in relation to this, when density is mentioned or a density value is indicated, such density is measured by the gravimetric method. The preferred measurement method is as follows. First, a cubic sample with dimensions of 10×10×10 cm is cut from the material and then dried in an oven at a temperature of 70 °C until the weight of the material remains constant. Next, the weight of the cubic sample is measured, and the density of the material (g / l) is obtained by dividing the measured weight (g) of the cube by 1 l.

[0015] In this regard, the term "low density" represents a density of 500 g / l or less.

[0016] According to an embodiment, the rigid inorganic foam of the present invention has a density of 500 g / l or less, particularly 300 g / l or less, specifically 200 g / l or less. For example, the density is 20 to 500 g / l, preferably 50 to 300 g / l, more preferably 70 to 200 g / l. However, in principle, higher densities are also possible.

[0017] Therefore, the preferred rigid inorganic foam of the present invention essentially does not contain water and has a compressive strength of at least 10 kPa, more preferably at least 50 kPa, even more preferably at least 100 kPa, measured at 10% compression in accordance with Standard DIN EN 826, and has a density of 20 to 500 g / l, preferably 50 to 300 g / l, more preferably 70 to 200 g / l. A particularly preferred rigid inorganic foam of the present invention further has a closed-cell structure.

[0018] Optionally, an additional liquid phase may be present in the rigid inorganic foam of the present invention.

[0019] In this context, the term "hardened mineral binder" refers to a substance that is essentially inorganic and at least partially, preferably completely, hardened. Hardening can occur by chemical reactions of the mineral binder, in particular hydration, or physical reactions of the mineral binder, in particular drying. Preferably, the reaction product is not water-soluble.

[0020] According to a preferred embodiment, the mineral binder is selected from cement, gypsum, lime, magnesia, alumina, geopolymers, latent hydraulic binders and / or pozzolans.

[0021] The cement can in particular be Portland cement of type CEM I, CEM II, CEM III, CEM IV or CEM V as described in standard EN 197-1, calcium aluminate cement and / or calcium sulfoaluminate cement as described in standard EN 14647. The term "gypsum" is meant to include various forms of CaSO4, in particular anhydrite CaSO4, α- and β-hemihydrates of CaSO4 and CaSO4 dihydrate. The term "lime" is meant to include natural hydraulic lime, formulated lime, hydraulic lime and air-hardening lime as described in standard EN 459-1:2015. The term "alumina" represents aluminum oxide, aluminum hydroxide and / or aluminum oxyhydroxide, such as gibbsite and boehmite, calcined or flash-calcined alumina, alumina obtained from the Bayer process, hydratable alumina, such as amorphous intermediate phase alumina and ρ-phase alumina. Pozzolans and latent hydraulic materials in particular represent type II concrete additives having latent hydraulic and / or pozzolanic characteristics according to EN 206-1. Pozzolans and latent hydraulic materials are preferably selected from the group consisting of slag, clay, calcined clay, in particular metakaolin, kiln dust, microsilica, fly ash, pyrogenic silica, precipitated silica, silica fume, zeolite, rice husk ash, calcined oil shale and natural pozzolans, such as pumice, trass and finely ground limestone.

[0022] Accordingly, in this regard, the cured mineral binder is preferably a fully hydrated or fully dried cement, gypsum, lime, magnesia, alumina, geopolymers, latent hydraulic binders and / or pozzolans. Particularly preferably, the cured mineral binder is a fully hydrated Portland cement or a fully hydrated aluminate cement or fully dried gypsum or a mixture thereof.

[0023] According to an embodiment, the cured mineral binder has a proportion of 9 to 99% by weight, preferably 25 to 85% by weight, more preferably 40 to 80% by weight, based on the total dry weight of the rigid inorganic foam.

[0024] At least one surfactant S can be selected from nonionic, anionic, cationic, zwitterionic and amphiphilic compounds and proteins or mixtures thereof. According to some embodiments, a combination of a nonionic surfactant and an anionic surfactant is used. Suitable anionic surfactants are diphenylene oxide sulfonates, alkane and alkylbenzene sulfonates, alkylnaphthalene sulfonates, olefin sulfonates, alkyl ether sulfonates, alkyl sulfates, alkyl ether sulfates, α-sulfo fatty acid esters, acylaminoalkane sulfonates, acyl isothionates, alkyl ether carboxylates, N-acyl sarcosinates, alkyl and alkyl ether phosphates. Examples of suitable anionic surfactants include C8-C18-alkyl sulfates, C8-C18-alkyl ether sulfates, C8-C18-alkyl sulfonates, C8-C18-alkylbenzene sulfonates, C8-C18-α-olefin sulfonates, C8-C18-sulfosuccinates, α-sulfo-C8-C18-fatty acid salts and C8-C18-fatty acid salts. Anionic surfactants generally exist as alkali metal salts, especially sodium salts. Examples of sodium salts of anionic surfactants are sodium lauryl sulfate, sodium myristyl sulfate, sodium cetyl sulfate, sodium sulfate of ethoxylated lauryl or myristyl alcohol with an ethoxylation degree of 2-10, sodium lauryl or cetyl sulfonate salt, sodium hexadecylbenzene sulfonate salt, sodium C14 / C16-α-olefin sulfonate salt, sodium lauryl or cetyl sulfosuccinate salt, disodium 2-sulfolaurate, sodium stearate or mixtures thereof. Suitable nonionic surfactants include alkylphenol polyglycol ethers, fatty alcohol polyglycol ethers, fatty acid polyglycol ethers, fatty acid alkanolamides, block copolymers, amine oxides, glycerol fatty acid esters, sorbitan esters or alkyl polyglucosides.Examples of suitable non-ionic surfactants include C8-C18-fatty alcohol ethoxylates, block copolymers of ethylene oxide and propylene oxide or C8-C18-alkyl polyglycosides or mixtures thereof. An example of a block copolymer is a poloxamer. A poloxamer is a block copolymer of ethylene oxide and propylene oxide, and preferred poloxamers contain 2 to 130 ethylene oxide units and 10 to 70 propylene oxide units. Examples of cationic surfactants are alkyltriammonium salts, alkylbenzyldimethylammonium salts or alkylpyridinium salts. A suitable zwitterionic surfactant is betaine. An example of a zwitterionic surfactant is cocamidopropyl betaine, especially lauramidopropyl betaine.

[0025] Both vegetable and animal proteins or mixtures thereof can be used as protein-based surfactants. Examples of proteins suitable as surfactants include keratin, hydrolyzed keratin, collagen, hydrolyzed collagen or soy-based proteins.

[0026] According to a preferred embodiment, at least one surfactant S is selected from non-ionic and anionic surfactants, preferably C14-C16-alkyl sulfonates, esters of 2-sulfo-butanedioic acid, alkyl polyglycosides or mixtures thereof or cocamidopropyl betaine or protein-based surfactants.

[0027] According to one or more embodiments, the proportion of at least one surfactant S is 0.1 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight, based on the total dry weight of the rigid inorganic foam.

[0028] The particles N of the present invention preferably have a particle size of 10 nm to 500 μm, preferably 20 nm to 300 μm, more preferably 25 nm to 150 μm, even more preferably 30 nm to 100 μm, and particularly 30 nm to 1 μm. The particle size can be determined by laser diffraction as described in ISO 13320:2009. In particular, a Mastersizer 2000 instrument equipped with a Hydro 2000G disperser and Mastersizer 2000 software from Malvern Instruments GmbH (Germany) is used. As the measurement medium, for example, isopropanol is suitable. Preferably, the particle size of non-spherical or irregular particles is represented by the equivalent volume sphere diameter. Throughout the present invention, when a range of particle sizes is given, the lower limit value of the range given herein for the particle size always represents the D10 value of each particle size distribution, and the upper limit value of the range represents the D90 value.

[0029] According to some embodiments, the particles N of the present invention are nanoparticles. This means that the particles N have a particle size in the nanometer range, particularly the particle size D50.

[0030] In particular, the particles N are selected from inorganic particles, particularly oxides, hydroxides, carbides, nitrides, phosphates, carbonates, silicates, and sulfates of pure metals and mixed metals. According to an embodiment, the particles N are selected from clay, talc, silica, calcium carbonate, ferrite, gibbsite, titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, zirconium oxide, tin oxide, cerium oxide, spinel, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, silicon carbide, boron carbide, silicon nitride, boron nitride, calcium phosphate, nickel carbonate, calcium carbonate, magnesium carbonate, fumed silica, fly ash, quartz, powdered glass, slag, calcium silicate, mullite, cordierite, zeolite, diatomaceous earth, cement, calcium sulfate particles and / or carbon black particles. In particular, the particles are silica particles.

[0031] According to another preferred embodiment, the particles are selected from organic particles, particularly polymer particles, particularly polystyrene particles and / or poly(methyl methacrylate) particles.

[0032] The proportion of particles N, when present, is in particular 1 to 50% by volume, particularly 2 to 20% by volume, particularly 3 to 10% by volume, with respect to the total volume of the inorganic form present and cured.

[0033] The rigid foam contains at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine. Such polymers contain urethane groups and / or urea groups. Other groups such as allophanate groups or biuret groups may also be included. Polyurethane and / or polyurea (polyurethane) are common names for such polymers. For the sake of readability, the term "polyurethane" is used throughout the present invention to mean a polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine. Accordingly, in this context, the term "polyurethane" encompasses polyurethanes, polyureas, and polymers containing other groups such as allophanate groups or biuret groups in addition to urethane and / or urea groups.

[0034] According to an embodiment, the polyurethane of the present invention contains anionic groups in an amount such as to give an anionic charge density of 0.01 to 100 meq per gram of polymer, preferably 0.01 to 10 meq per gram of polymer, more preferably 0.05 to 1 meq per gram of polymer, even more preferably 0.2 to 0.5 meq per gram of polymer. Throughout the present invention, the term "meq" represents "milliequivalent" and refers to the amount of anionic charge (mmol).

[0035] The term "polyisocyanate" is meant to encompass organic molecules having two or more isocyanate groups, including diisocyanates.

[0036] Diisocyanates suitable for the production of polyurethanes are aromatic, aliphatic or cycloaliphatic diisocyanates with a molecular weight of less than 500 g / mol. Examples of suitable aromatic diisocyanates are all isomers of toluene diisocyanate (TDI) (either in an isomerically pure form or as a mixture of several isomers), naphthalene-1,5-diisocyanate (NDI), naphthalene-1,4-diisocyanate (NDI), diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-2,4'-diisocyanate and mixtures of 4,4'-diphenylmethane diisocyanate and the 2,4'-isomer, xylylene diisocyanate (XDI), 4,4'-di-phenyldimethylmethane diisocyanate, di- and tetraalkyl-diphenylmethane diisocyanates, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate. Examples of suitable cycloaliphatic diisocyanates are the hydrogenation products of the above-mentioned aromatic diisocyanates, such as 4,4'-dicyclohexylmethane diisocyanate (H12MDI), cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate (H6XDI), 1-methyl-2,4-diisocyanato-cyclohexane, hydrogenated p-tetramethylxylylene diisocyanate (m-TMXDI, p-TMXDI). Further suitable diisocyanates are 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl-cyclohexane (isophorone diisocyanate, IPDI) and dimer fatty acid diisocyanate. Examples of aliphatic diisocyanates include tetramethoxybutane-1,4-diisocyanate, butane-1,4-diisocyanate, hexane-1,6-diisocyanate (HDI), 1,6-diiso-cyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, lysine diisocyanate and 1,12-dodecane diisocyanate (C12DI). According to an embodiment, the diisocyanate is an aliphatic diisocyanate, preferably selected from IPDI, HDI and H12MDI, particularly IPDI.According to a further embodiment, the diisocyanate is an aromatic diisocyanate, preferably selected from TDI and MDI.

[0037] Mixtures of different polyisocyanates can also be used for the production of polyurethanes. Examples include isomers of toluene diisocyanate (TDI), naphthalene-1,4-diisocyanate (NDI), diphenylmethane 2,4'-diisocyanate (MDI), isophorone diisocyanate (IPDI) or hydrogenated 2,4'-MDI. According to an embodiment, polyisocyanates having isocyanate groups of different reactivities are used for the production of polyurethanes.

[0038] A polyol suitable for the production of polyurethanes is a polyhydroxy compound selected from polyether polyols or polyester polyols. Preferably, the polyhydroxy compound is an organic molecule having two or three hydroxyl groups per molecule, with a molecular weight range of 200 to 3000 g / mol, preferably 400 to 2000 g / mol. Examples include bifunctional and / or trifunctional polypropylene glycols or polyethylene glycols. One particularly useful example is linear bifunctional polyethylene glycol monomethyl ether. Random and / or block copolymers of ethylene oxide and propylene oxide can also be used. Another group of polyether polyols useful for the production of polyurethanes is, for example, polytetramethylene glycol (poly(oxytetramethylene) glycol, polyTHF) produced by acid polymerization of tetrahydrofuran.

[0039] Suitable polyols are also polyesters produced by the condensation of dicarboxylic acids or tricarboxylic acids, such as adipic acid, sebacic acid, glutaric acid, azelaic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, dimer fatty acids or mixtures thereof, with low molecular weight diols or triols, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, dimer fatty alcohols, glycerol, trimethylolpropane or mixtures thereof. Another group of polyols used according to the present invention are polyesters based on ε-caprolactone, also called polycaprolactone.

[0040] Polyester polyols derived from oleochemistry can also be used. Such polyester polyols can be prepared, for example, by completely ring-opening the epoxidized triglyceride of a fat mixture containing at least partially olefinically unsaturated fatty acids with one or more alcohols having 1 to 12 carbon atoms, followed by a partial transesterification reaction of the triglyceride derivative to obtain an alkyl ester polyol having 1 to 12 carbon atoms in the alkyl radical. This can be, for example, castor oil.

[0041] Other suitable polyols are polycarbonate polyols, polycaprolactone diols, dimer diols or hydroxy-functional polybutadiene.

[0042] More suitable polyols are aliphatic alkylene diols. These can be linear or branched C2-C24 diols having OH groups at the ends or sides of the carbon chain. Examples include ethylene glycol, propylene glycol, butanediol-1,4, pentanediol-1,5, hexanediol-1,6, heptanediol-1,7, octanediol-1,8 and their higher homologues or isomers. Higher functionality alcohols such as glycerol, trimethylolpropane, pentaerythritol or sugar alcohols are also suitable. However, such higher functionality polyols are less preferred and should be present only in small amounts in the polyol.

[0043] Even more suitable polyols are dimethylolpropionic acid (DMPA), tartaric acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid and N-methyl-diethanolamine.

[0044] Naturally, mixtures of the above polyols can also be used.

[0045] The polyol is preferably a liquid. The molecular weight should preferably be less than 2000 g / mol, especially less than 1500 g / mol (number average molecular weight, MN determinable by GPC). It is preferred to use a diol or a mixture thereof.

[0046] Suitable polyamines are aliphatic, alicyclic or arylaliphatic primary diamines such as ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,3-pentanediamine (DAMP), 1,5-pentanediamine, 1,5-di-amino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,2-, 1,3- and 1,4-diaminocyclohexane, bis-(4-aminocyclohexyl)methane (H12-MDA), bis-(4-amino-3-methylcyclohexyl)methane, bis-(4-amino-3-ethylcyclohexyl)methane, bis-(4-amino-3,5-dimethylcyclohexyl)methane, bis-(4-amino-3-ethyl-5-methylcyclohexyl)methane (M-MECA), 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine or IPDA), 2- and 4-methyl-1,3-diaminocyclohexane and mixtures thereof, 1,3- and 1,4-bis-(aminomethyl)cyclohexane, 2,5(2,6)-bis-(aminomethyl)bicyclo[2.2.1]heptane (NBDA), 1,4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1,8-menthanediamine, 3,9-bis-(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane and 1,3- and 1,4-bis-(aminomethyl)-benzene.

[0047] More suitable polyamines are aliphatic, alicyclic or arylaliphatic primary triamines, such as 4-aminomethyl-1,8-octanediamine, 1,3,5-tris-(aminomethyl)benzene, 1,3,5-tris-(aminomethyl)cyclohexane, tris-(2-aminoethyl)amine, tris-(2-aminopropyl)amine and tris-(3-aminopropyl)amine.

[0048] Further suitable polyamines are ether group-containing aliphatic primary diamines, such as in particular bis-(2-aminoethyl) ether, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecane-1,10-diamine, 4,7-dioxadecane-2,9-diamine, 4,9-dioxadodecane-1,12-diamine, 5,8-dioxadodecane-3,10-diamine, 4,7,10-trioxatridecane-1,13-diamine and higher oligomers of these diamines, bis-(3-aminopropyl) polytetrahydrofuran and other polytetrahydrofuran diamines and polyoxyalkylene diamines. The latter usually represent products from the amination of polyoxyalkylene diols and are available, for example, under the trade name Jeffamine® (from Huntsman), the name polyetheramine (from BASF) or the trade name PC Amine® (from Nitroil). Particularly suitable polyoxyalkylene diamines are Jeffamine® D-230, Jeffamine® D-400, Jeffamine® D-2000, Jeffamine® D-4000, Jeffamine® XTJ-511, Jeffamine® ED-600, Jeffamine® ED-900, Jeffamine® ED-2003, Jeffamine® XTJ-568, Jeffamine® XTJ-569, Jeffamine® XTJ-523, Jeffamine® XTJ-536, Jeffamine® XTJ-542, Jeffamine® XTJ-559, Jeffamine® EDR-104, Jeffamine® EDR-148, Jeffamine® EDR-176; polyetheramine D230, polyetheramine D400 and polyetheramine D2000, PC Amine® DA250, PC Amine® DA400, PC Amine® DA650 and PC Amine® DA2000.

[0049] Further suitable polyamines are usually primary polyoxyalkylene triamines which are products from the amination of polyoxyalkylene triols, such as those with the name Jeffamine® (from Huntsman), the name polyetheramine (from BASF) or the name PC Amine® (from Nitroil), for example especially Jeffamine® T-403, Jeffamine® T-3000, Jeffamine® T-5000, polyetheramine T403, polyetheramine T5000 and PC Amine® TA403, which are available.

[0050] Further suitable polyamines are polyamines having a tertiary amino group together with two primary aliphatic amino groups, such as especially N,N'-bis-(aminopropyl)-piperazine, N,N-bis-(3-aminopropyl)methylamine, N,N-bis-(3-aminopropyl)ethylamine, N,N-bis-(3-aminopropyl)propylamine, N,N-bis-(3-aminopropyl)-cyclo-hexylamine, N,N-bis-(3-aminopropyl)-2-ethyl-hexylamine and products from the dicyanoethylation of fatty amines derived from natural fatty acids and subsequent reduction thereof, such as N,N-bis-(3-aminopropyl)dodecylamine and N,N-bis-(3-aminopropyl)tallow alkylamine available as Triameen® Y12D and Triameen® YT (from Akzo Nobel).

[0051] Further suitable polyamines are polyamines containing a tertiary amino group together with three primary aliphatic amino groups, such as especially tris-(2-aminoethyl)amine, tris-(2-aminopropyl)amine and tris-(3-aminopropyl)amine.

[0052] Further suitable polyamines are polyamines containing a secondary amino group together with two primary aliphatic amino groups, such as in particular 3-(2-aminoethyl)amino-propylamine, bis-hexamethylenetriamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA) and higher homologues of linear polyethyleneamines, such as polyethylene polyamines having 5 to 7 ethyleneamine units (so-called "higher ethylene polyamines", HEPA), primary diamines having at least two primary amino groups and products from multiple cyanoethylations or cyanobutylations of polyamines followed by hydrogenation, such as dipropylenetriamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), N,N'-bis(3-aminopropyl)-1,4-diaminobutane, N5-(3-aminopropyl)-2-methyl-1,5-pentanediamine, N3-(3-aminopentyl)-1,3-pentanediamine, N5-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine and N,N'-bis-(3-amino-1-ethylpropyl)-2-methyl-1,5-pentanediamine.

[0053] More suitable polyamines are polyamines having primary and secondary amino groups, such as in particular N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine, N-hexyl-1,2-ethanediamine, N-(2-ethylhexyl)-1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, 4-aminomethyl-piperidine, N-(2-aminoethyl)piperazine, N-methyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-(2-ethylhexyl)-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 3-methylamino-1-pentylamine, 3-ethylamino-1-pentylamine, 3-cyclohexylamino-1-pentylamine, fatty diamines, such as N-cocoalkyl-1,3-propanediamine and primary aliphatic diamines, and products from Michael addition reactions (reaction in a molar ratio of 1:1) with acrylonitrile, maleic or fumaric acid diesters, citraconic acid diesters, acrylic and methacrylic acid esters, acrylic and methacrylic acid amides and itaconic acid diesters, products from partial reductive alkylation of primary aliphatic polyamines with benzaldehyde or modified aldehydes or ketones and partially styrenated polyamines, such as Gaskamine® 240 (from Mitsubishi Gas Chemical Company, Inc. (MGC)).

[0054] Further suitable polyamines are aromatic polyamines such as, in particular, m- and p-phenylenediamine, 4,4'-, 2,4' and 2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenyl-methane (MOCA), 2,4- and 2,6-toluenediamine, a mixture of 3,5-dimethylthio-2,4- and -2,6-toluenediamine (available from Albemarle as Ethacure® 300), a mixture of 3,5-diethyl-2,4- and -2,6-toluenediamine (DETDA), 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA), 3,3',5,5'-tetraethyl-2,2'-dichloro-4,4'-diaminodiphenylmethane (M-CDEA), 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane (M-MIPA), 3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane (M-DIPA), 4,4'-diaminodiphenylsulfone (DDS), 4-amino-N-(4-aminophenyl)benzenesulfonamide, 5,5'-methylenediantranilic acid, dimethyl(5,5'-methylenediantranilate), 1,3-propylenebis-(4-aminobenzoate), 1,4-butylenebis-(4-aminobenzoate), polytetramethylene oxide bis-(4-aminobenzoate) (available from Air Products as Versalink®), 1,2-bis-(2-aminophenylthio)ethane, 2-methylpropyl-(4-chloro-3,5-diaminobenzoate) and tert-butyl-(4-chloro-3,5-diaminobenzoate).

[0055] Further suitable polyamines are polyamideamines which are reaction products of monovalent or polyvalent carboxylic acids or their esters or anhydrides, in particular dimer fatty acids, with aliphatic, cycloaliphatic or aromatic polyamines used in stoichiometric excess, in particular polyalkyleneamines such as DETA or TETA, especially the commercially available polyamideamines Versamid® 100, 125, 140 and 150 (from Cognis), Aradur® 223, 250 and 848 (from Huntsman), Euretek® 3607 and 530 (from Huntsman) and Beckopox® EH 651, EH 654, EH 655, EH 661 and EH 663 (from Cytec); and phenolamines, also called Mannich bases, which are reaction products of phenol, in particular cardanol, with aldehydes, in particular formaldehyde and polyamines, especially the commercially available phenolamines Cardolite® NC-541, NC-557, NC-558, NC-566, Lite 2001 and Lite 2002 (from Cardolite), Aradur® 3440, 3441, 3442 and 3460 (from Huntsman) and Beckopox® EH 614, EH 621, EH 624, EH 628 and EH 629 (from Cytec).

[0056] Preferred polyamines are 1,3-pentanediamine (DAMP), 1,5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl-1,5-pentanediamine (C11-neodiamine), 1,6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1,12-dodecanediamine, 1,3-diaminocyclohexane, bis-(4-aminocyclohexyl)methane (H12-MDA), bis-(4-amino-3-methylcyclohexyl)methane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane (IPDA), 1,3-bis-(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)benzene (MXDA), bis-hexamethylenetriamine (BHMT), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylene-hexamine (PEHA) and higher homologues (HEPA) of linear polyethyleneamines such as polyethyleneamines having 5 to 7 ethyleneamine units, dipropylene-triamine (DPTA), N-(2-aminoethyl)-1,3-propanediamine (N3-amine), N,N'-bis(3-aminopropyl)ethylenediamine (N4-amine), polyoxyalkylenediamines and polyoxyalkylenetriamines having a molecular weight in the range of 200 to 500 g / mol, in particular of the type Jeffamine® D-230, Jeffamine® D-400 and Jeffamine® T-403, polyanilideamine, phenalkamine, polyamines selected from the group consisting of compounds of the above-mentioned polyamines which are fully or partially alkylated at the primary amino groups.

[0057] Naturally, mixtures of the above-mentioned polyamines can also be used.

[0058] Suitable methods for producing at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine are essentially known to those skilled in the art. For example, German Patent No. 10315175 or European Patent No. 2493951 discloses suitable methods for producing at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine.

[0059] It is important that at least one polyurethane, i.e., a polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine, contains anionic groups. Such polyurethanes have been found to provide particularly advantageous properties of the rigid inorganic foams of the present invention. In particular, polyurethanes having such anionic groups result in rigid inorganic foams with low density and increased compressive strength.

[0060] According to an embodiment, the polymer obtained from the combination of the polyisocyanate and the polyol and / or the polyamine of the present invention contains anionic groups in an amount that gives an anionic charge density of the polymer of 0.01 to 100 meq per gram of polymer, preferably 0.01 to 10 meq per gram of polymer, more preferably 0.05 to 1 meq per gram of polymer, and even more preferably 0.2 to 0.5 meq per gram of polymer. Throughout the present invention, the term "meq" represents "milliequivalent" and refers to the amount (mmol) of anionic charge. The anionic groups are preferably carboxylic acid groups, sulfonic acid groups, sulfinic acid groups, phosphonic acid groups and / or phosphoric acid groups, particularly carboxylic acid groups.

[0061] Polyurethanes containing phosphonic acid groups and / or phosphoric acid groups have the additional advantage of having flame retardant properties.

[0062] The polyurethane having an anion group of the present invention can be produced by the reaction of an isocyanate containing an anion group with a conventional diol, triol, polyol and / or the reaction of a diol, triol, polyol containing an anion group with a conventional isocyanate. Naturally, the isocyanate containing an anion group can be used in combination with an isocyanate not containing an anion group. Similarly, the diol, triol, polyol containing an anion group can be used in combination with a diol, triol, polyol not containing an anion group. It is also possible to use an anion-functionalized isocyanate together with an anion-functionalized diol, triol, polyol, optionally together with an isocyanate and / or a diol, triol, polyol having no anion group. Particularly suitable diols containing an anion group are dimethylolpropionic acid (DMPA), tartaric acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid and diethyl-bis-(2-hydroxyethyl)-aminomethylphosphonate.

[0063] According to an embodiment, the polyurethane of the present invention includes at least one segment derived from a hydrophobic polyol and at least one segment derived from a bifunctional and / or trifunctional polypropylene glycol or polyethylene glycol. Suitable hydrophobic polyols include polypropylene glycol, polytetramethylene glycol (poly(oxytetramethylene) glycol, polyTHF), 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and adipic acid, sebacic acid, glutaric acid, azelaic acid, undecanedioic acid, dodecanedioic acid, 3,3-dimethylglutaric acid, terephthalic acid, isophthalic acid, hexahydrophthalic acid, dimer fatty acid or a mixture thereof, and a polyester produced by condensation with a low molecular weight diol or triol such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, dimer fatty alcohol, glycerol, trimethylolpropane or a mixture thereof. Particularly preferably, the polyurethane of the present invention includes at least one segment derived from polytetramethylene glycol (poly(oxytetramethylene) glycol, polyTHF). Suitable bifunctional and / or trifunctional polypropylene glycols or polyethylene glycols are, in particular, linear bifunctional polyethylene glycol monomethyl ether.

[0064] When at least one segment derived from a branched monomethyl ether of polypropylene glycol or polyethylene glycol and having two primary hydroxyl groups is contained within the backbone of the polyurethane of the present invention, it has been found that particularly stable aqueous dispersions of such polyurethanes are obtained. This is particularly the case when the aqueous dispersion of the polyurethane further contains cement, i.e., when it is an aqueous cement slurry. Thus, according to an embodiment, at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine is derived from a branched monomethyl ether of polypropylene glycol or polyethylene glycol and includes at least one segment having two primary hydroxyl groups.

[0065] The polyurethane of the present invention includes a backbone obtained from the reaction of a polyisocyanate with a polyol and / or a polyamine. It has been found that the compatibility of the polyurethane of the present invention with at least one surfactant S and / or particles N of the present invention can be increased by optimizing the backbone of the polyurethane. For example, a polyurethane backbone based on a combination of a polyol, particularly a hydrophobic polyol, and 4,4'-dicyclohexylmethane diisocyanate is particularly suitable when a protein-based surfactant is used. For example, a polyurethane backbone based on a combination of a polyol, particularly a hydrophobic polyol, and 1-isocyanatomethyl-3-isocyanato-1,5,5-trimethyl-cyclohexane is particularly suitable when a surfactant having a sulfonic acid group is used.

[0066] The polymer obtained from the combination of a polyisocyanate and a polyol and / or a polyamine, i.e., the polyurethane, is present in the rigid inorganic foam in an amount of 0.1 to 20% by weight, preferably 0.5 to 13% by weight, more preferably 1 to 8% by weight, even more preferably 2 to 7% by weight, particularly 5 to 6% by weight, based on the total dry weight of the rigid inorganic foam.

[0067] According to an embodiment, the rigid inorganic foam of the present invention may additionally contain a polymer P based on an ethylenically unsaturated monomer, particularly vinyl alcohol, vinyl ester, (meth)acrylate, vinyl aromatic compound, olefin, 1,3-diene and / or vinyl halide. The additional use of the polymer P further increases the mechanical strength, particularly the compressive strength, of the rigid inorganic foam of the present invention.

[0068] Suitable vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate and vinyl esters of α-branched monocarboxylic acids having 9 to 11 carbon atoms, such as VeoVa9R or VeoVa10R (available from Resolution). Suitable (meth)acrylates are methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate. Suitable vinyl aromatic compounds are styrene, methylstyrene and vinyltoluene. Suitable vinyl halide is vinyl chloride. Suitable olefins are ethylene and propylene. Suitable 1,3-dienes are 1,3-butadiene and isoprene.

[0069] Particularly suitable polymers P are (i) a copolymer of vinyl acetate and 1 to 50% by weight of ethylene, (ii) a copolymer of vinyl acetate, 1 to 45% by weight of ethylene and optionally at least one of vinyl propionate, vinyl laurate and vinyl esters of α-branched monocarboxylic acids having 9 to 11 carbon atoms in an amount of 1 to 45% by weight, (iii) a copolymer of vinyl acetate, 1 to 35% by weight of ethylene and 1 to 60% by weight of (meth)acrylates of branched or unbranched aliphatic alcohols, particularly n-butyl acrylate or 2-ethylhexyl acrylate, (iv) A copolymer of vinyl acetate, 1 to 30% by weight of vinyl laurate, 1 to 35% by weight of ethylene, and 1 to 30% by weight of a (meth)acrylate of a branched or unbranched aliphatic alcohol, in particular n-butyl acrylate or 2-ethylhexyl acrylate, (v) A copolymer of vinyl acetate, 1 to 40% by weight of ethylene, and 1 to 55% by weight of vinyl chloride, (vi) Polyvinyl alcohol having a degree of hydrolysis of 80 to 94 mol% and a Heppler viscosity (Heppler method at 20 °C according to standard DIN 53015) in a 4% aqueous solution of particularly 1 to 30 mPas selected from.

[0070] Polymer P may additionally contain up to 10% by weight of monomers selected from ethylenically unsaturated carboxylic acids or dicarboxylic acids, ethylenically unsaturated carboxylic acid amides or nitriles, esters of fumaric acid or maleic acid, and ethylenically unsaturated sulfonic acids.

[0071] Polymer P may have a glass transition temperature Tg of -25 °C to +35 °C, preferably -10 °C to +15 °C, more preferably -10 °C to +20 °C. Tg can be measured by differential scanning calorimetry in an essentially known manner. Tg can also be calculated using the Fox equation published in Bull. Am. Phys. Soc. 1, 123 (1956).

[0072] Polymer P is preferably prepared in an aqueous medium, preferably by an emulsion polymerization or suspension polymerization process as described, for example, in German Patent Application Publication No. A 102008043988.

[0073] Polymer P may additionally contain a protective colloid. Preferred protective colloids are polyvinyl alcohols, for example partially or fully saponified polyvinyl alcohols having a degree of hydrolysis of in particular 80 to 100 mol%. Partially saponified polyvinyl alcohols having a degree of hydrolysis of 80 to 94 mol% and a Heppler viscosity (Heppler method at 20 °C, DIN 53015) in a 4% aqueous solution of in particular 1 to 30 mPas are particularly preferred. The protective colloids mentioned can be obtained by methods known to those skilled in the art. The protective colloid is generally present in an amount of 1 to 20% by weight in total, based on the total weight of polymer P.

[0074] Polymer P is preferably present in the form of a powder stabilized with a protective colloid that is redispersible in water. When a polymer powder stabilized with a protective colloid that is redispersible in water is dispersed, a protective colloid-stabilized polymer P in the form of an aqueous dispersion is obtained. The powder preferably contains 3 to 30% by weight, particularly preferably 5 to 20% by weight, of polyvinyl alcohol, in particular the above-mentioned polyvinyl alcohol, based on the dry weight of the powder.

[0075] According to an embodiment, polymer P is present in the rigid inorganic foam of the present invention in an amount of 0.5 to 30% by weight, preferably 1 to 25% by weight, more preferably 2 to 20% by weight, particularly 10 to 15% by weight, based on the total dry weight of the rigid inorganic foam.

[0076] According to an embodiment, the rigid inorganic foam of the present invention contains further additives selected from the list consisting of rheology modifiers, thickeners, accelerators, retarders, pigments, biocides, fibers, flame retardants, plasticizers, superplasticizers and / or fillers.

[0077] Thus, according to an embodiment, the rigid inorganic foam of the present invention contains one or more thickeners selected from polysaccharides such as cellulose ethers and modified cellulose ethers, cellulose esters, starch ethers, guar gum, xanthan gum, polycarboxylic acids such as polyacrylic acid and its partial esters, casein and / or related thickeners.

[0078] According to a further embodiment, the rigid inorganic foam of the present invention comprises an accelerator selected from amino alcohols, alkali metal and alkaline earth metal nitrates, alkali metal and alkaline earth metal nitrites, alkali metal and alkaline earth metal thiocyanates, alkali metal and alkaline earth metal halides, alkali metal and alkaline earth metal carbonates, glycerol, glycerol derivatives, glycols, glycol derivatives, aluminum salts, aluminum hydroxide, alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal silicates, alkali metal and alkaline earth metal oxides, crystallization nuclei, particularly hydrated calcium silicate compounds in fine powder form, and mixtures thereof.

[0079] According to a further embodiment, the rigid inorganic foam of the present invention comprises a retarder selected from phosphates, phosphonates, hydroxycarboxylic acids, particularly citric acid, tartaric acid or lactic acid.

[0080] According to a further embodiment, the rigid inorganic foam of the present invention comprises a plasticizer and / or a superplasticizer for mineral binders selected from polycarboxylate ethers, polycarboxylate esters, melamine sulfonates, melamine formaldehyde resins, naphthalene sulfonates and / or lignosulfonates. However, it is preferred that no plasticizer or superplasticizer is added or that only a very small amount is added.

[0081] According to a further embodiment, the rigid inorganic foam of the present invention comprises sands, particularly river sand or quartz sand, quartz powder, crushed limestone, crushed dolomite, clay, chalk, slag, rubber granules, aluminum silicate, corundum, basalt, carbides such as silicon carbide or titanium carbide, and / or bio-based fillers such as hemp fibers or sunflower pith.

[0082] According to an embodiment, the rigid inorganic foam of the present invention is (based on the total dry weight of the rigid inorganic foam) a) 9 to 99% by weight, preferably 25 to 85% by weight, more preferably 40 to 80% by weight of at least one hardened mineral binder, preferably at least one cement, in particular Portland cement, b) 0.1 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight of at least one surfactant S, c) 0.1 to 20% by weight, preferably 0.5 to 13% by weight, more preferably 1 to 8% by weight, even more preferably 2 to 7% by weight, in particular 5 to 6% by weight of at least one polymer obtained from a combination of polyisocyanate and polyol and / or polyamine, characterized in that it contains anionic groups d) Optionally, 0.5 to 30% by weight, preferably 1 to 25% by weight, more preferably 2 to 20% by weight, even more preferably 10 to 15% by weight of polymer P, e) Optionally, 0.01 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight of further additives selected from the list consisting of rheology modifiers, thickeners, accelerators, retarders, pigments, biocides, fibers, flame retardants, plasticizers, superplasticizers and / or fillers comprising or consisting of these.

[0083] In a second aspect, the invention relates to a method for producing a rigid inorganic foam, said method comprising: (A) an inorganic foam comprising: a) at least one mineral binder; b) at least one surfactant S and / or particles N; c) at least one polymer obtained from a combination of polyisocyanate and polyol and / or polyamine; d) water characterized in that at least one polymer obtained from a combination of polyisocyanate and polyol and / or polyamine contains anionic groups; (B) curing the inorganic foam of step (A). comprising.

[0084] The weight ratio of water to at least one mineral binder is preferably from 0.2 to 1.5, more preferably from 0.2 to 1.1, and even more preferably from 0.4 to 1.1.

[0085] The gas phase contained in the inorganic form provided in step (A) can be introduced by mechanical, physical or chemical foaming. Non-limiting examples of gases include air, nitrogen, noble gases, carbon dioxide, hydrocarbons and mixtures thereof.

[0086] For example, the gas phase present within the form can be introduced by mechanical foaming in the presence of each gas. Mechanical foaming can be carried out using a kitchen mixer, or by a vibration process, or by a stator-rotor process. The gas phase can also be introduced into the form by physical or chemical foaming, and the physical or chemical foaming process is suitable for releasing the gas. Preferably, a blowing agent that reacts with or decomposes with water and / or an acid to release the gas is used. Non-limiting examples of blowing agents include peroxides such as hydrogen peroxide, dibenzoyl peroxide, peroxybenzoic acid, peroxyacetic acid, alkali metal peroxides, perchloric acid, peroxymonosulfonic acid, dicumyl peroxide or cumyl hydroperoxide, carbonic acid and bicarbonates such as CaCO3, Na2CO3 and NaHCO3 (preferably used in combination with an acid, a metal powder such as aluminum powder, an azide, a hydrazide or hydrazine). Foaming by the blowing agent can be promoted by the use of a catalyst.

[0087] In the method of the present invention, it is particularly preferred that at least one polymer obtained from the combination of the polyisocyanate of the present invention with a polyol and / or a polyamine is used in the form of a dispersion in water. Thus, according to an embodiment, in the method for producing a rigid inorganic foam of the present invention, at least one polymer obtained from the combination of a polyisocyanate with a polyol and / or a polyamine is in the form of an aqueous dispersion of said polymer. The solids content of such an aqueous dispersion is not particularly limited. The solids content can be 20% to 50% by weight, particularly 30 to 40% by weight. The aqueous dispersion of the polymer obtained from the combination of the polyisocyanate according to the present invention with a polyol and / or a polyamine may contain further additives, in particular biocides and / or pigments.

[0088] The curing of the inorganic foam usually starts when at least one mineral binder comes into contact with water. The curing can be carried out, for example, at a temperature of 5 to 50 °C and a pressure of 1 atmosphere. In this context, curing at a higher temperature and / or a higher pressure is not preferred. A rigid inorganic foam is obtained when the mechanical strength, in particular the impact resistance, flexural strength and / or compressive strength, does not increase significantly further over time. Usually, a rigid inorganic foam is obtained after curing at 20 °C and a pressure of 1 atmosphere for 28 days. During step (B), it may be advantageous to coat the inorganic foam. Coating prevents rapid evaporation of water and higher compressive strength can be obtained. It is possible to further dry the rigid inorganic foam at a high temperature, for example 40 to 90 °C.

[0089] The method for producing the rigid inorganic foam of the present invention can be carried out at a given site. Thus, the rigid inorganic foam of the present invention can be produced on site, for example at a construction site or at the site where a system using such a rigid inorganic foam is manufactured. Similarly, the method for producing the rigid inorganic foam of the present invention can also be carried out off-site. Thus, the rigid inorganic foam of the present invention can be prefabricated and transported to the site for installation or to the site where the rigid inorganic foam is subsequently used to manufacture a further system.

[0090] The rigid inorganic foam of the present invention can be used in systems for heat insulation, sound insulation and / or passive fire protection. Thus, in a further aspect, the present invention relates to the use of the above-mentioned rigid inorganic foam in articles or systems for heat insulation, sound insulation and / or passive fire protection.

[0091] In particular, the rigid inorganic foam of the present invention can be used in articles or systems for passive fire protection that comply with Class A1 or A2 according to standard EAD 350454-00-1104:2017 and / or standard EN 13501-1.

[0092] According to an embodiment, the rigid inorganic foam of the present invention can be used for heat insulation, sound insulation, lightweight structures and / or passive fire protection. It can be used in horizontal or vertical applications, such as load-bearing or non-load-bearing structures, walls, panels, facades, roofs, floors or primers.

[0093] Alternatively or in addition, the above-mentioned rigid inorganic foam can also be used for filling cavities. One example is the filling of cavities in bricks. Another example is the filling of double walls.

[0094] The following examples will provide additional ways for those skilled in the art to practice the present invention.

Example

[0095] All raw materials were purchased of high quality and used as received.

[0096] Preparation of polyurethane dispersion (PUD) An aqueous dispersion (PUD) of a polymer obtained from a combination of a polyisocyanate and a polyol and / or polyamine of the present invention was prepared as follows.

[0097] In the first step, prepolymers were prepared from combinations of polyisocyanates and polyols and / or polyamines. The respective raw materials for each prepolymer were as shown in Table 1 below. Thus, in a glass reactor equipped with a reflux condenser, thermometer, vacuum pump, dropping funnel, and magnetic stirrer, linear difunctional polyethylene glycol monomethyl ether and the respective poly(alkylene) glycols were mixed in the amounts shown in Table 1 below. The mixture was heated to 95 °C, the pressure was reduced to less than 50 mbar, and mixing was continued for 10 minutes. Next, the respective diisocyanates in the amounts shown in Table 1 below were added at 95 °C via the dropping funnel, and stirring was continued for 10 minutes. Next, 0.04 wt% tin neodecanoate based on the polyalkylene glycol was added, and stirring was continued for 30 minutes. Next, a mixture of the respective amounts of dimethylolpropionic acid shown in Table 1 below and 0.04 wt% tin neodecanoate based on the polyalkylene glycol was added, and stirring was continued for 3 hours. Next, the resulting mixture was cooled to obtain prepolymers obtained from combinations of polyisocyanates and polyols and / or polyamines.

[0098] In the second step, solid NaOH was dissolved in water to achieve a pH of 12.6. The aqueous NaOH solution was heated to a temperature of 85 °C while stirring with a dissolver. 38 g of each prepolymer obtained from combinations of polyisocyanates and polyols and / or polyamines (prepared as in the first step above) was added to 54 g of the aqueous NaOH solution while stirring with a dissolver at 85 °C. Stirring was continued at 1500 rpm for 3 minutes. Next, a mixture of 1.9 g of ethylenediamine in 6 g of water was added over 2 - 5 minutes while stirring at 1000 rpm. The temperature of the resulting dispersion was cooled to 23 °C, and stirring was continued at 1000 rpm for 10 minutes. The resulting dispersion was tempered in an oven at 40 °C for 16 hours and then left at 23 °C for an additional 8 hours. Thereafter, the dispersion was filtered through a 100 μm filter cloth, and the resulting aqueous dispersion had a solids content of approximately 40 wt%.

[0099]

Table 1

[0100] Preparation of Rigid Inorganic Foam The rigid inorganic foam of the present invention was prepared as follows.

[0101] A device of the type "Foamed Concrete Laboratory Mixer - SBL" from GERTEC Maschinen - und Anlagenbau GmbH (Germany) was used. Thereby, an aqueous foam having a predetermined density was generated in a first container, and separately, a cement slurry was generated in a second container. Subsequently, to obtain the inorganic foam, the aqueous foam and the cement slurry were driven by pressurized air through the static mixing device of the device.

[0102] The cement slurry was prepared from 25 kg of CEM I type Portland cement, an amount of water to achieve a mass ratio of water to cement of 0.4, 50 g of a PCE - based superplasticizer, and the PUD prepared as described above in the types and amounts shown in Table 2 below. The water introduced together with the PUD was considered in the calculation of the water - to - cement ratio. Optionally, additional polymers shown in Table 2 below were added to the cement slurry. The aqueous foam was prepared from water containing 3 wt% of each surfactant shown in Table 2 below.

[0103] Foam production was started with the Gertec SBL device, and the foam was produced by putting a layer having a thickness of 14 cm and the target density shown in the following table into a mold. The surface of this layer was flattened, and each foam was left at 23°C / 50% r.h. After 1 day, the foam was taken out of the mold and left at 23°C / 50% r.h. for a total of 28 days for curing.

[0104] Details of the foam thus produced are reported in Table 1 below.

[0105] The compressive strength was measured at 10% compression in accordance with standard DIN EN 826, 28 days after hardening.

[0106] The water absorption was measured in accordance with standard DIN EN 16535.

[0107] Table 2 below shows an overview and results of rigid inorganic foams 1 to 16. Rigid inorganic foams 1 to 4 do not conform to the present invention and are included for comparison.

[0108]

Table 2

[0109]

Table 3

[0110]

Table 4

[0111]

Table 5

Claims

1. A rigid inorganic foam, a) at least one cured mineral binder, b) at least one surfactant S and / or particles N, c) at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine comprising, wherein the at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine contains anionic groups, a rigid inorganic foam.

2. The rigid inorganic foam according to claim 1, having a density of 500 g / l or less, in particular 300 g / l or less, especially 200 g / l or less.

3. The at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine according to the present invention contains anionic groups in an amount that gives an anionic charge density of 0.01 to 100 meq per g of the polymer, preferably 0.01 to 10 meq per g of the polymer, more preferably 0.05 to 1 meq per g of the polymer, even more preferably 0.2 to 0.5 meq per g of the polymer, the rigid inorganic foam according to claim 1 or 2.

4. The at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine contains at least one segment derived from a branched monomethyl ether of polypropylene glycol or polyethylene glycol and having two primary hydroxyl groups, the rigid inorganic foam according to any one of claims 1 to 3.

5. The at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine contains at least one segment derived from an aliphatic diisocyanate, the rigid inorganic foam according to any one of claims 1 to 4.

6. The rigid inorganic foam according to any one of claims 1 to 5, additionally comprising a polymer P based on an ethylenically unsaturated monomer, in particular vinyl alcohol, vinyl ester, (meth)acrylate ester, vinyl aromatic compound, olefin, 1,3-diene and / or vinyl halide.

7. The additional polymer P is present in an amount of 0.5 to 30% by weight, preferably 1 to 25% by weight, more preferably 2 to 20% by weight, even more preferably 10 to 15% by weight, based on the total dry weight of the rigid inorganic foam. The rigid inorganic foam according to claim 5, characterized in that.

8. The at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine is present in an amount of 0.1 to 20% by weight, preferably 0.5 to 13% by weight, more preferably 1 to 8% by weight, even more preferably 2 to 7% by weight, particularly 5 to 6% by weight, based on the total dry weight of the rigid inorganic foam. The rigid inorganic foam according to any one of claims 1 to 7, characterized in that.

9. The at least one surfactant S is selected from non-ionic and anionic surfactants, preferably C14-C16-alkyl sulfonates, esters of 2-sulfo-butanedioic acid, alkyl polyglucosides or mixtures thereof, or cocamidopropyl betaine, or protein-based surfactants. The rigid inorganic foam according to any one of claims 1 to 8, characterized in that.

10. Further additives selected from the list consisting of rheology modifiers, thickeners, accelerators, retarders, pigments, biocides, fibers, flame retardants, plasticizers, superplasticizers and / or fillers are included. The rigid inorganic foam according to any one of claims 1 to 9, characterized in that.

11. A rigid inorganic foam according to any one of claims 1 to 10, (each based on the total dry weight of the rigid inorganic foam) comprising or consisting of the following: a) 9 to 99% by weight, preferably 25 to 85% by weight, more preferably 40 to 80% by weight of at least one cured mineral binder, preferably at least one cement, particularly Portland cement, b) 0.1 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 15% by weight of at least one surfactant S, c) 0.1 to 20% by weight, preferably 0.5 to 13% by weight, more preferably 1 to 8% by weight, even more preferably 2 to 7% by weight, particularly 5 to 6% by weight of at least one polymer obtained from a combination of a polyisocyanate and a polyol and / or a polyamine, d) Optionally, 0.5 to 30% by weight, preferably 1 to 25% by weight, more preferably 2 to 20% by weight, even more preferably 10 to 15% by weight of polymer P, e) Optionally, 0.01 to 25% by weight, preferably 0.5 to 20% by weight, more preferably 1 to 10% by weight of a further additive selected from the list consisting of rheology modifiers, thickeners, accelerators, retarders, pigments, biocides, fibres, flame retardants, plasticisers, superplasticisers and / or fillers, 、 characterised in that the at least one polymer obtained from a combination of polyisocyanate and polyol and / or polyamine contains anionic groups. Hard inorganic foam.

12. A method for producing a hard inorganic foam, comprising: (A) an inorganic foam, comprising: a) at least one mineral binder; b) at least one surfactant S and / or particles N; c) at least one polymer obtained from a combination of polyisocyanate and polyol and / or polyamine; d) water and providing an inorganic foam containing the same; characterised in that the at least one polymer obtained from a combination of polyisocyanate and polyol and / or polyamine contains anionic groups; and (B) curing the inorganic foam of step (A). A method comprising the above.

13. A method for producing a hard inorganic foam according to claim 12, characterised in that the at least one polymer obtained from a combination of polyisocyanate and polyol and / or polyamine is in the form of an aqueous dispersion of the polymer.

14. Use of the hard inorganic foam according to any one of claims 1 to 11 in an article or system for thermal insulation, sound insulation, lightweight construction and / or passive fire protection.

15. Use of the hard inorganic foam according to any one of claims 1 to 11 for filling cavities.

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