Accelerator for the reaction of high-silica aluminosilicate with water

Abstract

The present invention relates to a promoter for the reaction of high-silica aluminosilicate with water. The promoter is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof. The present invention also relates to a binder containing high-silica aluminosilicate and the promoter, and their use in construction materials.

Description

Technical Field

[0001] The present invention relates to an accelerator for the reaction of high-silica aluminosilicate with water. The present invention also relates to a binder containing high-silica aluminosilicate and said accelerator, and their use in construction materials.

Background Art

[0002] Cement-based building materials, particularly concrete or mortar, rely on cementitious materials as binders. Cementitious binders are typically mineral hydraulic binders, and the most abundant of them is cement, particularly ordinary Portland cement (OPC). However, the use of cement, particularly ordinary Portland cement, has a high environmental footprint. One major reason is the high CO2 emissions associated with cement production. Many efforts have thus been made to at least partially replace cement as a binder from building materials.

[0003] One possibility is the use of materials having cementitious properties, so-called supplementary cementitious materials (SCM). Supplementary cementitious materials may have hydraulic properties, pozzolanic properties, and / or latent hydraulic properties. Supplementary cementitious materials known for many years include limestone, steelmaking slag, calcined clay, natural pozzolan, such as volcanic ash, silica fume, or fly ash.

[0004] It is well known in the art that supplementary cementitious materials can be activated to play their role as hydraulic binders.

[0005] For example, International Publication No. 2020 / 025504 pamphlet (St.Gobain) discloses a binder based on clay minerals, and teaches that a flocculant, particularly a polycationic polymer, improves the adhesion of such a clay-based binder.

[0006] International Publication No. WO 2019 / 110134 pamphlet (Ecocem) discloses a binder based on slag having an activator for slag / water reaction selected from alkali metal carbonates, mineral waste, silica fume, rice husk ash, and / or phosphoric acid. Soluble chlorides, fluorides, and / or sulfates are described as suitable co-activators. Further, chelating agents selected from phosphonates, phosphates, carboxylates, and amines are disclosed.

[0007] One class of supplementary cementitious materials is aluminosilicates and, for example, high silica aluminosilicates.

[0008] It is well known in the art that aluminosilicates can be activated to react with water to form so-called geopolymers, for example, by highly alkaline components such as alkali metal silicate salts, alkali metal hydroxides, or lime (see International Publication No. WO 2010 / 079414 pamphlet (S. Alter)). SUMMARY OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION

[0009] There is still a need for supplementary cementitious materials for making such high silica aluminosilicates useful in water-solidifying compositions, particularly alternative accelerators for high silica aluminosilicates. Typically, very alkaline chemicals and / or accelerators that result in high dust emissions during handling should be avoided. MEANS FOR SOLVING THE PROBLEM

[0010] An object of the present invention is to provide an accelerator for the reaction of high silica aluminosilicates with water. Specifically, the accelerator should have high activation ability, good availability, low alkalinity, and be safe to handle.

[0011] It is also an object of the present invention to provide a high silica aluminosilicate-based binder that can be used to replace an OPC-based binder.

[0012] Another object of the present invention is to provide construction materials based on high silica aluminosilicate-based binders, particularly concrete and mortar compositions.

[0013] It has surprisingly been found that chemical substances selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids and their salts, amino acids and their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof are suitable accelerators for the reaction of high silica aluminosilicates with water.

[0014] Thus, the present invention relates to the use of an accelerator for the reaction of high silica aluminosilicates with water, said accelerator being selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids and their salts, amino acids and their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

[0015] The accelerator of the present invention has been found to result in an increase in the strength, particularly the compressive strength, of a mixture comprising high silica aluminosilicate, water, and the accelerator, when measured according to EN12190 at a given time point after the addition of water to the high silica aluminosilicate, compared to the strength, particularly the compressive strength, of a mixture of the same ratio of high silica aluminosilicate and water but without the added accelerator, and measured after the same time. The time is always measured from the time of addition of water to the high silica aluminosilicate.

[0016] It has further been found that the accelerator of the present invention can have a favorable effect on the rheology of a mixture of high-silica aluminosilicate with water. By favorable effect is meant, in this context, that the viscosity of a mixture comprising high-silica aluminosilicate, water, and the accelerator is lower compared to the viscosity of a mixture of high-silica aluminosilicate and water in the same ratio but without the addition of the accelerator.

[0017] It has further been found that the accelerator of the present invention can have a favorable effect on the water demand of a mixture of high-silica aluminosilicate with water. By favorable effect is meant, in this context, that the water demand for achieving the same consistency of a mixture of high-silica aluminosilicate and water in the same ratio but without the addition of the accelerator is lower compared to the water demand for achieving the same consistency after mixing a mixture comprising high-silica aluminosilicate, water, and the accelerator.

[0018] It has further been found that the accelerator of the present invention can have a favorable effect on the reduction of fluidity over time after wet mixing. By favorable effect is meant, in this context, that the loss of fluidity of a mixture comprising high-silica aluminosilicate, water, and the accelerator is lower compared to the loss of fluidity of a mixture of high-silica aluminosilicate and water in the same ratio but without the addition of the accelerator.

[0019] A further aspect of the present invention is the subject of the independent claims. Preferred embodiments of the present invention are the subject of the dependent claims.

DETAILED DESCRIPTION OF THE INVENTION

[0020] In a first aspect, the present invention relates to the use of an accelerator for the reaction of high-silica aluminosilicate with water, wherein the accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids and their salts, amino acids and their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

[0021] The high-silica aluminosilicates in this situation are pozzolanic and / or latent hydraulic materials having aluminosilicates as constituents, and are characterized by the high content of silica (SiO2) in their chemical compositions. The chemical composition of the high-silica aluminosilicates can be determined by XRF as described in EN196-2:2013. The high-silica aluminosilicates of the present invention may contain other oxides in addition to SiO2 and Al2O3. The other oxides can be, for example, boron oxide, calcium oxide, titanium oxide, iron oxide, zinc oxide. The term "oxide" generally also encompasses the respective hydroxides and / or mixed oxides / hydroxides.

[0022] The high content of SiO2 can be expressed as a weight percentage relative to the total dry weight of the high-silica aluminosilicates. Thus, the high-silica aluminosilicates of the present invention can be characterized by a SiO2 content of 40 wt% or more, preferably 50 wt% or more, determined by XRF relative to the total dry weight of each high-silica aluminosilicate and as described in EN196-2:2013.

[0023] The high-silica aluminosilicates of the present invention can be characterized by their chemical composition, where the weight ratio of SiO2 to Al2O3 is from 50:50 to 100:0, preferably from 65:35 to 95:5. Preferred high-silica aluminosilicates of the present invention have a weight ratio of (SiO2 + Al2O3) to CaO of from 75:25 to 100:0, preferably from 83:17 to 100:0, more preferably from 90:10 to 99:1, and at the same time have a weight ratio of SiO2 to Al2O3 of from 50:50 to 100:0, preferably from 65:35 to 95:5.

[0024] Suitable high-silica aluminosilicates in this situation are selected from vitreous pumice, vitreous volcanic ash, zeolitized tuff, diatomaceous earth, fly ash, silica fume, kiln dust, microsilica, pyrogenic silica, precipitated silica, burnt oil shale, burnt shells of organic substances, and mixtures thereof. Fly ash is in particular class F fly ash according to standard ASTM C618.

[0025] In this situation, the high-silica aluminosilicate is not steelmaking slag, in particular not ground granulated blast-furnace slag (GGBS) or basic oxygen furnace slag (BOS), and not class C fly ash according to standard ASTM C618. Furthermore, in this situation, the high-silica aluminosilicate is not a clay mineral or fired clay.

[0026] The particle size of the high-silica aluminosilicate can be analyzed, for example, by sieve analysis as described in standard ASTM C136 / C136M. The process separates the fine particles from the coarser particles by passing the material through several sieves of different mesh sizes. The material to be analyzed is vibrated through a series of successively finer sieves using horizontal movement, vertical movement, or rotation movement alone, or in combination. As a result, the percentage of particles retained on a sieve of a given size is obtained.

[0027] Another measure of the fineness of the high-silica aluminosilicate is the Blaine surface. The Blaine surface can be determined by NF EN196-6. According to a preferred embodiment, the high-silica aluminosilicate is 1000 - 8000 cm 2 / g, preferably 2000 - 6000 cm 2 / g, more preferably 3000 - 5000 cm 2It has a brain surface of / g. This is because the accelerator promotes the reaction of the highly siliceous aluminosilicate with water to such an extent that coarser SCMs can also be used. Coarser SCMs can have the advantages of better availability and lower cost compared to finer SCMs. However, it is also possible to use highly siliceous aluminosilicates with a higher specific surface area.

[0028] The present invention relates to the use of an accelerator for the reaction of a highly siliceous aluminosilicate with water. When the highly siliceous aluminosilicate reacts with water, a hydration reaction occurs and different mineral phases are formed. Thereby, water and SCM are consumed, hardening progresses, and strength is generated. A suitable method for measuring the reaction of the highly siliceous aluminosilicate with water is thus the measurement of strength, in particular compressive strength. A higher compressive strength corresponds to a higher progress of the reaction, i.e., more mineral phases are formed. The promotion of the reaction of the highly siliceous aluminosilicate with water can thus be determined by comparing the strength, in particular the compressive strength, of different mixtures after a given time of the reaction, for example, after 2 days, 7 days, and / or 28 days. The accelerator for the reaction of the highly siliceous aluminosilicate with water brings about an increase in the strength, in particular the compressive strength, of a mixture comprising the highly siliceous aluminosilicate, water, and the accelerator after a given point in time (measured after the same time compared to the strength, in particular the compressive strength, of a mixture of the highly siliceous aluminosilicate and water in the same ratio but without the addition of the accelerator). The time is always measured from the point in time of the addition of water to the highly siliceous aluminosilicate. A suitable procedure for the measurement of compressive strength is described in EN12190.

[0029] The accelerator for the reaction of the highly siliceous aluminosilicate with water is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids and their salts, amino acids and their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

[0030] One type of suitable accelerator is alkanolamine. The alkanolamine is preferably selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine (TEA), diethanolisopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), isopropanolamine, diisopropanolamine, triisopropanolamine (TIPA), N-methyldiisopropanolamine (MDIPA), N-methyldiethanolamine (MDEA), tetrahydroxyethylethylenediamine (THEED), and tetrahydroxyisopropylethylenediamine (THIPD), and mixtures of two or more of these alkanolamines.

[0031] Preferred alkanolamines are triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), and ethanol diisopropanolamine (EDIPA). Particularly preferred alkanolamines are diethanolisopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), and triisopropanolamine (TIPA).

[0032] Another type of suitable accelerator is sugar. "Sugar" in the meaning of the present invention is a carbohydrate having an aldehyde group. In a particularly preferred embodiment, the sugar belongs to the group of monosaccharides or disaccharides. Examples of sugars include, but are not limited to, glyceraldehyde, threose, erythrose, xylose, lyxose, ribose, arabinose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fructose, sorbose, lactose, maltose, sucrose, lactulose, trehalose, cellobiose, chitobiose, isomaltose, palatinose, mannobios, raffinose, and xylobiose. Sugars can also be used in the form of dextrin, fermentation residues, or molasses. Both the D-form and L-form of sugars are equally preferred. Particularly preferred sugars are fructose, mannose, maltose, glucose, galactose, dextrin, fermentation residues, and molasses.

[0033] Another type of suitable accelerator is a sugar acid or a salt thereof. "Sugar acid" in the context of the present invention is a monosaccharide having a carboxyl group. This can belong to any of the classes of aldonic acids, ursonic acids, uronic acids, or alduronic acids. Preferably, this is an aldonic acid. Examples of sugar acids useful in connection with the present invention include, but are not limited to, gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, and saccharic acid. The sugar acid can be in the form of the free acid or as a salt. According to an embodiment, the salt of the sugar acid can be a salt having a metal of Group Ia, IIa, Ib, IIb, IVb, VIIIb of the periodic table of the elements. Preferred salts of sugar acids are salts of alkali metals, alkaline earth metals, iron, cobalt, copper, or zinc. Particularly preferred are salts having sodium, potassium, and calcium. Both the D-form and L-form of sugar acids are equally preferred. Particularly preferred sugar acid is gluconic acid and its salts, especially sodium gluconate.

[0034] Another type of suitable accelerator is an amino acid or a salt thereof. The amino acids are preferably selected from the group consisting of glycine, lysine, glutamate, glutamic acid, aspartic acid, polyaspartic acid, methionine, nitrilotriacetic acid (NTA), iminodiacetic acid, methylglycine-N,N-diacetic acid, and N,N-bis(carboxymethyl)glutamic acid, ethylenediaminedisuccinic acid (EDDS), ethylenediaminetetraacetic acid (EDTA), hexamethylenediaminetriacetic acid (HEDTA), diethylenetriaminepentaacetic acid (DTPA) or a salt thereof. Particularly preferred are salts of alkali metals or alkaline earth metals. In particular, the salts are selected from the group consisting of tetrasodium N,N-bis(carboxymethyl)glutamate, trisodium methylglycine-N,N-diacetic acid, tetrasodium iminodiacetate (IDS), trisodium ethylenediaminedisuccinate, tetrasodium ethylenediaminetetraacetate, and tetrasodium hexamethylenediaminetetraacetate.

[0035] Another type of suitable accelerator is a carboxylic acid or a salt thereof. The term "carboxylic acid" means a carboxylic acid or any organic molecule having a carboxylate group, excluding sugar acids or amino acids as described above. Particularly preferred carboxylic acids are formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and salicylic acid. The carboxylic acid can be in the form of a free acid or a salt. According to an embodiment, the salt of the carboxylic acid can be a salt having a metal of groups Ia, IIa, Ib, IIb, IVb, VIIIb of the periodic table of the elements. Preferred salts of sugar acids are salts of alkali metals, alkaline earth metals, iron, cobalt, copper or zinc. Particularly preferred are salts having sodium, potassium, and calcium. Preferred salts of carboxylic acids are calcium malonate, calcium succinate, calcium lactate, potassium citrate, and sodium citrate.

[0036] Another type of suitable accelerator is a reducing agent. In this context, a reducing agent is a material having a reduction potential measured under standard conditions with respect to a standard reference hydrogen half-cell of less than 0.77V. That is, a suitable reducing agent has a half-cell potential lower than that of the couple Fe 3+ / Fe 2+ . The reducing agent is preferably selected from the group consisting of thiosulfate, thiocyanate, and sulfide, preferably sodium thiocyanate, sodium thiosulfate, or potassium sulfide. The reducing agent does not belong to any of the groups of alkanolamines, sugars, sugar acids, carboxylic acids and their salts, or amino acids and their salts as described above in this context.

[0037] Other suitable accelerators are sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), and etidronic acid.

[0038] Another type of suitable accelerator is a mineral salt. In this context, a mineral salt is a salt selected from the group consisting of alkali metal or alkaline earth metal nitrates, alkali metal or alkaline earth metal nitrites, alkali metal or alkaline earth metal chlorides, aluminum sulfate, aluminum chloride, sodium sulfate, and calcium sulfate. Particularly preferred mineral salts are sodium chloride, calcium nitrite, calcium nitrate, calcium chloride, magnesium chloride, aluminum sulfate, aluminum chloride, sodium sulfate, and calcium sulfate.

[0039] According to the embodiment, the accelerator is selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), fructose, mannose, maltose, glucose, galactose, dextrin, fermentation residue, molasses, gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, saccharic acid and their sodium, potassium or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, salicylic acid and their sodium, potassium or calcium salts, glycine, glutamic acid, aspartic acid, polyaspartic acid, tetrasodium iminodisuccinate (IDS), diethylenetriaminepentaacetic acid (DTMA), nitrilotriacetic acid (NTA), sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, sodium thiocyanate, sodium chloride, calcium nitrite, calcium nitrate, calcium chloride, magnesium chloride, calcium sulfate, aluminum sulfate, aluminum chloride, sodium sulfate, thiosulfate, particularly sodium thiosulfate, thiocyanate, and sulfide, particularly potassium sulfide.

[0040] According to a particularly preferred embodiment, the accelerator is selected from the group consisting of diethanolisopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), lactic acid, calcium lactate, oxalic acid, malonic acid, succinic acid, adipic acid, malic acid, tartaric acid, citric acid, sodium citrate, potassium citrate, gluconic acid, sodium gluconate, glycine, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, tetrasodium iminodisuccinate (IDS), nitrilotriacetic acid (NTA), and calcium sulfate.

[0041] According to a further preferred embodiment, the accelerator is a mixture of two alkanolamines or of an alkanolamine with at least one further accelerator different from the alkanolamine.

[0042] According to a particularly preferred embodiment, the accelerator is a mixture of diethanol isopropanolamine (DEIPA) and triisopropanolamine (TIPA).

[0043] According to a further embodiment, the accelerator is an alkanolamine selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanol isopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), and / or methyldiethanolamine (MDEA), in particular TIPA and / or DEIPA, and a mixture of one further accelerator selected from the group consisting of fructose, mannose, maltose, glucose, galactose, dextrin, fermentation residues, molasses, gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, saccharic acid and their sodium, potassium or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, salicylic acid and their sodium, potassium or calcium salts, glycine, glutamic acid, aspartic acid, polyaspartic acid, iminodisuccinic acid tetrasodium (IDS), diethylenetriaminepentaacetic acid (DTMA), nitrilotriacetic acid (NTA), sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, sodium thiocyanate, sodium chloride, calcium nitrite, calcium nitrate, calcium chloride, magnesium chloride, calcium sulfate, aluminum sulfate, aluminum chloride, sodium sulfate, thiosulfate, in particular sodium thiosulfate, thiocyanate, and sulfide, in particular potassium sulfide.

[0044] Preferred embodiments of the accelerator of the present invention are a mixture of TIPA and / or DEIPA with at least one of lactic acid, malic acid, tartaric acid, citric acid, sodium citrate, potassium citrate, malonic acid, succinic acid, adipic acid, glycine, sulfamic acid, or salts thereof, pyrocatechol, sugars, particularly fructose, iminodisuccinic acid tetrasodium (IDS), calcium chloride, and calcium sulfate.

[0045] Particularly preferred embodiments of the accelerator of the present invention are a mixture of TIPA and / or DEIPA with sugars, preferably fructose.

[0046] Even more particularly preferred embodiments of the accelerator of the present invention are a mixture of TIPA and / or DEIPA with citric acid or a salt thereof, particularly citric acid, sodium citrate, potassium citrate, or calcium citrate.

[0047] According to a further embodiment, the accelerator is an alkanolamine selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), and / or methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and a mixture of two further accelerators. The first further accelerator is selected from sugars, particularly fructose, mannose, maltose, glucose, or galactose, and the second further accelerator is selected from the group consisting of mineral salts and reducing agents, preferably sodium thiocyanate, sodium chloride, calcium chloride, magnesium chloride, calcium nitrite, calcium nitrate, aluminum sulfate, aluminum chloride, sodium sulfate, calcium sulfate, sodium thiosulfate, and potassium sulfide.

[0048] A further particularly preferred embodiment of the accelerator of the present invention is a mixture of TIPA and / or DEIPA with a sugar, preferably fructose, and with a carboxylic acid or its salt, preferably citric acid, sodium citrate, potassium citrate, or calcium citrate.

[0049] A further particularly preferred embodiment of the accelerator of the present invention is a mixture of TIPA and / or DEIPA with a sugar, preferably fructose, and with at least one of sodium thiocyanate, sodium chloride, aluminum sulfate, or calcium nitrite.

[0050] A further particularly preferred embodiment of the accelerator of the present invention is a mixture of TIPA and / or DEIPA with calcium sulfate or calcium nitrate.

[0051] According to a further embodiment, the accelerator is an alkanolamine selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethyldiisopropanolamine (EDIPA), and / or methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and a mixture of two further accelerators. The first further accelerator is selected from sugars, particularly fructose, mannose, maltose, glucose, or galactose, and the second further accelerator is selected from the group consisting of sugar acids, carboxylic acids, and sulfamic acid, particularly gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, saccharic acid, salicylic acid, and their sodium, potassium, or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and their sodium, potassium, or calcium salts.

[0052] According to a further embodiment, the accelerator is selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), and / or methyldiethanolamine (MDEA), in particular alkanolamines selected from the group consisting of TIPA and / or DEIPA, and a mixture of three further accelerators, wherein the first further accelerator is selected from sugars, preferably fructose, mannose, maltose, glucose, or galactose, the second further accelerator is selected from sugar acids, carboxylic acids, and sulfamic acid, preferably gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, mucic acid, saccharic acid, and their sodium, potassium, or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, salicylic acid, and their sodium, potassium, or calcium salts, and the third further accelerator is selected from mineral salts and reducing agents, preferably sodium thiocyanate, sodium chloride, calcium chloride, magnesium chloride, calcium nitrite, calcium nitrate, aluminum sulfate, aluminum chloride, sodium sulfate, calcium sulfate, sodium thiosulfate, and potassium sulfide.

[0053] According to an embodiment, the accelerator of the present invention is used in a pure undiluted form.

[0054] According to different embodiments, the accelerator of the present invention is used as a mixture or as part of a mixture. The mixture comprises or consists of an accelerator or a mixture of accelerators and optionally further components. Such further components can be, for example, a solvent, in particular water, a biocide, or a pigment. The accelerator of the present invention can thus also be used in a dispersed or dissolved state, in particular dispersed or dissolved in water.

[0055] When the accelerator of the present invention is a mixture of two or more such accelerators, or when a mixture is used, the accelerator or mixture can exist as a one-component, two-component, or multi-component composition. This means that the individual components that form the accelerator or mixture of the present invention are already mixed in one container and can form a one-component composition. The accelerator can also be present in two or more spatially separated containers and can form a two-component or multi-component composition. This can have advantages regarding the shelf life of the accelerator mixture. This can also facilitate mixing the accelerator with high silica aluminosilicate and water in an indefinite ratio. When the accelerator of the present invention is present in a two-component or multi-component composition, they can be premixed, or added individually at the same time, or added individually at different times.

[0056] According to an embodiment, the accelerator of the present invention is added in a total amount of 0.005 to 25% by weight, based on the total dry weight of the high silica aluminosilicate. The total amount refers to the sum of the weight percentages of all accelerators present.

[0057] According to a preferred embodiment, the alkanolamine is added in a total amount of 0.005 to 5% by weight, preferably 0.01 to 3% by weight, based on the total dry weight of the high silica aluminosilicate.

[0058] According to a preferred embodiment, the sugar is added in a total amount of 0.005 to 5% by weight, preferably 0.01 to 3% by weight, based on the total dry weight of the high silica aluminosilicate.

[0059] According to a preferred embodiment, the carboxylic acid is added in a total amount of 0.005 to 5% by weight, preferably 0.01 to 3% by weight, based on the total dry weight of the high silica aluminosilicate.

[0060] According to a preferred embodiment, the amino acid is added in a total amount of 0.005 to 5% by weight, preferably 0.01 to 3% by weight, based on the total dry weight of the high silica aluminosilicate.

[0061] According to a preferred embodiment, a reducing agent, particularly sodium thiocyanate, is added in a total amount of 0.05 to 10% by weight, preferably 0.1 to 6% by weight, based on the total dry weight of the high-silica aluminosilicate.

[0062] According to a preferred embodiment, the mineral salt is added in a total amount of 0.005 to 25% by weight, preferably 0.1 to 10% by weight or 2 to 25% by weight, more preferably 0.1 to 6% by weight or 10 to 25% by weight, based on the total dry weight of the high-silica aluminosilicate. The range of 2 to 25% by weight, preferably 10 to 25% by weight, is particularly relevant to the use of sodium chloride, aluminum sulfate, or calcium sulfate as the mineral salt.

[0063] According to an embodiment, any of sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), and etidronic acid is added in an amount of 0.05 to 10% by weight, preferably 0.1 to 6% by weight, based on the total dry weight of the high-silica aluminosilicate.

[0064] It has been found that accelerators in dosages too high for the high-silica aluminosilicate reduce the accelerating effect.

[0065] When a mixture of two or more of the above accelerators is used, - alkanolamine and sugar, - alkanolamine and carboxylic acid, - alkanolamine and amino acid, - sugar and amino acid, - carboxylic acid and amino acid, or - alkanolamine, sugar, carboxylic acid, and amino acid and any of sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), and etidronic acid if any, preferably has a weight ratio in the range of 1:50 to 50:1, more preferably 1:20 to 20:1.

[0066] When a mixture of two or more of the above accelerators is used, the weight ratio of any selection or combination of (if present) alkanolamine, sugar, carboxylic acid, amino acid, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), and etidronic acid to any selection or combination of mineral salts and reducing agents is preferably in the range of 1:5000 to 1:1000, more preferably 1:2500 to 1:1000.

[0067] It is possible to promote the reaction of high-silica aluminosilicate with water in the presence of a binder. In particular, it is possible to promote the reaction of high-silica aluminosilicate with water in the presence of Portland cement, limestone, gypsum, or a mixture thereof. According to an embodiment, the above use is thus characterized in that the reaction of high-silica aluminosilicate with water is promoted in the presence of Portland cement and optionally limestone and / or gypsum.

[0068] The present invention also relates to a method for promoting the reaction of high-aluminosilicate with water, the method comprising the step of mixing at least one high-silica aluminosilicate with water and an accelerator selected from the group consisting of alkanolamine, reducing agent, sugar, sugar acid, carboxylic acid and its salts, amino acid and its salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or a mixture thereof.

[0069] All of the above features and embodiments are also applicable in this case.

[0070] In another aspect, the present invention also relates to a high-silica aluminosilicate-based binder for use preferably as a binder in concrete or mortar, the binder comprising a) at least one high-silica aluminosilicate, preferably pumice, glassy volcanic ash, zeolitized tuff, or a mixture thereof, b) At least one accelerator for the reaction of the high-silica aluminosilicate with water (said accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof), c) Optionally at least one binder d) Optionally a further additive different from b) comprising or consisting of these.

[0071] Any embodiment particularly related to the high-silica aluminosilicate and at least one accelerator described as preferred above should also be understood to apply to the binder based on the high-silica aluminosilicate of the present invention. In particular, preferably, the high-silica aluminosilicate has a SiO2 content of 40% by weight or more, preferably 50% by weight or more, based on the total dry weight of each high-silica aluminosilicate and determined by XRF as described in EN196-2:2013.

[0072] According to some embodiments, the binder based on the high-silica aluminosilicate of the present invention comprises an accelerator selected from the group consisting of diethanol isopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), lactic acid, calcium lactate, oxalic acid, malonic acid, succinic acid, adipic acid, malic acid, tartaric acid, citric acid, gluconic acid, sodium gluconate, glycine, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, iminodisuccinic acid tetrasodium (IDS), nitrilotriacetic acid (NTA), and calcium sulfate.

[0073] According to a further embodiment, the high silica aluminosilicate-based binder of the present invention comprises an accelerator which is a mixture of diethanol isopropanolamine (DEIPA) and triisopropanolamine (TIPA).

[0074] According to a further embodiment, the high silica aluminosilicate-based binder of the present invention comprises an accelerator which is a mixture of an alkanolamine selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanol isopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), and / or methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and a further accelerator selected from the group consisting of lactic acid, malic acid, tartaric acid, citric acid, malonic acid, succinic acid, adipic acid, glycine, sulfamic acid, or salts thereof, pyrocatechol, sugars, particularly fructose, iminodisuccinic acid tetrasodium (IDS), calcium chloride, and calcium sulfate.

[0075] According to a further embodiment, the high silica aluminosilicate-based binder of the present invention comprises an accelerator which is a mixture of an alkanolamine selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanol isopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), and / or methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and two further accelerators, wherein the first further accelerator is selected from sugars, particularly fructose, mannose, maltose, glucose, or galactose, and the second further accelerator is selected from mineral salts, preferably from the group consisting of sodium chloride, calcium chloride, calcium nitrite, calcium nitrate, aluminum sulfate, aluminum chloride, sodium sulfate, and calcium sulfate.

[0076] The binder in this situation is an inorganic binder selected from the group consisting of cement, gypsum, lime, calcined magnesia, caustic magnesia, alumina, latent hydraulic binder, limestone, and / or pozzolan. The latent hydraulic binder and / or pozzolan used as the binder is chemically different from the high silica aluminosilicate as defined above. In particular, slag, for example, blast furnace slag fine powder and basic oxygen slag, clay minerals, in particular, calcined clay, and / or class C fly ash are latent hydraulic binders and / or pozzolans that are chemically different from the high silica aluminosilicate of the present invention and can be used as the binder. The cement may be portland cement of type CEM I, CEM II, and CEM IV, except in particular CEM II / A-S and CEM II / B-S as described in standard EN197-1, calcium aluminate cement as described in standard EN14647, and / or calcium sulfoaluminate cement. The term "gypsum" means to include various forms of CaSO4, in particular, CaSO4 anhydrite, CaSO4 α- and β- hemihydrates, and CaSO4 dihydrate. The term "lime" means to include natural hydraulic lime, formulated lime, hydraulic lime, and air-hardening lime as described in standard EN459-1:2015. The term "alumina" means aluminum oxide, aluminum hydroxide, and / or aluminum oxyhydroxide, such as gibbsite and boehmite, calcined or flash calcined alumina, alumina resulting from the Bayer process, hydratable alumina, such as amorphous intermediate phase alumina and low phase alumina. Limestone preferably complies with standard EN197-1:2011. Preferably, the binder is selected from the group consisting of portland cement, calcium aluminate cement, calcium sulfoaluminate cement, gypsum, hydraulic lime, air-hardening lime, calcined magnesia, caustic magnesia, calcined alumina, hydratable alumina, aluminum hydroxide, slag, for example, blast furnace slag fine powder and basic oxygen slag, limestone, clay minerals, in particular, calcined clay, and / or class C fly. Particularly preferably, the binder is selected from portland cement, limestone, and / or gypsum.

[0077] According to an embodiment, when a binder is present, the weight ratio of the high silica aluminosilicate in the binder based on high silica aluminosilicate, in particular, pumice glass, volcanic ash glass, zeolitized tuff, burnt oil shale to the binder is 1:19 to 19:1, preferably 1:9 to 15:1, more preferably 1:6 to 12:1, even more preferably 1:5 to 9:1, highly preferably 1:3 to 6:1, and particularly 1:1 to 5:1.

[0078] Optionally, the slag-based binder of the present invention further contains additional additives different from the accelerator for the reaction of the high silica aluminosilicate with water. According to an embodiment, such additional additives are selected from the group consisting of plasticizers, superplasticizers, shrinkage reducing agents, air-entraining solvents, deaerators, stabilizers, viscosity modifiers, thickeners, water reducing agents, setting retarders, water resistance agents, fibers, foaming agents, defoaming agents, redispersible polymer powders, dust control agents, chromate reducing agents, pigments, biocides, corrosion inhibitors, and steel passivators.

[0079] According to some embodiments, the high silica aluminosilicate-based binder of the present invention a) 75 to 99.995% by weight, preferably 95 to 99.99% by weight of at least one high silica aluminosilicate, preferably pumice glass, volcanic ash glass, zeolitized tuff, burnt oil shale, b) 0.005 to 25% by weight, preferably 0.01 to 5% by weight of at least one accelerator for the reaction of at least one high silica aluminosilicate with water comprises or consists of these (in either case, based on the total dry weight of the binder) wherein the accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

[0080] According to a further embodiment, the high-silica aluminosilicate-based binder of the present invention is a) 74.9 to 99.895% by weight, preferably 74.99 to 99.89% by weight of at least one high-silica aluminosilicate, preferably pumice, volcanic ash, zeolitized tuff, burnt oil shale, b) 0.005 to 25% by weight, preferably 0.01 to 5% by weight of at least one accelerator for the reaction of at least one high-silica aluminosilicate with water, c) 0.1 to 25% by weight of a binder selected from cement or lime comprising or consisting of these (in each case relative to the total dry weight of the binder), wherein the accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

[0081] According to a further embodiment, the high-silica aluminosilicate-based binder of the present invention is a) 74.9 to 99.895% by weight, preferably 74.99 to 99.89% by weight of at least one high-silica aluminosilicate, preferably pumice, volcanic ash, zeolitized tuff, burnt oil shale, b) 0.005 to 25% by weight, preferably 0.01 to 5% by weight of at least one accelerator for the reaction of at least one high-silica aluminosilicate with water, c) 0.1 to 25% by weight of a binder selected from calcium sulfoaluminate cement comprising or consisting of these (in each case relative to the total dry weight of the binder), Here, the accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

[0082] According to a further embodiment, the high-silica aluminosilicate-based binder of the present invention a) 49.995 to 99.895% by weight, preferably 49.99 to 99.89% by weight of at least one high-silica aluminosilicate, preferably pumice, vitric tuff, zeolitized tuff, burnt oil shale, b) 0.005 to 25% by weight, preferably 0.01 to 5% by weight of at least one accelerator for the reaction of at least one high-silica aluminosilicate with water, c) a cobinder selected from a combination of calcium aluminate cement with calcium sulfate or a combination of calcium sulfoaluminate cement with calcium sulfate comprises or consists of these (in each case relative to the total dry weight of the binder), Here, the accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

[0083] The preferred accelerators in any of these embodiments are the same as above.

[0084] In yet another aspect, the present invention also relates to a building material comprising a high-silica aluminosilicate-based binder as described above, in particular mortar or concrete.

[0085] Thus, in particular, the present invention also relates to a building material, preferably a) A binder based on 5 to 95% by weight, preferably 5 to 60% by weight, of high-silica aluminosilicate (the binder is a1) At least one high-silica aluminosilicate, preferably pumice, volcanic ash, zeolitized tuff, burnt oil shale, a2) Containing or consisting of at least one accelerator for the reaction of at least one high-silica aluminosilicate with water, the accelerator being selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof, preferably selected from the accelerators described as preferred above), b) 5 to 95% by weight, preferably 30 to 90% by weight, of at least one aggregate, c) 0 to 90% by weight, preferably 5 to 30% by weight, of at least one co-binder (the co-binder being different from the high-silica aluminosilicate-based binder a), the co-binder being selected from the group consisting of cement, gypsum, lime, calcined magnesia, caustic magnesia, alumina, limestone, clay minerals, calcined clay, slag, class C fly ash), d) 0 to 10% by weight of further additives, and e) Optionally an amount of water to achieve a water:dry composition mass ratio of 0.1 to 0.6, preferably 0.2 to 0.5, particularly 0.2 to 0.35 (in each case relative to the total dry weight of the construction material), relating to a concrete or mortar composition.

[0086] The high-silica aluminosilicate-based binder, cobinder, and further additives are preferably as described above. In particular, preferably, the high-silica aluminosilicate has a SiO2 content of 40 wt% or more, preferably 50 wt% or more, based on the total dry weight of each high-silica aluminosilicate and as determined by XRF as described in EN196-2:2013.

[0087] It may also be preferable to combine two or more further additives in the construction material of the present invention. Thus, the construction material of the present invention comprises at least one high-silica aluminosilicate as described above, and an accelerator selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), and etidronic acid, alkali metal or alkaline earth metal nitrates or nitrites or chlorides, aluminum sulfate, aluminum chloride, sodium sulfate, calcium sulfate, or mixtures thereof as described above.

[0088] According to a preferred embodiment, the construction material comprises at least one cobinder in an amount of 5 to 90 wt%, preferably 5 to 30 wt%, and the cobinder is selected from Portland cement, calcium aluminate cement, calcium sulfoaluminate cement, gypsum, calcium sulfate, lime, heavy calcium carbonate, pozzolan, caustic magnesia, and latent hydraulic binders, where pozzolan and latent hydraulic binders do not include high-silica aluminosilicates.

[0089] The aggregate may be any material that is non-reactive in the hydration reaction of the binder. The aggregate may be any aggregate typically used for construction materials. Typical aggregates are, for example, rock, crushed stone, gravel, and sand. The aggregate can also be a fine aggregate or a filler. The aggregates useful in the present invention can have any shape and size typically encountered for such aggregates. Particularly preferred aggregates are sand. Sand is a naturally occurring granular material composed of pulverized rock or mineral particles. It is available in various forms and sizes. Examples of suitable sand are quartz sand, river sand, or crushed aggregate. Suitable sand is described, for example, in standard ASTM C778 or EN196-1.

[0090] According to an embodiment, the aggregate may also be one or more of the following (i) to (iv). (i) Preferably, a bio-derived material of plant origin, more preferably a bio-derived material of plant origin essentially composed of cellulose and / or lignin, particularly a bio-derived material originating from hemp, flax, cereal straw, oats, rice, rapeseed, corn, sorghum, flax, kaya, rice husk, sugarcane, sunflower, kenaf, coconut, olive stone, bamboo, wood, or a mixture thereof. According to an embodiment, the bio-derived material of plant origin preferably has a distinct form selected from fibers, root hairs, dust, coarse flour, powder, shavings, pith, particularly the pith of sunflower, corn, rapeseed, and mixtures thereof. (ii) Synthetic non-mineral materials, preferably including or selected from thermoplastic plastics, thermosetting plastics or resins, elastomers, rubbers, plastic materials reinforced with textile fibers, glass or carbon fibers. The synthetic non-mineral materials can be filled or unfilled with fillers. (iii) Inorganic aggregates from the destruction of civil or building structures, preferably including or selected from waste concrete, mortar, bricks, natural stone, asphalt, tiles, tiles, lightweight concrete, clinker, metal scrap. (iv) Organic aggregates from the recycling of industrial products, in particular composite materials that are difficult to recycle, in particular recycled electrical insulation materials. Particularly preferred examples are polystyrene, polyurethane, epoxy resin, phenolic resin, wooden insulation materials, and mixtures thereof.

[0091] Most preferably, the aggregate is in a specific form.

[0092] Throughout the present invention, when calculating the mass ratio of water to the dry composition, the total dry weight of the high-silica aluminosilicate-based binder and any optional cobinder present should be taken into account. No correction should be made to compensate for any degree of hydraulicity. The term dry composition relates in this context to all the powdery components of the composition, in particular the high-silica aluminosilicate-based binder, the aggregate, and the cobinder.

[0093] The weight ratio of water to the binder can be adjusted to control the rheology and / or strength of the wet construction material. A greater amount of water results in a wet composition with greater fluidity, and a lesser amount of water results in a paste-like wet composition. The rheology can be adjusted by the amount of water to yield a wet composition having a rheology ranging from self-leveling to very thick. Typically, a lesser amount of water also results in an increase in strength.

[0094] According to an embodiment, when a cobinder is present, the weight ratio of the high-silica aluminosilicate-based binder to the cobinder in the construction material as described above is 1:19 to 19:1, preferably 1:9 to 15:1, more preferably 1:6 to 12:1, even more preferably 1:5 to 9:1, highly preferably 1:3 to 6:1, and particularly 1:1 to 5:1.

[0095] According to an embodiment, the water-solidifying composition of the present invention contains 15 to 85% by weight, preferably 35 to 80% by weight, and particularly 50 to 75% by weight (each based on the total dry weight of the composition) of sand.

[0096] The further additives may be any additives common in the mortar and concrete industries. In particular, the further additives may be selected from plasticizers, superplasticizers, shrinkage reducing agents, air-entraining agents, deaerators, stabilizers, viscosity modifiers, thickeners, water reducing agents, setting retarders, water resistance agents, fibers, foaming agents, defoaming agents, redispersible polymer powders, dust suppressants, chromate reducing agents, pigments, biocides, corrosion inhibitors, and steel passivators.

[0097] According to an embodiment, the construction material of the present invention, in particular, concrete or mortar, contains at least one superplasticizer selected from the group consisting of lignosulfonate, sulfonated vinyl copolymer, polynaphthalene sulfonate, sulfonated melamine formaldehyde condensate, polyethylene oxide phosphonate, polycarboxylate ether (PCE), or mixtures thereof. Preferably, the construction material of the present invention, in particular, concrete or mortar, contains PCE. Such PCE is particularly suitable for enabling good workability of the water-solidifying composition even at low water contents.

[0098] According to an embodiment, the construction material of the present invention, in particular, concrete or mortar, contains at least one thickener selected from the group consisting of starch, pectin, amylopectin, modified starch, cellulose, modified cellulose, such as carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, methylhydroxyethyl cellulose, casein, xanthan gum, diutan gum, welan gum, galactomannan, such as guar gum, tara gum, locust bean gum, velvet bean gum or cassia gum, alginate, tragacanth gum, dextran, polydextrose, layered silicates, such as sepiolite, bentonite or vermiculite, and mixtures thereof.

[0099] According to an embodiment, the construction material of the present invention, in particular, concrete or mortar, contains at least one redispersible polymer powder. The term redispersible polymer powder refers to a powder that contains a polymer and forms a stable dispersion after introduction into water. The redispersible polymer powder typically includes not only the polymer but also, for example, protective colloids, emulsifiers, and mixtures thereof with support materials. The redispersible polymer powder can be produced, for example, by spray drying a polymer dispersion as described in European Patent No. 1042391. Suitable redispersible powders are available, for example, under the trade name Vinnapas from Wacker Chemie AG. The use of redispersible powders of synthetic organic polymers is preferred for the purposes of the present invention. Synthetic organic polymers can be produced by radical polymerization of monomers selected from the group consisting of ethylene, propylene, butylene, isoprene, butadiene, styrene, acrylonitrile, acrylic acid, methacrylic acid, esters of acrylic acid, esters of methacrylic acid, vinyl esters, and vinyl chloride in the context of the present invention. The synthetic polymer is preferably a copolymer synthesized from two or more, preferably two different monomers. The copolymer sequence can be alternating, block, or random. Preferred synthetic organic polymers are copolymers of vinyl acetate and ethylene, vinyl acetate and ethylene and methyl methacrylate, vinyl acetate and ethylene and vinyl ester, vinyl acetate and ethylene and acrylic acid ester, vinyl chloride and ethylene and vinyl laurate, vinyl acetate and vinyl versatate, acrylic acid ester and styrene, acrylic acid ester and styrene and butadiene, acrylic acid ester and acrylonitrile, styrene and butadiene, acrylic acid and styrene, methacrylic acid and styrene, styrene and acrylic acid ester, styrene and methacrylic acid ester. The glass transition temperature (Tg) of the synthetic organic polymer can vary over a wide range. The Tg of a suitable synthetic organic polymer can be, for example, -50°C to +60°C, preferably -45°C to +35°C, more preferably -25°C to +15°C.

[0100] The construction materials of the present invention, in particular, concrete or mortar, may also contain liquid additives. Such liquid additives can be mixed with the dry composition of the construction materials to result in a construction material having a powdery or pasty consistency. The liquid additive can be, for example, an aqueous solution or dispersion of a plasticizer or a superplasticizer. When water or an aqueous additive is added to a construction material intended to be a dry mix, the amount of water should be limited to 0.5% by weight or less based on the total dry weight of the construction material.

[0101] According to a preferred embodiment, the construction materials, in particular, concrete or mortar formulations, (in each case, based on the total dry weight of the construction materials) a) 5 to 95% by weight, preferably 5 to 60% by weight of a high-silica aluminosilicate-based binder (the binder is a1) at least one high-silica aluminosilicate, preferably vitreous pumice, vitreous volcanic ash, zeolitized tuff, burnt oil shale, a2) including at least one accelerator for the reaction of at least one high-silica aluminosilicate with water, the accelerator being selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or their salts, amino acids or their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), and etidronic acid, mineral salts, or mixtures thereof), b) 5 to 95% by weight, preferably 30 to 90% by weight of at least one aggregate, c) 0 to 90% by weight, preferably 5 to 30% by weight of at least one binder (the binder is selected from Portland cement, calcium aluminate cement, calcium sulfoaluminate cement, gypsum, hydraulic lime, air-hardening lime, calcined magnesia, caustic magnesia, blast furnace slag fine powder, basic oxygen slag, limestone, clay minerals, in particular, calcined clay, Class C fly ash), d) 0 to 10% by weight of further additives, and e) An amount of water that optionally realizes a mass ratio of water to dry composition of 0.1 to 0.6, preferably 0.2 to 0.5, particularly 0.2 to 0.35 is included.

[0102] All the features described as preferred above also apply in this case.

[0103] According to another embodiment, the present invention also a) A binder based on 5 to 95% by weight, preferably 5 to 60% by weight of a high-silica aluminosilicate (the binder a1) contains at least one high-silica aluminosilicate, preferably vitreous pumice, vitreous volcanic ash, zeolitized tuff, burnt oil shale, a2) at least one accelerator for the reaction of at least one high-silica aluminosilicate with water as described above or consists of these), b) 5 to 95% by weight, preferably 30 to 90% by weight of at least one aggregate, c) Optionally 20 to 80% by weight, preferably 40 to 80% by weight of at least one binder selected from the group consisting of Portland cement, calcium aluminate cement, calcium sulfoaluminate cement, gypsum or mixtures thereof, d) 0 to 10% by weight of further additives, and e) An amount of water that optionally realizes a mass ratio of water to dry composition of 0.1 to 0.6, preferably 0.2 to 0.5, particularly 0.2 to 0.35 is included or consists of these (in any case, based on the total dry weight of the construction material), relating to a construction material, preferably a concrete or mortar composition.

[0104] The construction materials of the present invention can be produced by mixing components, in particular, a binder based on highly siliceous aluminosilicate, aggregates, and optionally present cobinders, further additives, and water by conventional means. Suitable mixers are, for example, horizontal single-shaft mixers, twin-shaft paddle mixers, vertical shaft mixers, ribbon blenders, orbital mixers, change can mixers, rotating vessels, vertical stirring chambers or pneumatic stirring operations. The mixing can be continuous or batchwise.

[0105] According to a preferred embodiment, the construction material of the present invention is a one-component mixture. This means that all the individual components are mixed. A one-component composition is particularly easy to handle and eliminates the risk of misappropriation or incorrect dosing of the individual components by the user.

[0106] However, it is in principle possible to provide the construction materials of the present invention as two-component or even multi-component compositions. Two-component or multi-component compositions, for example, make it possible to adjust the construction materials for specific applications.

[0107] Typically, the dry construction materials of the present invention are mixed with water immediately prior to their application. This is because upon contact with water, the construction materials of the present invention begin to harden. Thus, it is particularly preferred to first produce dry construction materials such as dry mortar or dry concrete as described above, and then mix this dry construction material with water at or near the place of application.

[0108] The methods and devices for mixing dry construction materials with water are not particularly limited and are known to those skilled in the art. The mixing can be continuous, semi-continuous or batchwise. Continuous mixing realizes the advantage of high material processing capacity.

[0109] The construction materials of the present invention, in particular, concrete or mortar can thus be dry construction materials or wet construction materials.

[0110] According to an embodiment, the dry construction material is, in particular, dry mortar, ready-mix mortar, or dry concrete. According to a further embodiment, the dry composition as described above is prepared on-site, for example, by mixing at least one of the components with the other components of the dry composition and / or by mixing two or more components of a multi-component material.

[0111] The construction material of the present invention can be a cementitious tile adhesive, a grouting material, a self-leveling underlayment, a self-leveling overlayment, a primer, a repair mortar, a masonry joint mortar or concrete, a screed, a wall leveling material for indoor or outdoor use, a non-shrinking grout, a joint mortar, a waterproof mortar, or an anchoring mortar. The cementitious tile adhesive particularly complies with the standard EN12004-1. The grouting material particularly complies with the standard EN13888. The self-leveling underlayment or the self-leveling overlayment particularly complies with the standard EN13813. The primer particularly complies with the standard EN998-1. The repair mortar particularly complies with the standard EN1504-3. The masonry mortar or concrete particularly complies with the standards EN998-2 and EN206-1. The screed particularly complies with the standard EN13813. The non-shrinking grout particularly complies with the standard EN1504-6. The joint mortar particularly complies with the standard EN998-2. The waterproof mortar particularly complies with the standard EN1504-2. The anchoring mortar particularly complies with the standard EN1504-6.

[0112] By mixing with water, the construction material of the present invention, in particular, concrete or mortar begins to solidify and harden. The solidification and hardening of the construction material proceed with time, and physical properties, such as compressive strength, are generated thereby.

[0113] In a last aspect, the present invention relates to a hardened body obtained by hardening a concrete or mortar composition as described above, wherein the high-silica aluminosilicate-based binder or construction material is mixed with water in an amount to achieve a water:dry composition mass ratio of 0.1 to 0.6, preferably 0.2 to 0.5, particularly 0.2 to 0.35.

[0114] Any embodiment described above as preferred, particularly in relation to high silica aluminosilicates and at least one accelerator, should also be understood to apply to this aspect. In particular, preferably, the high silica aluminosilicate has a SiO2 content of 40 wt% or more, preferably 50 wt% or more, based on the total dry weight of each high silica aluminosilicate and as determined by XRF as described in EN196-2:2013.

[0115] The conditions for curing are not particularly limited and are known to those skilled in the art. In particular, curing can be carried out at a temperature of 5°C to 200°C and a pressure of 1 atm to 12 atm. Curing is possible under normal atmosphere, or in a water-saturated atmosphere, or in any other atmosphere. Curing is preferably carried out at a pressure of 1 atm and at 5°C to 35°C.

Examples

[0116] The following raw materials were used for the examples. Triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanol diisopropanolamine (EDIPA), NaCl, dextrin (from potato starch), sucrose, and sodium gluconate (Na gluconate) were purchased from Sigma Aldrich and used as received. Portland clinker, limestone, and gypsum were in accordance with the standard EN197-1:2011, where the Portland clinker was ground to approximately 3500 cm 2 / g of Blaine surface without addition. The vitreous pozzolan was used as a high silica aluminosilicate. The high silica aluminosilicates (aluminosilicates 1-3) used had a SiO2 content of 45-57 wt%, an Al2O3 content of 16-21 wt%, a CaO content of 6-16 wt%, and an Fe2O3 content of 4-9 wt% (determined by XRF as described in EN196-2:2013).

[0117] For the preparation of the following examples, a 450 g mixture of each of Portland clinker, limestone, pozzolan, and gypsum (as shown in the table below) was mixed with 225 g of mixing water to yield a water / binder ratio of 0.5. Each admixture as shown in the table below was added together with the mixing water (ppm relative to the total dry weight of the binder). Mixing was carried out on a mortar mixer according to standard EN196. Using prisms (40×40×160 mm), after 28 days of curing, tests were carried out to determine the compressive strength according to EN196-1:2016 and EN12190:1998. The first 24 hours of curing was carried out at 20 °C and at least 95% relative humidity, and the remainder of the curing was carried out at 20 °C in water saturated with Ca(OH)2.

[0118]

Table 1

[0119]

Table 2

[0120] From the results in Table 2 above, it can be seen that mixtures of TEA / TIPA, TIPA / DEIPA / NaCl / dextrin, TEA / TIPA / NaCl / dextrin, and TEA / TIPA / NaCl / dextrin / sucrose result in a higher increase in compressive strength compared to cements containing the same amount of limestone when used with cements containing high silica aluminosilicate.

[0121]

Table 3

[0122]

Table 4

[0123] From the results in Table 3 above, it can be seen that mixtures of TEA / TIPA, TEA / TIPA / sodium gluconate, TIPA / DEIPA, and TEA / TIPA / dextrin, and TIPA / dextrin result in a higher increase in compressive strength when used with cement containing high silica aluminosilicate compared to cement containing the same amount of limestone.

[0124]

Table 5

[0125]

Table 6

[0126]

Table 7

[0127]

Table 8

[0128] From the results in Table 4 above, it can be seen that any of these mixtures of TEA, TIPA, DEIPA, and EDIPA, and dextrin result in a higher increase in compressive strength when used with cement compared to cement not containing high silica aluminosilicate, where some of the cement is replaced with high silica aluminosilicate.

[0129] The above examples show that the promotion of the reaction of high silica aluminosilicate with water is possible by the use of alkanolamines, sugars, sugar acids, mineral salts, or mixtures thereof.

Claims

1. Use of an accelerator for the reaction of high silica aluminosilicate with water, wherein the accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids and their salts, amino acids and their salts, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof.

2. The high silica aluminosilicate is such that, relative to the total dry weight of each high silica aluminosilicate, it contains 40% by weight or more, preferably 50% by weight or more, of SiO2, as determined by XRF as described in EN196-2:2013. ２ The use according to claim 1, characterized by having the content of [the specified amount].

3. The accelerators include triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanoldiisopropanolamine (EDIPA), fructose, mannose, maltose, glucose, galactose, dextrin, fermentation residue, molasses, gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, musylic acid, saccharic acid and their sodium, potassium or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, salicylic acid and their sodium, potassium or calcium salts. The use according to claim 1, characterized in that it is selected from the group consisting of salts, glycine, glutamic acid, aspartic acid, polyaspartic acid, tetrasodium iminodisuccinate (IDS), diethylenetriaminepentaacetic acid (DTMA), nitrilotriacetic acid (NTA), sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, sodium thiocyanate, sodium chloride, calcium nitrite, calcium nitrate, calcium chloride, magnesium chloride, calcium sulfate, aluminum sulfate, aluminum chloride, sodium sulfate, thiosulfates, particularly sodium thiosulfate, thiocyanates, and sulfides, particularly potassium sulfide.

4. The use according to claim 1, characterized in that the accelerator is a mixture of two alkanolamines or one alkanolamine with at least one further accelerator different from an alkanolamine.

5. The alkanolamine is selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanoldiisopropanolamine (EDIPA), and methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and the at least one further accelerator is fructose, mannose, maltose, glucose, galactose, dextrin, fermentation residue, molasses, gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, musylic acid, saccharic acid and their sodium, potassium or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and The use according to claim 4, characterized in that it is one further accelerator selected from the group consisting of dipic acid, salicylic acid and their sodium, potassium or calcium salts, glycine, glutamic acid, aspartic acid, polyaspartic acid, tetrasodium iminodisuccinate (IDS), diethylenetriaminepentaacetic acid (DTMA), nitrilotriacetic acid (NTA), sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, sodium thiocyanate, sodium chloride, calcium nitrite, calcium nitrate, calcium chloride, magnesium chloride, calcium sulfate, aluminum sulfate, sodium sulfate, aluminum chloride, thiosulfates, particularly sodium thiosulfate, thiocyanates, and sulfides, particularly potassium sulfide.

6. The use according to claim 4, characterized in that the alkanolamine is selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanoldiisopropanolamine (EDIPA), and methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and that there are two further accelerators, the first further accelerator being selected from sugars, particularly fructose, mannose, maltose, glucose, or galactose, and the second further accelerator being selected from the group consisting of inorganic salts and reducing agents, preferably from the group consisting of sodium thiocyanate, sodium chloride, calcium chloride, magnesium chloride, calcium nitrite, calcium nitrate, aluminum sulfate, aluminum chloride, sodium sulfate, calcium sulfate, sodium thiosulfate, and potassium sulfide.

7. The alkanolamine is selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanoldiisopropanolamine (EDIPA), and methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and there are two further promoters, the first of which is selected from sugars, particularly fructose, mannose, maltose, glucose, or galactose, and the second The use according to claim 4, characterized in that the further accelerator of 2 is selected from the group consisting of sugar acids, carboxylic acids, and sulfamic acids, particularly gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, iduronic acid, musylic acid, saccharic acid, salicylic acid and their sodium, potassium or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and their sodium, potassium or calcium salts.

8. The alkanolamine is selected from the group consisting of triethanolamine (TEA), triisopropanolamine (TIPA), diethanolisopropanolamine (DEIPA), ethanoldiisopropanolamine (EDIPA), and methyldiethanolamine (MDEA), particularly TIPA and / or DEIPA, and there are three further promoters, the first further promoter being selected from sugars, preferably fructose, mannose, maltose, glucose, or galactose, and the second further promoter being sugar acids, carboxylic acids, and sulfamic acids, preferably gluconic acid, ascorbic acid, neuraminic acid, glucuronic acid, galacturonic acid, etc. The use according to claim 4, characterized in that a third further accelerator is selected from the group consisting of ronic acid, musylic acid, saccharic acid and their sodium, potassium or calcium salts, formic acid, glycolic acid, citric acid, lactic acid, malic acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, salicylic acid and their sodium, potassium or calcium salts, and a third further accelerator is selected from the group consisting of inorganic salts and reducing agents, preferably from sodium thiocyanate, sodium chloride, calcium chloride, magnesium chloride, calcium nitrite, calcium nitrate, aluminum sulfate, aluminum chloride, sodium sulfate, calcium sulfate, sodium thiosulfate, and potassium sulfide.

9. The use according to at least one of claims 1 to 8, characterized in that the accelerator is added in a total amount of 0.005 to 25% by weight relative to the total dry weight of the high silica aluminosilicate.

10. The use according to at least one of claims 1 to 8, characterized in that the reaction of the high silica aluminosilicate with water is promoted in the presence of Portland cement and optionally limestone and / or gypsum.

11. A binder based on high silica aluminosilicate, preferably for use as a binder in concrete or mortar, wherein the binder is (a) at least one high silica aluminosilicate, preferably glassy pumice, glassy volcanic ash, zeolitized tuff, burnt oil shale, (b) At least one accelerator for the reaction of the at least one high silica aluminosilicate with water (the accelerator is selected from the group consisting of alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or salts thereof, amino acids or salts thereof, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof), (c) At least one type of cobinder, (d) Optionally, additional additives different from (b), A binder based on high silica aluminosilicate, containing or comprising these.

12. A binder based on high silica aluminosilicate according to claim 11, characterized in that the accelerator is selected from the accelerators described in claim 3, or the accelerator is a mixture described in any one of claims 4 to 8.

13. Construction materials, preferably concrete or mortar compositions, (a) 5 to 95% by weight, preferably 5 to 60% by weight, of a binder based on high silica aluminosilicate (the binder is, (a1) At least one high silica aluminosilicate, preferably glassy pumice, glassy volcanic ash, zeolite tuff, burnt oil shale, (a2) At least one accelerator for the reaction of at least one high silica aluminosilicate with water, The accelerator comprises or consists of the following, wherein the accelerator is preferably selected from the group consisting of the accelerator described in claim 4 or a mixture of accelerators, and includes alkanolamines, reducing agents, sugars, sugar acids, carboxylic acids or salts thereof, amino acids or salts thereof, sulfamic acid, glyoxal, acetylacetone, pyrocatechol, nitrilotri(methylphosphonic acid), etidronic acid, mineral salts, or mixtures thereof. (b) 5 to 95% by weight, preferably 30 to 90% by weight, at least one type of aggregate, (c) 0 to 90% by weight, preferably 5 to 30% by weight, of at least one cobinder (unlike binder (a) which is based on high silica aluminosilicate, the cobinder is selected from the group consisting of cement, gypsum, lime, calcined magnesia, caustic magnesia, alumina, limestone, clay minerals, calcined clay, slag, and Class C fly ash). (d) 0 to 10% by weight of further additives, (e) an amount of water that achieves a water:dry component mass ratio of 0.1 to 0.6, preferably 0.2 to 0.5, and particularly 0.2 to 0.35, optionally. Construction materials comprising or consisting of (in either case, relative to the total dry weight of the construction materials).

14. The construction material according to claim 13, wherein the construction material comprises 5 to 90% by weight, preferably 5 to 30% by weight, of at least one cobinder, and the cobinder is selected from Portland cement, calcium aluminate cement, calcium sulfoaluminate cement, gypsum, hydraulic lime, air-hardening lime, calcined magnesia, caustic magnesia, blast furnace slag powder, basic oxygen slag, limestone, clay minerals, particularly calcined clay, and Class C fly ash.

15. A binder based on high silica aluminosilicate as described in claim 11, or a construction material as described in any one of claims 13 to 14, characterized in that a cobinder is present, and the weight ratio of high silica aluminosilicate, particularly glassy pumice, glassy volcanic ash, zeolitized tuff, and burnt oil shale to the cobinder is 1:19 to 19:1, preferably 1:9 to 15:1, more preferably 1:6 to 12:1, even more preferably 1:5 to 9:1, highly preferably 1:3 to 6:1, and particularly 1:1 to 5:

1.

16. A cured body obtained by curing a binder based on high silica aluminosilicate as described in claim 11 or a construction material as described in claim 13 or 14, wherein the binder or construction material is mixed with water in an amount that achieves a water:dry powder mass ratio of 0.1 to 0.6, preferably 0.2 to 0.5, and particularly 0.2 to 0.35.