• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    USE OF AT LEAST ONE ORGANIC COMPOUND CONTAINING NITROGEN AND/OR A SALT OF THE SAME IN COMBINATION WITH AT LEAST ONE AROMATIC CARBOXYLIC ACID AND/OR A SALT OF THE SAME AND ALKALINE ACTIVATION ALUMINOSILICATE BINDER. nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof to improve freeze-thaw stability of an alkaline activating aluminosilicate binder, and a nitrogen aluminosilicate binder preferential alkaline activation comprising sodium benzoate and (epsilon)-caprolactam as freeze-thaw stabilizers.
    公开号:BR112015005433B1
    申请号:R112015005433-1
    申请日:2013-09-26
    公开日:2021-05-11
    发明作者:Samuele Beraldo；Nicola Montagner；Alessandro Dal Bo
    申请人:Construction Research & Technology Gmbh；
    IPC主号:
    专利说明:

    [0001] The present invention relates to the use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof to improve the freeze-thaw stability of an alkaline activating aluminosilicate binder, as well as a stabilized alkaline activating aluminosilicate binder.
    [0002] Similar systems are described in WO 10/130582. In particular, it is stated that certain organic additives (especially amines) considerably reduce the tendency of the alkaline activated aluminosilicate binder to shrink.
    [0003] The stability of construction products to external influences is generally of great importance. The present invention will mainly focus on the aspect of freeze-thaw stability as this is an essential feature of construction products.
    [0004] Freeze-thaw cycles refer to climatic changes in temperatures around the freezing point of water. Particularly in mineral binders such as concrete, freeze-thaw cycles are a mechanism of deterioration. These building materials exhibit a porous capillary structure and are not waterproof. If such a water-impregnated structure is subjected to a temperature below 0 °C, the water freezes inside the pores. Due to the abnormal density of water, ice now expands. This results in deterioration of the durability of the building material. Furthermore, there is a capillary pumping effect because of the expansion and contraction of the material itself through these freeze-thaw cycles which increase water absorption and thus deterioration. The number of freeze-thaw cycles to which the building material is exposed during its lifetime is thus a major influence on this deterioration process. For this reason, test methods have been generated to simulate the effects brought about by the freeze-thaw cycles of construction products (from http://de.wikipedia.org/wiki/Frost-Tau-Wechsel, retrieved October 10, 2012). These methods (eg ASTM C 679-92) provide an indication of the freeze-thaw stability and therefore the durability of the construction product itself.
    [0005] Portland cement was first mentioned in British Patent BP 5022 and has been continuously developed since then. Modern Portland Cement contains about 70% by weight of CaO + MgO, about 20% by weight of SiO2 and about 10% by weight of Al2O3 + Fe2O3. Due to its high CaO content, it hardens hydraulically. Cured Portland Cement, however, exhibits capillary pores into which water tends to migrate during hot periods and disintegrate the cured cement during periods of freezing.
    [0006] Particular wastes from metallurgical processes can be used as latent hydraulic binders as additions to Portland cement. Activation via strong alkalis such as alkali metal hydroxides or silicate solutions is also possible. They can be used as mortars or concretes when mixing with fillers (eg silica sand having an appropriate particle size) and additives. Blast furnace waste, a typical latent hydraulic binder, generally comprises from about 30 to 45% by weight of CaO, from about 4 to 17% by weight of MgO, from about 30 to 45% by weight of SiO2 and from about 5 to 15% by weight Al2O3, typically about 40% by weight CaO, about 10% by weight MgO, about 35% by weight SiO2 and about 12% by weight of Al2O3. Cured products generally have the properties of hydraulic hardening systems.
    [0007] Inorganic binder systems based on insoluble compounds reacting with water based on SiO2 in combination with Al2O3, which cures in aqueous alkaline medium, are also generally known. Such cured binder systems are also referred to as "alkaline activated aluminosilicate binders" or "geopolymers" and are described, for example, in US 4,349,386, WO 85/03699 and US 4,472,199. Such systems generally comprise from 50 to 60% by weight of SiO2, from 20 to 25% by weight of Al2O3, little or no CaO and from 15 to 30% by weight of M2O (M = Na, K).
    [0008] As a reactive oxide mixture, it is possible to use microsilica, metakaolin, residues, fly ash, activated clay or mixtures thereof. The alkaline medium for activating the binder generally comprises aqueous solutions of alkali metal carbonates, alkali metal hydroxides, alkali metal aluminates and/or soluble silicate solution.
    [0009] WO 08/012438 further describes a geopolymer cement based on F-type low CaO fly ash, blast furnace residue and aqueous alkali metal silicate having a SiO2:M2O ratio greater than 1.28, preferably greater that 1.45. In the examples calculated on the basis of anhydrous oxides, from about 45 to 50% by weight of SiO2, from about 20 to 26% by weight of Al2O3, from about 9 to 10% by weight of CaO and from about 3 to 3 to 4% by weight of K2O are present.
    [0010] Compared to cements, geopolymers can be cheaper and more stable and can have a more favorable CO2 emission balance. They generally tend to be acid resistant but less resistant to alkali. These alkaline activating aluminosilicate binders, in contrast to cement, exhibit less porous surfaces and thus freeze stability - improved thaw. However, the required properties such as applicability, strength development, dimensional stability, texture, etc. they can often be achieved only through complex formulations. For example, fillers, thickeners, accelerators, water-retaining agents, defoamers, and/or pigments are often employed. Because of these additional components, porosity often increases, which in turn decreases the freeze-thaw stability of these products.
    [0011] EP 1236702 A1 describes a mixture of building material containing silicate solution for the production of chemical resistant mortars based on a latent hydraulic binder, silicate solution and a metal salt from the group consisting of " metal hydroxide, metal oxide, metal salt containing carbon, metal salt containing sulfur, metal salt containing nitrogen, metal salt containing phosphorus, metal salt containing halogen" as a controlling agent. The constituent latent hydraulics can be granulated blast furnace waste. Alkali metal salts, in particular lithium salts, are mentioned and used as the metal salt.
    [0012] EP 1081114 A1 describes a building material mixture for producing chemical resistant mortars, wherein the building material mixture contains silicate solution powder and at least one silicate solution hardener. Furthermore, more than 10% by weight of at least one latent hydraulic binder is present, and the building material mixture comprises at least one inorganic filler.
    [0013] WO 11/064005 describes systems in which the binder cures in the form of a hybrid matrix in which a calcium silicate hydrate matrix and a geopolymer matrix are present in an appropriate ratio to one another and thus interpenetrate so that the overall matrix is both acid resistant and alkali resistant. However, the content of an organic compound containing nitrogen and/or a salt thereof and an aromatic carboxylic acid and/or a salt thereof according to the present invention is absent in these binder systems.
    [0014] According to EP 0512269 A2, for coating a large area of various substrates in the building trade, a mixture of alkali silicate solution, powdery latent hydraulic material and additive is applied, for example, by the spraying process of dense flow. Additives comprise inert additives and/or opening materials or fillers, reinforcing agents, setting accelerators and mixing regulators. The cured coating material has high mechanical, thermal and chemical stability. Alcohols, amines and/or alkanolamines are used as mixing regulators.
    [0015] The inventors themselves set the goal of substantially avoiding at least some of the disadvantages of the prior art discussed above. In particular, it is an object of the invention to substantially improve the freeze-thaw stability of an alkaline activating aluminosilicate binder.
    [0016] The objective mentioned above is achieved by the characteristics of the independent claims. The dependent claims refer to preferred embodiments.
    [0017] It has been found that the nitrogen-containing organic compound together with the aromatic carboxylic acid and/or its respective salts synergistically improve the freeze-thaw stability of alkaline-activated aluminosilicate binders.
    [0018] The present invention thus provides as a first subject the use of at least one nitrogen-containing organic compound and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof to improve the freeze-thaw stability of an alkaline activating aluminosilicate binder.
    [0019] The nitrogen-containing organic compound suitable for the purposes of the present invention is suitably selected from the group consisting of amines, imidazole, guanidine, amides, imide, lactam, aminoalcohol, amino acids, and betaine.
    [0020] Amines can be selected from primary, secondary and tertiary amines, and amine salts are selected from primary, secondary and tertiary amine salts and also quaternary ammonium salts. Amines can be aliphatic and/or aromatic amines. Tertiary amines are possible, secondary amines are preferred and primary amines are particularly preferred. In the case of amines the system must not contain any curable epoxides. Generally, the system should not contain any alkyl siliconate.
    [0021] The molecular weight of the amines used can vary within a wide range. Relatively high molecular weight compounds, such as polyvinylamines and polyethyleneimines, which can be obtained, for example, from BASF SE under the trade names of Lupamin® and Lupasol®, respectively, are suitable. Low molecular weight amines having a molecular weight less than 400 g/mol, preferably less than 300 g/mol and in particular less than 200 g/mol, are particularly suitable for the purposes of the present invention.
    [0022] Preferably, the nitrogen-containing organic compound suitable for the purposes of the present invention may be selected from the group consisting of propylamine, butylamine, pentylamine, hexylamine, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, neopentanediamine, diaminohexane, diethylenetriamine, tetraethylenepentaminae, N,N,N',N'-tetramethylethylenediamine, hexamethylenetetramine, 3-ethoxypropylamine, 2-(diethylamine)ethylamine, 3-(methylamine)propylamine, 3-(dimethylamine)propylamine, dibutylamine, 4,9-diose dodecane-1,12-diamine, bis-(2-dimethylaminoethyl) ether, polyetheramines (such as Polyetheramine D 230 from BASF SE), morpholine, N-ethyl morpholine, 2-pyrrolidone, N-methylpyrrolidone, imidazolidone, imidazolidone hemihydrate, 2-piperidone, N,N'-dimethyl piperazine, milamine, 1,3,5-triazine, 2,4-diamino-1,3,5-triazine, ε-caprolactam, urea, and betaine.
    [0023] ε-Caprolactam is the most preferred as it is in powder form and easily miscible in a mixture in powder form. Plus, it's cheap and odourless. Many amines are liquid and often less miscible or stable in a high pH aluminosilicate binder.
    [0024] Furthermore, the organic nitrogen-containing compound suitable for the purpose of the present invention can be selected from the imidazole group. The molecular weight of the imidazole used can vary over a wide range. Imidazole having a molecular weight of less than 400 g/mol, in particular less than 200 g/mol, is particularly suitable for the purpose of the present invention. Preference is given to an imidazole from the group consisting of imidazole, N-(3-aminopropyl) imidazole, 1-methylimidazole, 1-ethylimidazole, 1-propylimidazole, 1-butylimidazole, 1-ethyl-3-methylimidazole, 1-n -butyl-3-ethylimidazole, 1,3-dimethylimidazole, 1,2,3-trimethylimidazole, 1-n-butyl-3-methylimidazole, 1,3,4,5-tetramethylimidazole, 1,3,4-trimethylimidazole, 1 ,2-dimethylimidazole, 1-butyl-2,3-dimethylimidazole, 3,4-dimethylimidazole, 2-ethyl-3,4-dimethylimidazole, 3-methyl-2-ethylimidazole, 3-butyl-1-methylimidazole, 3-butyl -1-ethylimidazole, 3-butyl-1,2-dimethylimidazole, 1,3-di-n-butylimidazole, 3-butyl-1,4,5-trimethylimidazole, 3-butyl-1,4-dimethylimidazole, 3-butyl -2-methylimidazole, 1,3-dibutyl-2-methylimidazole, 3-butyl-4-methylimidazole, 3-butyl-2-ethyl-4-methylimidazole, 3-butyl-2-ethylimidazole, 1-methyl-3-octylimidazole and 1-decyl-3-methylimidazole.
    [0025] The organic nitrogen-containing compound suitable for the purpose of the present invention may also be selected from the group of guanidine. The molecular weight of the guanidine used can vary over a wide range. For the purpose of the present invention, guanidine having molecular weight less than 400 g/mol, in particular less than 150 g/mol, is particularly suitable. Preference is given to at least one guanidine from the group consisting of 1,1,3,3-tetramethylguanidine, 1,1-dimethylguanidine and 1,1-diethylguanidine.
    The organic nitrogen-containing compound suitable for the purpose of the present invention may also be an amide such as N,N-dimethylformamide, an amide such as maleimide, phthalimide, and succinimide, a lactam such as ε-caprolactam, δ-valerolactam , 2-pyrrolidone, 1-methyl-2-pyrrolidone or an amino alcohol. The molecular weight of the amino alcohol used can vary over a wide range. Amino alcohol having a molecular weight of less than 400 g/mol, in particular less than 150 g/mol, is particularly suitable for the purpose of the present invention. Preference is given to an amino alcohol from the group consisting of 3-amino-1-propanol, monoethanolamine, triethanolamine, choline, trimethylamineethylethanolamine, 1-(2-hydroxyethyl) piperazine, 2-(2-aminoethoxy) ethanol, 3-dimethylaminopropan -1-ol, 4-(2-hydroxyethyl)morpholine, butyldiethanolamine, butylethanolamine, dimethylamineethoxyethanol, N,N-dimethylethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine and N-(2-hydroxyethyl)-2-pyrrolidone.
    [0027] Furthermore, the salt of the nitrogen-containing organic compound can be a hydrogen halide salt or a quaternary ammonium salt. A preferred hydrogen halide would be hydrochloric acid. The quaternization of the nitrogen-containing organic compound can be carried out, for example, by reacting the nitrogen-containing organic compound with chloromethane or dimethyl sulphate.
    [0028] Imidazolium salts, guanidine salts and quaternary ammonium salts are highly suitable for the purpose of the present invention. Salts of this type having melting points below 100°C are also referred to as ionic liquids. Molecular weight can be varied over a wide range. Ionic liquids having a molecular weight of less than 400 g/mol, in particular less than 200 g/mol, are particularly suitable for the purpose of the present invention.
    [0029] For the purpose of the present invention, ionic liquids are preferably salts having at least one cation selected from the group consisting of choline, tris-2-(hydroxyethyl) methylammonia, methyl-tri-n-butylammonia, tetramethylammonia, tetrabutylammonium , 1-methylimidazolium, 1-ethylimidazolium, 1-propylimidazolium, 1-butylimidazolium, 2-ethylpyridinium, 1-ethyl-3-methylimidazolium, 1-n-butyl-3-ethylimidazolium, 1,2-dimethylpyridinium, 1-methyl-2 - ethylpyridinium, 1-methyl-2-ethyl-6-methylpyridinium, N-methylpyridinium, 1-butyl-2-methylpyridinium, 1-butyl-2-ethylpyridinium, 1-butyl-2-ethyl-6-methylpyridinium, N-butylpyridinium , 1-butyl-4-methylpyridinium, 1,3-dimethylimidazolium, 1,2,3-trimethylimidazolium, 1-n-butyl-3-methylimidazolium, 1,3,4,5-tetramethylimidazolium, 1,3,4-trimethylimidazolium , 1,2-dimethylimidazolium, 1-butyl-2,3-dimethylimidazolium, 3,4-dimethylimidazolium, 2-ethyl-3,4-dimethylimidazolium, 3-methyl-2-ethylimidazolium, 3-butyl-1-methylimidazolium, 3 -butyl-1-ethylimidazolium, 3-butyl-1,2-dimethylimidazolium , 1,3-di-n-butylimidazolium, 3-butyl-1,4,5-trimethylimidazolium, 3-butyl-1,4-dimethylimidazolium, 3-butyl-2-methylimidazolium, 1,3-dibutyl-2-methylimidazolium , 3-butyl-4-methylimidazolium, 3-butyl-2-ethyl-4-methylimidazolium, 3-butyl-2-ethylimidazolium, 1-methyl-3-octylimidazolium, 1-decyl-3-methylimidazolium and guanidinium and also at least an anion selected from the group consisting of chloride, bromide, iodide, acetate, methylsulfate, methanesulfonate, tosylate, sulfate, hydrogensulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, dialkylphosphate, and bis(trifluoromethanesulfonyl)imide.
    [0030] The aromatic carboxylic acid which is suitable for the purpose of the present invention may be selected from the group consisting of benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, and toluic acid.
    [0031] Furthermore, the aromatic carboxylic acid salt is suitably selected from the group consisting of alkali metal salts, alkaline earth metal salts, aluminum salts, first-tier transition metal salts, and mixtures thereof. The term "first row transition metal" is intended to denote transition metals from Sc to Zn. Sodium benzoate is particularly preferred because it is relatively inexpensive, readily available and performs satisfactorily.
    [0032] The alkaline activating aluminosilicate binder comprises at least one latent hydraulic and/or pozzolanic binder and at least one salt selected from alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, aluminates alkali metals, and mixtures thereof.
    [0033] The latent hydraulic binder is, for example, selected from waste, in particular, blast furnace waste, granulated blast furnace waste, surface granulated blast furnace waste, electrothermal phosphorus waste, iron waste and mixtures of the same. Waste can be either industrial waste, that is, waste products from industrial processes, or synthetically produced waste. The latter is advantageous as industrial waste is not always available in constant quantity and quality.
    [0034] For the purpose of the present invention a "latent hydraulic binder" is preferably a binder in which the molar ratio of (CaO + MgO):SiO2 is in the range from 0.8 to 2.5 and particularly preferably in the range from 1.0 to 2.0.
    [0035] Blast furnace waste is a waste product of the blast furnace process. Granulated blast furnace waste is sometimes called waste sand. Surface granulated blast furnace waste varies in fineness and particle size distribution depending on the origin and form of treatment, with fineness having an influence on reactivity. As a measure of fineness, use is made of the Blaine Value which is typically in the order of 200 to 1000, preferably from 300 to 500 m2kg-1. The finer the blast furnace residue is ground, the greater the reactivity. The typical composition of blast furnace waste was mentioned above.
    [0036] Electrothermal phosphorus waste is a waste product of electrothermal phosphorus production. It is less reactive than blast furnace waste and contains about 45 to 50% by weight of CaO, about 0.5% to 3% by weight of MgO, about 38 to 43% by weight of SiO2, about 2 to 5% by weight of Al2O3 and about 0.2 to 3% by weight of Fe2O3 and also fluoride and phosphate. Iron residue is a waste product from various iron production processes and has a greatly variable composition (see Caijun Shi, Pavel V. Krivenko, Della Roy, Alkali-Activated Cements and Concretes, Taylor & Francis, London & New York, 2006, pp. 42-51).
    [0037] The pozzolanic binder is, for example, selected from amorphous silica, preferably precipitated silica, silica and fumed microsilica, fine glass powder, fly ash, for example brown coal fly ash and coal fly ash, metakaolin, pozzolan natural, such as limestone tuff, volcanic ash and pumice tuff, synthetic and natural zeolites and mixtures thereof. An overview of pozzolanic binders that are suitable for the purpose of the present invention can also be found in Caijun Shi, Pavel V. Krivenko, Della Roy, pp. 51-63.
    [0038] Amorphous silica is preferably an X-ray amorphous silica, that is, a silica that does not demonstrate crystallinity in the powder diffraction pattern. For the purpose of this invention, glass powder should also be considered as amorphous silica.
    [0039] The amorphous silica used according to the invention suitably has an SiO2 content of at least 80% by weight, preferably at least 90% by weight. Precipitated silica is industrially obtained from silicate solution through precipitation processes. Depending on the production process, precipitated silica is also referred to as silica gel. Fumed silica is produced by the reaction of chlorosilanes such as silicon tetrachloride in an oxy-hydrogen flame. Fumed silica is an amorphous SiO2 powder having a particle diameter of 5 to 50 nm and a specific surface area of 50 to 600 m2 g-1.
    [0040] Microsilica is a by-product of silicon or silicon iron manufacture and also consists largely of amorphous SiO2 powder. Particles having diameters on the order of about 0.1 µm. The specific surface area is on the order of 15 to 30 m2 g-1. Commercial silica sand, on the other hand, is crystalline and has relatively large particles and a relatively low specific surface area. It is used according to the invention as an inert aggregate.
    [0041] Fly ash is formed, among other forms, in the combustion of coal in power stations. Class C fly ash contains, according to WO 08/012438, about 10% by weight of CaO, while class F fly ash contains less than 8% by weight, preferably less than 4% by weight and typically about 2% by weight of CaO.
    [0042] Metakaolin is formed in the dehydration of kaolin. Since kaolin gives off physically bound water from 100 to 200°C, dehydroxylation with lattice breakage and formation of metakaolin (Al2Si2O7) occurs from 500 to 800°C. Pure metakaolin therefore contains about 54% by weight of SiO2 and about 46% by weight of Al2O3.
    [0043] The salt mentioned above, which is selected from alkali metal oxides, alkali metal hydroxides, alkali metal carbonates, alkali metal silicates, and alkali metal aluminates, acts as an alkaline activator for the pozzolanic binder and/or hydraulic of latent. Alkali metal hydroxides and alkali metal silicates are preferred.
    [0044] The alkali metal silicate is suitably selected from compounds having the empirical formula m SiO2 . n M2O, where M is Li, Na, K or NH4, or a mixture thereof, preferably Na or K. (Ammonia is to be understood here although it is not an alkali metal). The molar ratio of m:n is from 0.5 to 3.6, preferably from 0.6 to 3.0 and in particular from 0.7 to 2.0.
    [0045] Furthermore, the alkali metal silicate is suitably a silicate solution, preferably a liquid silicate solution and in particular a sodium or potassium silicate solution.
    [0046] The ratio of m:n (also referred to as modulus) as indicated above, preferably, should not be exceeded otherwise a complete reaction of the components can no longer be expected. It is also possible to use lower modules, for example around 0.2. Silicate solutions having higher modulus must be brought into the modulus range according to the invention by means of a suitable aqueous alkali metal hydroxide before use.
    [0047] Potassium silicate solution in the proper modulus range is commercially available primarily as an aqueous solution as they are highly hygroscopic; potassium sodium silicate solutions in the proper modulus range are also commercially available as solids. The solid content of the sodium silicate solutions is generally from 20% by weight to 60% by weight, preferably from 30 to 50% by weight.
    [0048] Silicate solutions can be prepared industrially by melting silica sand with corresponding alkali metal carbonates. However, they can be obtained without difficulty from mixtures of reactive silica with the corresponding aqueous alkali metal hydroxides. It is therefore possible, according to the invention, to replace at least part of the alkali metal silicate by a mixture of reactive silica and the corresponding alkali metal hydroxide.
    [0049] In addition, a small amount of hydraulic binder may be present. The hydraulic binder is suitably selected from cements, in particular Portland cement, aluminate cement, and also mixtures thereof.
    [0050] As indicated by this, Portland Cement contains around 70% by weight of CaO + MgO, around 20% by weight of SiO2 and around 10% by weight of Al2O3 + Fe2O3. Aluminate cement (high alumina cement) contains about 20 to 40% by weight of CaO, up to about 5% by weight of SiO2, about 40 to 80% by weight of Al2O3 and up to about 20% by weight of Fe2O3. These types of cement are known in the state of the art.
    [0051] The ratio of the organic compound containing nitrogen and/or salt thereof to the aromatic carboxylic acid and/or salt thereof is suitably comprised within the range of 1:1 to 1:10, preferably, from 1:5 to 1 :10.
    [0052] A preferred alkaline activating aluminosilicate binder, which is suitable for the purpose of the present invention, comprises 5 to 95, preferably, 20 to 80% by weight of the latent pozzolanic and/or hydraulic binder, 5 to 50, preferably 10 to 40% by weight of the alkali metal silicate, 0.01 to 30, preferably 0.1 to 10 and in particular 0.1 to 3% by weight of the organic compound containing nitrogen and/or a salt of the same, 0.01 to 30, preferably 0.1 to 10, and in particular 0.5 to 5% by weight of the aromatic carboxylic acid and/or a salt thereof, and 0 to 20, preferably 0 to 10 and in particular 0 to 5% by weight of the hydraulic binder. Furthermore, from 0 to 90%, preferably from 30 to 70% by weight of inert fillers and/or from 0 to 15% by weight of additives may be present. The above proportions are to be selected in a way that they add up to 100% in weight.
    [0053] Possible inert fillers are, for example, gravel, sand and fine powders, for example those based on silica, limestone, barite or clay, in particular, silica sand. Lightweight fillers such as perlite, kieselguhr (diatomaceous earth), expanded mica (vermiculite) and foam sand can also be used.
    [0054] Possible additives are, for example, plasticizers, defoamers, water-retaining agents, dispersants, pigments, fibers, redispersible powders, wetting agents, impermeable additives, retarders, cure accelerators, complexing agents, and rheology modifiers.
    [0055] The amount of water required for adjustment, for the purpose of the invention, is not counted as a constituent of the binder. Generally from 10 to 50%, preferably from about 25 to about 35% by weight of water, based on 100% alkaline activating aluminosilicate binder, is required for adjustment.
    [0056] The alkaline activating aluminosilicate binder can be comprised in formulations of construction materials and/or construction products such as on-site concrete, finished concrete parts, concrete goods, concrete blocks and also on-site concrete, concrete spray, ready-mixed concrete, construction adhesives and composite thermal insulation system adhesives, concrete repair systems, one-component or two-component sealing paste, strips, scratch fillers and self-levelling compositions, tile adhesives, plasters and plasters, adhesives and sealants, coating systems, in particular for tunnels, wastewater channels, spray protection and condensed lines, dry mortars, joint grouts, drainage mortars and/or repair mortars.
    [0057] In addition, the present invention provides as a further subject an alkaline activating aluminosilicate binder comprising blast furnace waste, granulated blast furnace waste and/or surface granulated blast furnace waste as a latent hydraulic binder, microsilica, metakaolin and/or fly ash as a pozzolanic binder, sodium silicate solution and/or potassium silicate solution as an alkaline activator, and ε-caprolactam and sodium benzoate as a freeze-thaw stabilizer.
    [0058] The invention will now be illustrated by means of the following examples. EXAMPLES 1-12
    [0059] 10.0 g of surface granulated blast furnace waste (Blaine value around 3860 cm2/g) and 20.0 g of microsilica (Sublimated Silica, BET value around 11.6 m2/g ) were homogenized and mixed with 20.0 g of liquid aqueous potassium silicate solution (modules 1.0, solids contents 52%). The freeze-thaw stabilizer according to Table 1, if any, and 60 g of quartz sand were added and further mixed. Prismatic test specimens (4x2x16 cm) were molded and, after 24 h, were cured for 13 days at 60% relative humidity and 20 C. The specimens were subjected to 10, 15, 20 and 30 freeze-thaw cycles. The cycles were performed according to ASTM C 679-92, ie, 16 h at -19 °C and 8 h at +23 °C while the specimens were in a bath of 4% by weight of aqueous CaCl 2 solution.
    [0060]The respective weight losses in percent are listed in Table 1 below this. It can be seen that, starting from a formulation without freeze-thaw stabilizer, the addition of an organic compound containing nitrogen or sodium benzoate separately provides only a small improvement while the addition of an organic compound containing nitrogen in combination with sodium benzoate provides a significant increase that is often greater than the sum of the improvements from the individual additions. EXAMPLES 13-18
    The procedure of Examples 1-12 was followed with varying concentrations of sodium benzoate and ε-caprolactam. The results are shown in Table 2 below this. It can be seen that, starting with a formulation without freeze-thaw stabilizer, the addition of 1% or even 2% by weight of sodium benzoate or ε-caprolactam separately provides a much smaller improvement in freeze-thaw stability than does addition of 1% sodium benzoate in combination with 1% ε-caprolactam. This discovery unequivocally proves the existence of a synergistic effect.

    权利要求:
    Claims (12)
    [0001]
    1. USE OF AT LEAST ONE NITROGEN CONTAINING ORGANIC COMPOUND and/or a salt thereof in combination with at least one aromatic carboxylic acid and/or a salt thereof to improve the freeze-thaw stability of an alkaline activating aluminosilicate binder , characterized in that the aromatic carboxylic acid is selected from the group consisting of benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid and toluic acid, and the nitrogen-containing organic compound is selected from the group consisting of amines, lactams, amino alcohols and betaines.
    [0002]
    2. USE according to claim 1, characterized in that the salt of the nitrogen-containing organic compound is a hydrogen halide salt or a quaternary ammonium salt.
    [0003]
    Use according to any one of claims 1 to 2, characterized in that the aromatic carboxylic acid salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, aluminum salts, aluminum salts, metal salts. first row transition and blends thereof.
    [0004]
    4. USE according to any one of claims 1 to 3, characterized in that the alkaline activating aluminosilicate binder comprises at least one latent pozzolanic and/or hydraulic binder and at least one salt selected from alkali metal oxides, metal hydroxides alkali metals, alkali metal carbonates, alkali metal silicates, alkali metal aluminates and mixtures thereof.
    [0005]
    5. USE according to claim 4, characterized in that the latent hydraulic binder is selected from industrial and synthetic waste, in particular blast furnace waste, granulated blast furnace waste, surface granulated blast furnace waste, phosphorus waste electrothermal, iron residue and mixtures thereof.
    [0006]
    6. USE according to claim 4, characterized in that the pozzolanic binder is selected from amorphous silica, preferably precipitated silica, silica and fumed microsilica, fine glass powder, fly ash, preferably brown coal fly ash and coal fly ash , metakaolin, natural pozzolans such as limestone tuff, volcanic ash and pumice tuff, synthetic and natural zeolites and mixtures thereof.
    [0007]
    7. USE according to claim 4, characterized in that the alkali metal silicate is selected from compounds having the empirical formula m SiO2 . n M2O, where M is Li, Na or K or a mixture thereof, preferably Na or K.
    [0008]
    Use according to claim 7, characterized in that the molar ratio of m:n is from 0.5 to 3.6, preferably from 0.6 to 3.0 and in particular from 0.7 to 2.0.
    [0009]
    Use according to any one of claims 5 to 8, characterized in that a hydraulic binder selected from cements, in particular Portland cement, aluminate cement, and also mixtures thereof, is additionally present.
    [0010]
    10. USE according to any one of claims 5 to 9, characterized in that the ratio of the organic compound containing nitrogen and/or salt thereof to the aromatic carboxylic acid and/or salt thereof is comprised within the range of 1:1 to 1:10, preferably from 1:5 to 1:10.
    [0011]
    11. USE according to any one of claims 1 to 10, characterized in that the alkaline activating aluminosilicate binder is comprised in formulations of construction materials and/or construction products, such as in-situ concrete, finished concrete parts, goods concrete, concrete blocks as well as in-situ concrete, spray concrete, ready-mix concrete, construction adhesives and thermal insulation composite system adhesives, concrete repair systems, one-component or two-component sealing paste, strips, scratch fillers and self-levelling compositions, tile adhesives, plasters and plasters, adhesives and sealants, coating systems, in particular for tunnels, waste water channels, spray protection and condensed lines, dry mortar, joint grout , drainage mortars and/or repair mortars.
    [0012]
    12. ALKALINE ACTIVATION ALUMINOSILICATE BINDER, characterized in that it comprises blast furnace waste, granulated blast furnace waste and/or surface granulated blast furnace waste as a latent hydraulic binder, microsilica, metakaolin and/or fly ash as a pozzolanic binder, sodium silicate solution and/or potassium silicate solution as an alkaline activator, wherein ε-caprolactam and sodium benzoate are as freeze-thaw stabilizers for use as defined in claim 1.
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    EP2914562A1|2015-09-09|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-10-08| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-09-01| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 26/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP12190780|2012-10-31|
    EP12190780.2|2012-10-31|
    PCT/EP2013/070076|WO2014067721A1|2012-10-31|2013-09-26|Alkali-activated aluminosilicate binder with superior freeze-thaw stability|
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