Dry mortar composition containing a metal salt of a polyol

Abstract

The present invention relates to a dry mortar composition comprising: (a) a cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, (b) a metal salt of a polyol, wherein the polyol is selected from monosaccharides, oligosaccharides, water-soluble polysaccharides, compounds of general formula (P-I) or dimers or trimers of compounds of general formula (P-I), a metal salt of a polyol, (c) optionally, an external alumina source; (d) a sulfate source; (e) available aluminates calculated as Al(OH) from the calcium aluminate mineral phase + optional external aluminate source, 4 - wherein the total amount is at least 0.05 mol per 100 g of the cementitious binder (a), and the molar ratio of all available aluminates to sulfates is 0.4 to 2.0, available aluminates A dry mortar composition comprising, (f) an ettringite formation controller comprising (i) a hydroxycarboxylic acid, glyoxylic acid, glyoxylate, hydroxycarboxylic acid or its derivative or salt and / or a glyoxylic acid derivative and its salt; and / or a mixture of the foregoing, and (ii) a carbonate source, wherein the carbonate source is preferably an inorganic carbonate, an organic carbonate, or a mixture thereof having a water solubility of 0.1 g·L -1 or more at 25°C. The present invention further relates to a mixed mortar composition comprising the dry mortar composition and water, and an article obtained from the mixed mortar composition.

Description

Technical Field

[0001] The present invention relates to a dry mortar composition comprising (a) a cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, (b) a metal salt of a polyol; (c) optionally, an external alumina source; (d) a sulfate source; and an ettringite formation control agent. The present invention further relates to a mixed mortar composition comprising the dry mortar composition and water, and an article obtained from the mixed mortar composition.

[0002] Polyols, especially glycerin, are raw materials for many dry mortars. However, since glycerin is a liquid and not a solid, it needs to be provided in powder form.

[0003] WO 2020 / 0173723 discloses a construction material comprising a mixture containing at least one compound A selected from glyoxylic acid, its salts, and a condensation or addition product of glyoxylic acid or its salts; and at least one polyhydroxy compound B.

[0004] WO 2022 / 043347 describes a composition for construction materials comprising a cementitious binder, optionally an external aluminate source, a sulfate source, an ettringite formation control agent, and a polyol.

[0005] WO 2022 / 043348 describes a cement-reduced composition for construction materials comprising a cementitious binder, a fine material, a polyol, an ettringite formation control agent, and a co-retarder.

[0006] WO 2022 / 043349 discloses a limestone calcined cement composition for construction materials comprising a cementitious binder, an auxiliary cementitious material, optionally an external aluminate source, a sulfate source, a polyol, an ettringite former, and a co-retarder.

[0007] International Publication No. 2022 / 043350 describes a composition for construction materials containing a cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, and optionally a setting control composition containing an external aluminate source, a sulfate source, and a polyol.

[0008] When using a cementitious flow screed, robust and consistent hardening is an important criterion. Systems that accelerate over time become difficult to process for the processor.

[0009] Pure spraying onto the cement surface or dry mortar mixture is not feasible because it causes a strong aging effect during storage of the dry mortar in cement bags or silos. Subsequently, hydration is strongly accelerated and workability decreases dramatically over time.

[0010] Therefore, an object of the present invention was to provide a dry mortar composition having a constant setting time while exhibiting equivalent overall strength.

[0011] Surprisingly, it has been found that the above object can be solved by the following method.

[0012] Item 1: (a) A cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, (b) A metal salt of a polyol, wherein the polyol is selected from monosaccharides, oligosaccharides, water-soluble polysaccharides, compounds of general formula (P-I) or dimers or trimers of compounds of general formula (P-I),

Chemical formula

Chemical formula

[0013] Item 2: The composition according to item 1, further comprising a co-retarder (g) selected from (g-1) phosphonic acid and its salts, (g-2) polycarboxylic acid and its salts; and mixtures thereof.

[0014] Item 3: The composition according to item 1 or 2, wherein the composition is selected from (h) an alkali-activated binder, rock powder and an inorganic pigment or a mixture thereof, has a Dv90 of less than 200 μm, preferably less than 150 μm, and further comprises a fine material in a total amount of 20 to 200 parts by weight based on 100 parts by weight of the cementitious binder (a).

[0015] Item 4: The composition according to any one of items 1 to 3, wherein the metal salt (b) of the polyol is present in an amount of 0.15 to 2.5% by weight based on the amount of the cementitious binder (a).

[0016] Item 5: The composition according to any one of items 1 to 4, wherein the calcium salt (b) of the polyol is present in a crystalline form or an amorphous form.

[0017] Item 6: The composition according to any one of items 1 to 5, wherein the metal salt (b) of the polyol is a calcium salt of a compound of general formula (P-I) or a dimer or trimer of a compound of general formula (P-I), preferably a calcium salt of a compound of general formula (P-Ia), more preferably calcium glycerolate or a calcium salt of triethanolamine, and particularly preferably calcium glycerolate.

[0018] Item 7: - The binder (a) is present in an amount of 180 to 900 kg per 1 m 3 of the newly mixed mortar composition, and / or - The Blaine surface area of the binder (a) is at least 3800 cm 2 / g, preferably at least 4500 cm 2 / g, The composition according to any one of items 1 to 6.

[0019] Item 8: The available aluminate calculated as Al(OH) from the calcium aluminate mineral phase and optional external aluminate source is such that the total amount is 0.2 mol or less per 100 g of the cementitious binder a), and the composition according to any one of Items 1 to 7. 4 -

[0020] Item 9: The composition according to any one of Items 1 to 8, wherein the calcium aluminate mineral phase is selected from C3A, C4AF, and C12A7, particularly C3A and C4AF.

[0021] Item 10: The composition according to any one of Items 1 to 9, wherein the cementitious binder (a) is Portland cement, particularly ordinary Portland cement (OPC).

[0022] Item 11: The composition according to any one of Items 1 to 10, wherein the sulfate source (d) is a calcium sulfate source, preferably anhydrous calcium sulfate.

[0023] Item 12: The inorganic carbonate is selected from potassium carbonate, sodium carbonate, sodium hydrogen carbonate, lithium carbonate, and magnesium carbonate; the organic carbonate is selected from ethylene carbonate, propylene carbonate, and glycerol carbonate, and the composition according to any one of Items 1 to 11.

[0024] Item 13: The external aluminate source (c) is selected from non-calcareous aluminate sources such as aluminum(III) salts, aluminum(III) complexes, crystalline aluminum hydroxide, and amorphous aluminum hydroxide; and calcareous aluminate sources such as high alumina cement, sulfoaluminate cement, or synthetic calcium aluminate mineral phase, and the composition according to any one of Items 1 to 12.

[0025] Item 14: The composition further comprises a dispersant, preferably, the dispersant is - a comb polymer having a carbon-containing backbone to which a pendant cement-fixed group and a polyether side chain are bonded, ​- A nonionic comb polymer having a carbon-containing skeleton to which a pendant hydrolyzable group and a polyether side chain are bonded, and the hydrolyzable group releases a cement-fixing group upon hydrolysis. - Al 3+ 、Fe 3+ or Fe 2+ A colloidal dispersion preparation of a polyvalent metal cation such as and a polymer dispersant containing an anionic group and / or an anion-forming group and a polyether side chain, wherein the polyvalent metal cation is present in a superstoichiometric amount calculated as a cation equivalent based on the total of the anionic group and the anion-forming group of the polymer dispersant. - Sulfonated melamine-formaldehyde condensate - Lignosulfonate - Sulfonated ketone-formaldehyde condensate - Sulfonated naphthalene-formaldehyde condensate - Phosphate-containing dispersant - Phosphate-containing dispersant, and - Mixtures thereof The composition according to any one of items 1 to 13 selected from the group consisting of.

[0026] Item 15: - The alkali-activated binder is selected from a latent hydraulic binder and a pozzolan binder, and / or - The rock powder is a silicate or carbonate rock powder, preferably selected from limestone, dolomite, basalt and quartz powder, and / or - The inorganic pigment is selected from iron oxide, titanium dioxide, cobalt-chromium-aluminum-spinel, and chromium(III)-oxide. The composition according to any one of items 3 to 14.

[0027] Item 16: A mixed mortar composition comprising the dry mortar composition according to any one of items 1 to 15 and water, wherein the ratio of water to the cementitious binder (w / c) is 0.2 to 1.5, preferably 0.3 to 1.

[0028] Item 17: An article obtained by the blended mortar composition according to Item 16.

[0029] The inventors have surprisingly found that by using a metal salt of a polyol, such as calcium glycerolate, a dry mortar composition having a certain setting time while showing equivalent overall strength can be obtained. In particular, the powder is formed from a liquid polyol after neutralization. When the polyol was added as the calcium salt of the polyol to the remaining components of the dry mortar composition, aging of the dry mortar did not occur, and the dry mortar could be stably stored in a bag for several months.

[0030] The dry mortar composition of the present invention comprises (a) a cementitious binder containing one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, (b) a metal salt of a polyol, wherein the polyol is selected from monosaccharides, oligosaccharides, water-soluble polysaccharides, compounds of general formula (P-I) or dimers or trimers of compounds of general formula (P-I),

Chemical formula

Chemical formula

[0031] The cementitious binder (a) comprises one or more calcium silicate mineral phases and one or more crystalline calcium aluminate mineral phases.

[0032] For convenience, in this specification, the mineralogical phases are indicated by their cement notations. In cement notations, the main compounds are represented by the types of oxides: CaO is C, MgO is M, SiO 2 is S, Al 2 O 3 is A, SO 3 is $, Fe 2 O 3 is F, H 2 O is H.

[0033] Generally, the calcium silicate mineral phase and the calcium aluminate mineral phase constitute at least 90% by weight of the cementitious binder (a). Further, the calcium silicate mineral phase preferably constitutes at least 60% by weight, more preferably at least 65% by weight, and most preferably 65 - 75% by weight of the cementitious binder (a).

[0034] Suitably, the calcium silicate mineral phase is selected from C3S (alite) and C2S (belite). The calcium silicate mineral phase mainly provides the final strength properties.

[0035] Suitably, the calcium aluminate mineral phase is selected from C3A, C4AF and C12A7, especially C3A and C4AF.

[0036] In one embodiment, the cementitious binder (a) is Portland cement, especially ordinary Portland cement (OPC). The term "Portland cement" refers to cement compounds including Portland clinker, especially CEM I within the scope of Clause 5.2 of Standard EN197 - 1. The preferred cement is ordinary Portland cement (OPC) according to DIN EN197 - 1. The phases constituting Portland cement are mainly alite (C3S), belite (C2S), calcium aluminate (C3A), calcium ferroaluminate (C4AF) and other minor phases. Commercial OPC contains calcium sulfate (<7% by weight) or substantially no calcium sulfate (<1% by weight).

[0037] Suitably, the Blaine surface area of the cementitious binder (a) of the dry mortar composition is at least 3800 cm 2 / g, preferably at least 4500 cm 2 / g, and most preferably at least 5000 cm 2 / g. The Blaine surface area is used as a parameter for the fineness of grinding. Finer grinding results in higher reactivity. The Blaine surface area can be determined according to DIN EN196 - 6.

[0038] Preferably, the amount of the cementitious binder (a) in the dry mortar composition is in the range of 8 to 50% by weight, preferably 10 to 30% by weight, based on the solid content of the dry mortar composition.

[0039] Preferably, the binder (a) is present in an amount of 180 to 900 kg per 1 m 3 of the newly mixed mortar composition, preferably 180 - 600 kg per 1 m 3 of the newly mixed mortar composition.

[0040] According to the present invention, the dry mortar composition contains (b) a salt of a polyol, and the polyol is selected from monosaccharides, oligosaccharides, water-soluble polysaccharides, compounds of general formula (P-I) or dimers or trimers of compounds of general formula (P-I). [Chemical formula] In the formula, X is [Chemical formula] and R 1 is -H, -CH 3 ; R 2 is -H, -CH 3 ; R 3 is -CH 2 OH, -NH 2 ; R 4 is -H, -(CH 2 ) p CH 2 OH, -(CH 2 ) s CH(OH)CH 3 ; m is an integer from 1 to 4; n is an integer from 1 to 8; p is an integer from 1 to 4; s is an integer from 1 to 4.

[0041] When the dry mortar composition contains a metal salt of a polyol, particularly a calcium salt of a polyol, a dry mortar composition having a certain setting time can be obtained while showing equivalent overall strength.

[0042] The polyvalent metal salt is selected from the group consisting of alkali metals, alkaline earth metals, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and aluminum.

[0043] Alkaline earth metals include beryllium, magnesium, calcium, strontium, barium. In a preferred embodiment, the alkaline earth metal is calcium.

[0044] Alkali metals include lithium, sodium, potassium, rubidium, cesium and francium.

[0045] "Polyol" is intended to indicate a compound having at least two alcoholic hydroxyl groups, for example 3, 4, 5 or 6 alcoholic hydroxyl groups, in its molecule. Polyols having adjacent hydroxyl groups are preferred. Most preferred are polyols in which at least three hydroxyl groups are bonded in sequence to three carbon atoms.

[0046] In a preferred embodiment, polyol (b) is selected from compounds consisting of only carbon, hydrogen and oxygen and does not contain a carboxyl group (COOH) in its molecule.

[0047] In one embodiment, polyol (b) is selected from saccharides. Useful saccharides include monosaccharides such as glucose and fructose; disaccharides such as lactose and sucrose; trisaccharides such as raffinose; and water-soluble polysaccharides such as amylose and maltodextrin. Monosaccharides and disaccharides, particularly sucrose, are particularly preferred.

[0048] In another preferred embodiment, the polyol (b) is selected from compounds consisting of only carbon, hydrogen, and oxygen and contains neither a carboxyl group (COOH) nor a carbonyl group (C=O) in its molecule. The term "carbonyl group" is understood to include the tautomeric form of the C=O group, i.e., a pair of double-bonded carbon atoms adjacent to a hydroxyl group (-C=C(OH)-).

[0049] Compounds of formula (P-I) in which X is (P-la) are generally called sugar alcohols. Sugar alcohols are typically organic compounds obtained from sugars and contain one hydroxyl group (-OH) bonded to each carbon atom. Useful sugar alcohols are mannitol, sorbitol, xylitol, arabitol, erythritol, and glycerol. Among these, glycerol is particularly preferred. It is assumed that carbonates of polyhydric alcohols such as glycerol carbonate can act as a polyol source.

[0050] Compounds of formula (P-I) in which X is (P-lb) include pentaerythritol and tris(hydroxymethyl)aminomethane.

[0051] Compounds of formula (P-I) in which X is (P-lc) include diethanolamine, triethanolamine, triisopropanolamine, diisopropylamine, methyldiethanolamine, and methyldiisopropanolamine.

[0052] Dimers or trimers refer to compounds formally derived from a condensation reaction involving the removal of one or two water molecules, in which two or three molecules of general formula (P-I) are linked via ether bridges. Examples of dimers and trimers of compounds of formula (P-I) include dipentaerythritol and tripentaerythritol.

[0053] In a preferred embodiment, the calcium salt of polyol (b) is a calcium salt of a compound of general formula (PI) or a dimer or trimer of a compound of general formula (PI), preferably a calcium salt of a compound of general formula (P-Ia), more preferably calcium glycerolate or the calcium salt of triethanolamine, particularly preferably calcium glycerolate.

[0054] In one embodiment, the metal salt of polyol (b) is present in an amount of 0.15-2.5 wt.%, preferably 0.3-2.5 wt.%, more preferably 1.5-2.5 wt.%, based on the amount of cementitious binder (a).

[0055] In one embodiment, the metal salt of polyol (b) is present in crystalline or amorphous form.

[0056] According to the invention, the dry mortar composition contains, per 100 g of cementitious binder (a), a calcium aluminate mineral phase and optionally an external aluminate source, AI(OH). 4 - Preferably, the dry mortar composition contains at least 0.065 mol, in particular at least 0.072 mol, of total available aluminate per 100 g of cementitious binder (a).

[0057] Optimum performance in terms of open time before setting and early strength development is exhibited when the dry mortar composition contains at least 0.05 moles of total available aluminate per 100 g of cementitious binder (a).

[0058] According to the invention, the dry mortar composition contains, per 100 g of cementitious binder (a), a calcium aluminate mineral phase and optionally an external aluminate source, AI(OH). 4 -It contains 0.2 mol or less of available total aluminates calculated as such. Preferably, the dry mortar composition contains 0.15 mol or less, particularly 0.1 mol or less of available total aluminates per 100 g of the cementitious binder (a). When the cementitious binder contains more than 0.2 mol of available total aluminates per 100 g of the cementitious binder (a), the open time becomes short.

[0059] Generally, the approximate proportion of the main minerals in Portland cement is calculated by Bogue's formula based on the elemental composition of the clinker measured by, for example, fluorescence X-ray analysis (XRF). In such a method, the oxide composition of the elements is provided. This means that the amount of Al is reported as Al 2 O 3 It was found that cements with seemingly the same Al 2 O 3 content show completely different properties regarding the initial strength and the controllability by hydration control. Cement contains Al sources that are very different in terms of mineralogical properties and solubility. The inventors have found that not all Al is available or available for the formation of ettringite. Only the Al-containing mineral phases having sufficient solubility in the aqueous environment of the cement paste are involved in the formation of ettringite. Other Al-containing minerals such as crystalline aluminum oxide such as corundum do not produce aluminates in the aqueous environment due to their limited solubility. As a result, reliable values of available aluminates cannot be obtained only by elemental analysis.

[0060] Therefore, the present invention depends on the available aluminate (e) calculated as AI(OH) 4 - "Available aluminate" means including mineral phases and Al-containing compounds that can produce AI(OH) 4 - in an alkaline aqueous environment. C3A (Ca 3 Al 2 O 6Calcium aluminate phases such as dissolve in an alkaline aqueous environment to yield AI(OH) 4 - and Ca 2+ ions. For the purposes of the present invention, the concentration of mineral phases and Al-containing compounds capable of generating AI(OH) 4 - is expressed as the moles of AI(OH) 4 - per 100 g of the cementitious binder (a).

[0061] Common calcium aluminate mineral phases are thought to be sources of available aluminates, as opposed to crystalline aluminum oxide. Thus, the amount of available aluminate in a given cementitious binder can be determined by a method capable of identifying the mineral phases that make up the cementitious binder. A method useful for this purpose is the Rietveld refinement method of X-ray diffraction (XRD) powder patterns. This software technique is used to refine various parameters including lattice parameters, peak positions, intensities, and shapes. Thereby, a theoretical diffraction pattern can be calculated. When the calculated diffraction pattern is nearly identical to the data of the sample being examined, accurate quantitative information regarding the mineral phases contained can be determined.

[0062] Generally, calcium aluminate mineral phases capable of generating AI(OH) 4 - in an alkaline aqueous environment are tricalcium aluminate (C3A), monocalcium aluminate (CA), mayenite (C12A7), grossite (CA2), Q-phase (C20A 13M3S3), or tetracalcium aluminoferrite (C4AF). In practice, when the cementitious binder (a) is Portland cement, generally it is sufficient to evaluate only the following mineral phases: tricalcium aluminate (C3A), monocalcium aluminate (CA), mayenite (C12A7), and tetracalcium aluminoferrite (C4AF), particularly tricalcium aluminate (C3A) and tetracalcium aluminoferrite (C4AF).

[0063] Alternatively, the amount of available aluminate can be determined from the elemental composition of the cementitious binder (a) by, for example, determining the total amount of Al by XRF and then subtracting therefrom the amount of crystalline aluminum compounds that cannot produce available aluminate, which is determined by XRD and the Rietveld refinement method. This method also takes into account amorphous soluble aluminum compounds that can produce available aluminate. Such crystalline aluminum compounds that cannot produce available aluminate include compounds of the melilite group, such as gehlenite (C2AS), compounds of the spinel group, such as spinel (MA), mullite (Al 2 Al 2+2x Si 2-2x O 10-x ), and corundum (Al 2 O 3 ).

[0064] In one embodiment, the present invention utilizes a cementitious binder that contains available aluminate from calcium aluminate mineral phases, in an amount sufficient to meet the amounts specified above, as determined, for example, by XRD analysis.

[0065] Alternatively, if the concentration of available aluminate per 100 g of the cementitious binder (a) contained in the cementitious binder (a) is essentially insufficient, an external aluminate source (c) can be added. Thus, in some embodiments, the composition for construction materials contains an external aluminate source (c).

[0066] The external aluminate source (c) provides the available aluminate as defined above. Suitably, the external aluminate source (c) is selected from non-calcareous aluminate sources such as aluminum(III) salts, aluminum(III) complexes, crystalline aluminum hydroxide, amorphous aluminum hydroxide, etc.; and calcareous aluminate sources such as high alumina cement, sulfoaluminate cement or synthetic calcium aluminate mineral phases, etc.

[0067] Useful aluminum(III) salts are aluminum(III) salts that readily form AI(OH) 4 - in an alkaline aqueous environment. Suitable aluminum(III) salts include, but are not limited to, aluminum halides such as aluminum(III) chloride and their corresponding hydrates, amorphous aluminum oxide, aluminum hydroxide or their mixed forms, aluminum sulfate or sulfate-containing aluminum salts such as potassium alum and their corresponding hydrates, aluminum nitrate, aluminum nitrite and their corresponding hydrates, aluminum complexes such as aluminum triformate, aluminum triacetate, aluminum diacetate and aluminum monoacetate, aluminum-containing metal organic frameworks such as aluminum fumarate, such as Basollte™ A520, and M(II)-aluminum-oxo-hydrates such as hydrogamnet. Aluminum(III) hydroxide may be crystalline or amorphous. Preferably, amorphous aluminum hydroxide is used.

[0068] High alumina cement means a cement containing a high concentration, such as at least 30 wt% of calcium aluminate phase. More precisely, the said mineralogical phase of the aluminate type includes tricalcium aluminate (C3A), monocalcium aluminate (CA), mayenite (C12A7), tetracalcium aluminoferrite (C4AF), or some combination of these phases.

[0069] The ye’elimite (chemical formula 4CaO·3Al 2 O 3 .SO 3 or in cement notation C4A3$) content in sulfoaluminate cement typically exceeds 15 wt%.

[0070] Suitable synthetic calcium aluminate mineral phases include amorphous mayenite (C12A7).

[0071] The dry mortar composition contains a sulfate source (d). The sulfate source is a compound capable of supplying sulfate ions in an alkaline aqueous environment. Generally, the sulfate source has a water solubility of at least 0.6 mmol·L -1 at a temperature of 30 °C. The water solubility of the sulfate source is appropriately determined in water with an initial pH value of 7.

[0072] Specifically, the molar ratio of available total aluminate to sulfate is in the range of 0.4 - 2.0, preferably 0.57 - 0.8, particularly about 0.67. This means that the mixing ratio in the composition is adjusted so that the highest possible proportion of ettringite is formed from the available aluminate.

[0073] As described above, commercially available Portland cement typically contains a small amount of sulfate source. When the exact amount of sulfate is unknown, it can be determined by methods well known to those skilled in the art, such as elemental analysis by XRF. Sulfate sources commonly used in cement production, such as alkaline earth metal sulfates, alkali metal sulfates, or their mixed forms, e.g., gypsum, hemihydrate, anhydrite, arkanite, tenardite, syngenite, langbeinite, etc., are typically crystalline and their amounts can also be determined by XRD. When calculating the molar ratio of available total aluminate to sulfate, both the original amount of sulfate and the added external sulfate source are considered.

[0074] Generally, the external sulfate source may be a calcium sulfate source, preferably selected from calcium sulfate dihydrate, anhydrite, α- and β-hemihydrates, i.e., α-bassanite and β-bassanite, or mixtures thereof. Preferably, the calcium sulfate source is α-bassanite and / or β-bassanite. Other sulfate sources are alkali metal sulfates such as potassium sulfate or sodium sulfate.

[0075] The additive is expected to function as a source of both aluminate and sulfate, for example, aluminum sulfate hexadecahydrate or aluminum sulfate octadecahydrate.

[0076] In one embodiment, the sulfate source (d) is a calcium sulfate source, preferably anhydrous calcium sulfate. The calcium sulfate source is generally included in an amount of 3 to 20% by weight, preferably 10 to 15% by weight, based on the amount of the cementitious binder (a).

[0077] According to the present invention, the dry mortar composition includes an ettringite formation controller (f). The ettringite formation controller includes (i) glyoxylic acid, glyoxylate, hydroxycarboxylic acid or its derivative or salt, and / or glyoxylic acid derivative and its salt; and / or the aforementioned mixture; and a carbonate source. The carbonate source is preferably an inorganic carbonate, an organic carbonate, or a mixture thereof having a water solubility of 0.1 g·L -1 or more.

[0078] Component (i), i.e., glyoxylic acid, glyoxylate and / or glyoxylic acid derivative, glyoxylate, hydroxycarboxylic acid or its derivative or salt, and / or glyoxylic acid derivative and its salt; and / or the above mixture is considered to delay the formation of ettringite from the aluminate phase derived from the cementitious binder in combination with carbonate ions.

[0079] Preferably, (i) glyoxylic acid, glyoxylate and / or glyoxylic acid derivative, glyoxylate, hydroxycarboxylic acid or its derivative or salt, and / or glyoxylic acid derivative and its salt; and / or the aforementioned mixture is present in a total amount of 0.2 to 2% by weight, preferably 0.3 to 1% by weight, based on the amount of the cementitious binder (a).

[0080] Useful glyoxylates include alkali metal glyoxylates such as sodium glyoxylate and potassium glyoxylate.

[0081] Useful glyoxylic acid derivatives include glyoxylic acid polymers and glyoxylic acid adducts.

[0082] In one embodiment, the glyoxylic acid polymer is an amine-glyoxylic acid condensate. The term "amine-glyoxylic acid condensate" is intended to mean a condensate of glyoxylic acid with a compound containing an aldehyde-reactive amino group or amide group. Examples of compounds containing an aldehyde-reactive amino group or amide group include urea, thiourea, melamine, guanidine, acetoguanamine, benzoguanamine and other acylguanamines and polyacrylamide.

[0083] Preferably, the amine-glyoxylic acid condensate is a melamine-glyoxylic acid condensate, a urea-glyoxylic acid condensate, a melamine-urea-glyoxylic acid condensate and / or a polyacrylamide-glyoxylic acid condensate. The urea-glyoxylic acid condensate is particularly preferred. Useful amine-glyoxylic acid condensates and their production are described in International Publication No. WO 2019 / 077050, which is incorporated herein by reference.

[0084] The amine-glyoxylic acid condensate can be obtained by reacting glyoxylic acid with a compound containing an aldehyde-reactive amino group or amide group. Glyoxylic acid can be used as an aqueous solution or as a glyoxylate, preferably an alkali metal glyoxylate. Similarly, the amine compound can be used as a salt, for example, as a guanidinium salt.

[0085] Generally, the amine compound and glyoxylic acid are reacted at a molar ratio of 0.5 to 2 equivalents, preferably 1 to 1.3 equivalents of glyoxylic acid per aldehyde-reactive amino group or amide group. The reaction is carried out at a temperature of 0 to 120 °C, preferably 25 to 105 °C. A pH value of 0 to 8 is preferred. The viscous product obtained by the reaction can be used as it is, adjusted to the desired solid content by dilution or concentration, or evaporated to dryness by, for example, spray drying, drum drying or flash drying.

[0086] Generally, the amine-glyoxylic acid condensate has a molecular weight in the range of 500 to 25000 g / mol, preferably 1000 to 10000 g / mol, particularly preferably 1000 to 5000 g / mol.

[0087] A useful glyoxylic acid adduct is the glyoxylic acid bisulfite adduct of the following formula.

Chemical formula

[0088] Suitable hydroxycarboxylic acids or their derivatives or salts include α-hydroxy monocarboxylic acids or their salts.

[0089] Suitable α-hydroxy monocarboxylic acids or their salts include citric acid, tartaric acid, lactic acid, malic acid, glycolic acid, gluconic acid, and their salts and mixtures thereof. Sodium gluconate is particularly preferred.

[0090] The carbonate source (ii) may preferably be an inorganic carbonate having a water solubility of 0.1 g·L -1 or more at 25°C. The water solubility of the inorganic carbonate is appropriately determined in water with an initial pH value of 7. It is understood that the pH value at the dissolution limit is higher than the initial pH value.

[0091] Due to the presence of the carbonate source, the mixed water is initially concentrated with a high concentration of carbonate ions. The carbonate ions are considered to adsorb onto the mineral phase surface together with glyoxylic acid, glyoxylate, and glyoxylic acid derivatives.

[0092] Preferably, the carbonate source is present in an amount of 0.3 to 1% by weight, preferably 0.3 to 0.5% by weight, based on the amount of the cementitious binder (a).

[0093] The carbonate source may preferably be an inorganic carbonate having a water solubility of 0.1 g·L -1 or more.

[0094] "Inorganic carbonate" is intended to mean a salt of carbonic acid, i.e., a salt characterized by the presence of carbonate ions (CO 3 2- ) and / or hydrogen carbonate ions (HCO).

[0095] In one embodiment, the inorganic carbonate may be appropriately selected from alkali metal carbonates such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, or lithium carbonate, and alkaline earth metal carbonates that satisfy the required water solubility such as magnesium carbonate. Further suitable inorganic carbonates include carbonates of nitrogen bases such as guanidinium carbonate and ammonium carbonate. Sodium carbonate and sodium hydrogen carbonate, particularly sodium hydrogen carbonate, are particularly preferred.

[0096] Alternatively, the carbonate source is selected from organic carbonates. "Organic carbonate" represents an ester of carbonic acid. The organic carbonate is hydrolyzed in the presence of a cementitious system to release carbonate ions. In one embodiment, the organic carbonate is selected from ethylene carbonate, propylene carbonate, glycerol carbonate, dimethyl carbonate, di(hydroxyethyl) carbonate or mixtures thereof, preferably ethylene carbonate, propylene carbonate and glycerol carbonate or mixtures thereof, particularly ethylene carbonate and / or propylene carbonate. Mixtures of inorganic carbonates and organic carbonates can be used as well.

[0097] The weight ratio of component (i) to component (ii) is typically in the range of about 10:1 to about 1:10, preferably about 5:1 to about 1:5 or about 1:1 to about 1:4.

[0098] Preferably, the dry mortar composition of the present invention contains a co-retarder (g) selected from (g-1) phosphonic acid and its salts, (g-2) polycarboxylic acid and its salts, and mixtures thereof.

[0099] Preferably, the co-retarder (g) is present in a total amount of 0.05 to 1% by weight, preferably 0.05 to 0.2% by weight, based on the amount of the cementitious binder (a).

[0100] Suitable phosphonic acids and their salts (g-1) are, in particular, polyphosphonic acids and their salts, including 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), amino-tris(methylenephosphonic acid) (ATMP) or [[(2-hydroxyethyl)imino]bis(methylene)]-bisphosphonic acid, and their salts and their mixtures. The respective chemical formulas of preferred diphosphonates or triphosphonates are shown below. [Chemical formula]

[0101] Suitable polycarboxylic acids and their salts (g-2) include phosphonoalkylcarboxylic acids, aminocarboxylic acids and polymeric carboxylic acids, and their salts and their mixtures.

[0102] As used herein, the term polycarboxylic acid means a compound or polymer having two or more carboxyl groups on the molecule.

[0103] Suitable polycarboxylic acids include low molecular weight polycarboxylic acids (e.g., having a molecular weight of 500 or less), particularly aliphatic polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, malic acid, tartaric acid, and citric acid.

[0104] Suitable phosphonoalkylcarboxylic acids include 1-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 3-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobutane-1,2,4-tricarboxylic acid, 2,4-diphosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-1,2,3,4-tetracarboxylic acid, 1-methyl-2-phosphonopentane-1,2,4-tricarboxylic acid, or 1,2-phosphonoethane-2-dicarboxylic acid.

[0105] Suitable aminocarboxylic acids include ethylenediaminetetraacetic acid or nitrilotriacetic acid.

[0106] Suitable polymeric carboxylic acids include homopolymers of acrylic acid, homopolymers of methacrylic acid, polymaleic acid, copolymers such as ethylene / acrylic acid copolymers and ethylene / methacrylic acid copolymers, and copolymers of acrylic acid and / or methacrylic acid with monomers containing a sulfo group or a sulfonate group. In one embodiment, the monomer containing a sulfo group or a sulfonate group is selected from the group consisting of vinylsulfonic acid, (meth)allylsulfonic acid, 4-vinylphenylsulfonic acid, or 2-acrylamido-2-methylpropylsulfonic acid (ATBS), and ATBS is particularly preferred. One or more of the aforementioned monomers containing a sulfo group or a sulfonate group can be included in the copolymer.

[0107] Generally, the molecular weight of the polymeric carboxylic acid is in the range of 1000 to 30000 g / mol, preferably 1000 to 10000 g / mol. The molecular weight is measured by gel permeation chromatography (GPC) as detailed in the experimental section.

[0108] Preferably, assuming that all carboxyl groups of the polymeric carboxylic acid or its salt are in the non-neutralized form, the milliequivalent number of carboxyl groups is 3.0 meq / g or more, preferably 3.0 to 17.0 meq / g, more preferably 5.0 to 17.0 meq / g, and most preferably 5.0 to 14.0 meq / g.

[0109] Preferably, the dry mortar composition according to the present invention further includes a fine material (h) having a Dv90 of less than 200 μm, preferably less than 150 μm, more preferably less than 70 μm, or less than 50 μm.

[0110] DV90 (volume basis) corresponds to the 90th percentile of the particle size distribution. This means that 90% of the particles have a size less than Dv90 and 10% have a size greater than Dv90. Generally, Dv90 and other values of the same kind are characteristics of the particle size distribution (volume distribution) of a collection of particles or granules. Compliance with the requirement that 90% of the particles have a size of 200 μm or less is ensured when at least 90 volume% of the particles pass through a sieve with a mesh opening of 200 μm. Alternatively, Dv90 can also be calculated from the particle size distribution measured by static laser diffraction using a Malvern Mastersizer2000.

[0111] The particle size distribution affects the packing density, and the packing density affects the water requirement and mechanical properties of the dry mortar composition. The packing density of the dry mortar composition, especially of fine materials, should be made as high as possible in order to improve workability and reduce the water demand. Generally, the particle size of the fine material (h) ranges from 50 nm to 1 mm.

[0112] The dry mortar composition contains a fine material (h) selected from an alkali-activated binder, rock powder and inorganic pigment, or a mixture thereof, having a Dv90 of less than 200 μm, preferably less than 175 μm, more preferably less than 150 μm, in a total amount of 20 to 200 parts by weight based on 100 parts by weight of the cementitious binder (a).

[0113] The term "alkali-activated binder" means a material that hardens like cement in an aqueous alkaline environment. This term generally includes materials commonly called "latent hydraulic binders" and "pozzolanic binders".

[0114] For the purposes of the present invention, the "latent hydraulic binder" preferably has a molar ratio (CaO + MgO):SiO 2It is a binder with a value of 0.8 to 2.5, particularly 1.0 to 2.0. Generally speaking, the aforementioned potential hydraulic binder can be selected from industrial slag and / or synthetic slag, particularly blast furnace slag, electric furnace phosphorus slag, steelmaking slag, and mixtures thereof. "Pozolan binder" generally can be selected from amorphous silica, preferably precipitated silica, fumed silica and microsilica, ground glass, metakaolin, aluminosilicate, fly ash, preferably lignite fly ash and bituminous coal fly ash, natural pozzolan, such as tuff, trass and volcanic ash, calcined clay, calcined shale, rice husk ash, natural and synthetic zeolites, and mixtures thereof.

[0115] Slag can be either industrial slag, i.e., waste from industrial processes, or synthetic slag. Since industrial slag is not always available in a constant quantity and quality, the latter can be advantageous.

[0116] Blast furnace slag (BFS) is a waste from the blast furnace process. Other materials are granulated blast furnace slag (GBFS), and ground granulated blast furnace slag (GGBFS) obtained by finely grinding granulated blast furnace slag. The fineness and particle size distribution of ground granulated blast furnace slag are different, and these are determined by the origin and treatment method. Here, the fineness of grinding affects the reactivity.

[0117] However, for the purposes of the present invention, the expression "blast furnace slag" is intended to include materials resulting from all the aforementioned levels of treatment, grinding, and quality (i.e., BFS, GBFS, and GGBFS). Blast furnace slag generally contains 30 to 45 wt% CaO, about 4 to 17 wt% MgO, about 30 to 45 wt% SiO 2 、and about 5 to 15 wt% Al 2 O 3 、typically about 40 wt% CaO, about 10 wt% MgO, about 35 wt% SiO 2 and about 12 wt% Al 2 O 3 and contains.

[0118] Electric phosphorus slag is a waste product from the production of phosphorus by electrothermal means. Electric phosphorus slag has lower reactivity than blast furnace slag and contains approximately 45 - 50 wt% CaO, approximately 0.5 - 3 wt% MgO, approximately 38 - 43 wt% SiO 2 , approximately 2 - 5 wt% Al 2 O 3 and approximately 0.2 - 3 wt% Fe 2 O 3 , and also contains fluorides and phosphates.

[0119] Steelmaking slag is a waste product generated in various steelmaking processes, and its composition varies greatly.

[0120] Amorphous silica is preferably X-ray amorphous silica, that is, silica that does not show crystallinity by powder diffraction method. The content of SiO 2 in the amorphous silica of the present invention is preferably at least 80 wt%, more preferably at least 90 wt%.

[0121] Precipitated silica is obtained on an industrial scale by a precipitation process starting from water glass. Precipitated silica obtained by some manufacturing processes is also called silica gel.

[0122] Fumed silica is produced by reacting chlorosilane, such as silicon tetrachloride, in a hydrogen / oxygen flame. Fumed silica is an amorphous SiO 2 ·g -1 powder with a particle size of 5 - 50 nm and a specific surface area of 50 - 600 m 2 .

[0123] Microsilica is a by-product of silicon production or ferrosilicon production and also consists mostly of amorphous SiO 2 powder. The particles have a diameter on the order of 0.1 μm. The specific surface area is on the order of 15 - 30 m 2 ·g -1 .

[0124] Metakaolin is produced when kaolin is dehydrated. Kaolin releases physically bound water at 100 - 200 °C, but undergoes dehydroxylation at 500 - 800 °C, resulting in the collapse of the lattice structure and the formation of metakaolin (Al 2 Si 2 O 7 ). Therefore, pure metakaolin contains approximately 54 wt% SiO 2 , and approximately 46 wt% Al 2 O 3 .

[0125] Fly ash is produced especially during the combustion of coal in power plants. Class C fly ash (lignite fly ash) contains approximately 10 wt% CaO according to WO 08 / 012438, while class F fly ash (bituminous coal fly ash) contains less than 8 wt%, preferably less than 4 wt%, typically approximately 2 wt% CaO.

[0126] In another embodiment, the fine material (h) is selected from "rock powder". Rock powder consists of finely crushed rock and is abundantly available. These uses do not significantly contribute to carbon dioxide emissions. Generally, rock powder includes silicate or carbonate rock powder. Useful examples include limestone such as pulverized limestone and precipitated limestone, dolomite, basalt, quartz powder, etc.

[0127] In another embodiment, the fine material (h) is selected from inorganic pigments. Suitable inorganic pigments include iron oxide, titanium dioxide, cobalt - chromium - aluminum - spinel, and chromium(III) oxides such as chromium green. Preferably, the inorganic pigment does not exceed 5 wt%, preferably 3 wt% or less, of the total amount of the cementitious binder (a) and the fine material (h), and the remainder of the fine material (h) is an alkali - activated binder and / or rock powder.

[0128] Although not preferred, the dry mortar composition may contain a setting accelerator, such as a lithium salt, particularly lithium carbonate or lithium sulfate, as is conventionally used, for example, in repair mortars and self-leveling substrates. It is an advantageous feature of the present invention that the lithium setting accelerator can be omitted due to the early strength development of the dry mortar composition. Thus, in a preferred embodiment, the dry mortar composition does not contain a lithium setting accelerator. Since the lithium setting accelerator is a very expensive component, this also helps to reduce the cost of the dry mortar composition.

[0129] Preferably, the dry mortar composition according to the present invention further comprises at least one dispersant for the inorganic binder, particularly a dispersant for cementitious mixtures such as concrete or mortar.

[0130] Examples of useful dispersants include - Comb-shaped polymers having a carbon-containing backbone to which pendant cement-fixing groups and polyether side chains are bonded, - Nonionic comb-shaped polymers having a carbon-containing backbone to which pendant hydrolyzable groups and polyether side chains are bonded, and the hydrolyzable groups release cement-fixing groups by hydrolysis, - Al 3+ , Fe 3+ Or Fe 2+ A colloidal dispersion preparation of a polyvalent metal cation such as and a polymer dispersant containing an anionic group and / or an anion-forming group and a polyether side chain, wherein the polyvalent metal cation is present in a superstoichiometric amount calculated as a cation equivalent based on the total of the anionic groups and anion-forming groups of the polymer dispersant, - Sulfonated melamine-formaldehyde condensates, - Lignosulfonates, - Sulfonated ketone-formaldehyde condensates, - Sulfonated naphthalene-formaldehyde condensates, - Phosphate-containing dispersants, - Phosphate-containing dispersants, and - Mixtures thereof include;

[0131] Preferably, the dispersant is present in a total amount of 0.06 to 0.4% by weight, preferably 0.09 to 0.3% by weight, based on the amount of the cementitious binder (a).

[0132] A comb polymer having a carbon-containing skeleton to which a pendant cement-fixing group and a polyether side chain are bonded is particularly preferred. The cement-fixing group is an anionic group such as a carboxylic acid group, a phosphonic acid group or a phosphoric acid group or an anion thereof and / or an anion-forming group. The anionic group is an acidic group present in the polymer dispersant and can be converted into each anionic group under alkaline conditions.

[0133] Preferably, the structural unit containing an anionic group and / or an anion-forming group is one of the following general formulas (la), (lb), (lc) and / or (ld). [Chemical formula] In the formula, R 1 is H, C 1 -C 4 alkyl group, CH 2 COOH or CH 2 CO-X-R 3A , preferably H or methyl; X is NH-(C n H 2n ), O(C n H 2n )(where n = 1, 2, 3 or 4, and the nitrogen atom or oxygen atom is bonded to the CO group); R 2 is OM, PO 3 M 2 , or O-PO 3 M 2 (however, when R 2 is OM, X is a chemical bond); R is PO 3 M 2 , or O-PO 3 M 2 ; [Chemical formula] In the formula, R 3 is H or C 1 -C 4 alkyl, preferably H or methyl; n is 0, 1, 2, 3 or 4; R 4 is PO 3 M 2 , or O-PO 3 M 2 ; [Chemical formula] In the formula, R 5 is H or C 1 -C 4 alkyl, preferably H; Z is O or NR 7 ; R 7 is H, (C n H 2n )-OH, (C n H 2n )-PO 3 M 2 , (C n H 2n )-OPO 3 M 2 , (C 6 H 4 )-PO 3 M 2 , or (C 6 H 4 )-OPO 3 M 2 ; n is 1, 2, 3 or 4; [Chemical formula] In the formula, R 6 is H or C,-C, alkyl, preferably H; Q is NR 7 or O; R 7is H, (C n H 2n )-OH, (C n H 2n )-PO 3 M 2 , (C n H 2n )-OPO 3 M 2 , (C 6 H 4 )-PO 3 M 2 , or (C 6 H 4 )-OPO 3 M 2 , and n is 1, 2, 3 or 4; each M is independently H or a cation equivalent.

[0134] Preferably, the structural unit containing a polyether side chain is one of general formulas (lla), (llb), (llc) and / or (lld). [Chemical formula] wherein R 10 , R 11 and R 12 are independently of each other H or C 1 -C 4 alkyl, preferably H or methyl; Z is o or S; E is C 2 -C 6 alkylene, cyclohexylene, CH 2 -C 6 H 10 , 1,2-phenylene, 1,3-phenylene or 1,4-phenylene; G is O, NH or CO-NH; or E and G together are a chemical bond; A is C 2 -C 5 alkylene or CH 2 CH(C 6 H 5 ), preferably C2 -C 3 is an alkylene; n is 0, 1, 2, 3, 4 or 5; a is an integer from 2 to 350, preferably from 10 to 150, more preferably from 20 to 100; R 13 is H, unbranched or branched C 1 -C 4 alkyl group, CO-NH 2 or COCH 3 ;

Chemical formula

Chemical formula

Chemical formula

[0135] The molar ratio of structural unit (1) to structural unit (11) varies from 1:3 to about 10:1, preferably from 1:1 to 10:1, more preferably from 3:1 to 6:1. The polymer dispersant containing structural units (l) and (II) can be prepared by conventional methods, for example, by free radical polymerization or controlled radical polymerization. The preparation of the dispersant is described, for example, in European Patent No. 0894811, European Patent No. 1851256, European Patent No. 2463314 and European Patent No. 0753488.

[0136] Some useful dispersants contain carboxyl groups, their salts, or hydrolyzable groups that release carboxyl groups upon hydrolysis. Preferably, the milliequivalent number of carboxyl groups (or carboxyl groups that can be released upon hydrolysis of the hydrolyzable groups contained in the dispersant) contained in these dispersants is less than 3.0 meq / g assuming that all carboxyl groups are in the non-neutralized form.

[0137] More preferably, the dispersant is selected from the group of polycarboxylate ethers (PCE). In PCE, the anionic group is a carboxylic acid group and / or a carboxylate group. PCE is preferably obtained by radical copolymerization of a polyether macromonomer and a monomer containing an anionic and / or anion-generating group. Preferably, at least 45 mol%, preferably at least 80 mol% of all the structural units constituting the copolymer are structural units of the polyether macromonomer or the monomer containing an anionic group and / or an anion-generating group.

[0138] A further class of suitable comb polymers having a carbon-containing backbone to which a pendant cement fixing group and a polyether side chain are attached includes structural units (III) and (IV).

Chemical formula

[0139] The polymers containing structural units (III) and (IV) are obtained by polycondensation of aromatic or heteroaromatic compounds having polyoxyalkylene groups bonded to an aromatic or heteroaromatic core, aromatic compounds having carboxylic acid, sulfonic acid or phosphoric acid moieties, and aldehyde compounds such as formaldehyde.

[0140] In one embodiment, the dispersant is a nonionic comb polymer having a carbon-containing backbone to which a pendant hydrolyzable group and a polyether side chain are bonded, and the hydrolyzable group releases a cement-fixing group upon hydrolysis. Advantageously, the structural unit containing the polyether side chain is one of the general formulas (lla), (llb), (llc) and / or (lld) described above. The structural unit having a pendant hydrolyzable group is preferably an acrylate monomer, more preferably a hydroxyalkyl acrylate monoester and / or a hydroxyalkyl diester, and most preferably is derived from hydroxypropyl acrylate and / or hydroxyethyl acrylate. The ester functional group is hydrolyzed to an (deprotonated) acidic group when exposed to water, preferably at an alkaline pH, which is obtained by mixing the cementitious binder with water, and the resulting functional group then forms a complex with the cement component.

[0141] In one embodiment, the dispersant is a colloidal dispersion preparation of a polyvalent metal cation, such as Al 3+ , Fe 3+ or Fe 2+ , and is selected from polymer dispersants containing an anionic group and / or an anion-forming group and a polyether side chain. The polyvalent metal cation is present in a superstoichiometric amount calculated as a cation equivalent based on the total of the anionic group and the anion-forming group of the polymer dispersant. Such dispersants are described in more detail in International Publication No. WO 2014 / 013077, which is incorporated herein by reference.

[0142] Suitable sulfonated melamine-formaldehyde condensates are of the type frequently used as plasticizers for hydraulic binders (also called MFS resins). Sulfonated melamine-formaldehyde condensates and their preparation are described, for example, in Canadian Patent No. 217200435, German Patent No. 4411797, US Patent No. 4,430,469, US Patent No. 6,555,683 and Swiss Patent No. 686186, as well as in Ullmann’s Encyclopedia of lndustrial Chemistry, 5th Ed., vol. A2, page 131, and Concrete Admixtures Handbook-Properties, Science and Technology, 2.Ed., pages 411, 412. Preferred sulfonated melamine-formaldehyde condensates are (very simplified and idealized formula [Chemical formula] (where n generally represents from 10 to 300) units. The molar weight is preferably in the range of 2500 to 80000. Furthermore, other monomers can be incorporated into the sulfonated melamine units by condensation. Particularly suitable is urea. Furthermore, additional aromatic units such as gallic acid, aminobenzenesulfonic acid, sulfanilic acid, phenolsulfonic acid, aniline, ammoniobenzoic acid, dialkoxybenzenesulfonic acid, dialkoxybenzoic acid, pyridine, pyridinemonosulfonic acid, pyridinedisulfonic acid, pyridinecarboxylic acid and pyridinedicarboxylic acid can be incorporated by condensation. An example of a melamine sulfonic acid-formaldehyde condensate is the Melment® product sold by Master Builders Solutions Deutschland GmbH.

[0143] Suitable lignosulfonates are products obtained as by-products in the paper industry. They are described in Ullmann’s Encyclopedia of lndustrial Chemistry, 5th Ed., vol. A8, pages 586, 587. These include units of very simplified and idealized formulas. [Chem.]

[0144] Lignosulfonates have a molar weight between 2000 and 100,000 g / mol. Generally, they exist in the form of their sodium salts, calcium salts and / or magnesium salts. Examples of suitable lignosulfonates are the Borresperse products sold by Borregaard LignoTech, Norway.

[0145] Suitable sulfonated ketone-formaldehyde condensates are products incorporating a monoketone or diketone as the ketone component, preferably acetone, butanone, pentanone, hexanone or cyclohexanone. This type of condensate is known and is described, for example, in WO 2009 / 103579. Sulfonated acetone-formaldehyde condensates are preferred. They generally have the formula (according to J. Plank et al., J. Appl. Poly. Sci. 2009, 2018 - 2024); [Chem.] (wherein m and n are generally from 10 to 250 each, M is an alkali metal ion such as Na, and the ratio of m:n is generally in the range of about 3:1 to about 1:3, more specifically about 1.2:1 to 1:1.2) It contains units of . Furthermore, it is also possible to incorporate other aromatic units such as gallic acid, aminobenzenesulfonic acid, sulfanilic acid, phenolsulfonic acid, aniline, ammoniobenzoic acid, dialkoxybenzenesulfonic acid, dialkoxybenzoic acid, pyridine, pyridinemonosulfonic acid, pyridinedisulfonic acid, pyridinecarboxylic acid, pyridinedicarboxylic acid, etc. by condensation. An example of a suitable sulfonated acetone-formaldehyde condensate is the Melcret K1 L product sold by Master Builders Solutions Deutschland GmbH.

[0146] Suitable sulfonated naphthalene-formaldehyde condensates are products obtained by sulfonation of naphthalene and subsequent polycondensation with formaldehyde. They are described in references including Concrete Admixtures Handbook - Properties, Science and Technology, 2.Ed., pages 411 - 413 and in Ullmann’s Encyclopedia of lndustrial Chemistry, 5th Ed., vol. AB, pages 587, 588. They include the following formula. [Chemical formula]

[0147] Typically, a molar weight (Mw) between 1000 and 50000 g / mol is obtained. Furthermore, it is also possible to incorporate other aromatic units such as gallic acid, aminobenzenesulfonic acid, sulfanilic acid, phenolsulfonic acid, aniline, ammoniobenzoic acid, dialkoxybenzenesulfonic acid, dialkoxybenzoic acid, pyridine, pyridinemonosulfonic acid, pyridinedisulfonic acid, pyridinecarboxylic acid, pyridinedicarboxylic acid, etc. by condensation. An example of a suitable sulfonated β-naphthalene-formaldehyde condensate is the Melcret 500L product sold by Master Builders Solutions Deutschland GmbH.

[0148] Generally, phosphonate-containing dispersants incorporate phosphonic acid groups and polyether side groups.

[0149] Suitable phosphonate-containing dispersants are of the following formula R-(OA 2 ) n6 -N-[CH 2 -PO(OM 3 2 ) 2 2 wherein, R is H or a hydrocarbon residue, preferably a C 1 -C 15 alkyl radical, A 2 is independently C 2 -C 18 alkylene, preferably ethylene and / or propylene, most preferably ethylene, n6 is an integer from 5 to 500, preferably from 10 to 200, most preferably an integer from 10 to 100, M 3 is H, an alkali metal, 1 / 2 an alkaline earth metal and / or an amine.

[0150] The dry mortar construction material composition may further include at least one aggregate.

[0151] The term "aggregate" is understood to relate to fillers, i.e., inert materials that do not essentially form hydration products. Aggregates can be selected from quartz, sand, marble, such as crushed marble, glass spheres, granite, basalt, limestone, sandstone, calcite, marble, serpentine, travertine, dolomite, feldspar, gneiss, alluvial sand, and mixtures thereof. The packing density of the aggregates should be as high as possible, and their particle size distribution should ideally constitute a Fuller-type sieve curve.

[0152] ​The aggregates can be classified by particle size. Fine aggregates, such as sand, generally have a diameter distribution of 150 μm to 5 mm. Coarse aggregates generally have a diameter distribution exceeding 5 mm.

[0153] The dry mortar composition is obtained by mixing a powdery component C containing a cementitious binder (a) and a sulfate source (d), components (i) and (ii), and a calcium salt of a polyol (b). An optional external aluminate source (c) is included in component C. The calcium salt of the polyol is preferably obtained by reacting the polyol with a calcium compound, such as calcium hydroxide of calcium oxide.

[0154] The present invention also relates to a mixed mortar composition containing the dry mortar composition according to the present invention and water. Preferably, the ratio of water to the cementitious binder (a) is 0.2 to 1.5, preferably 0.3 to 1, more preferably 0.3 to 0.7, and most preferably 0.3 to 0.5.

[0155] In addition to the dry mortar composition, the mixed mortar composition can include concrete or grout. The term "mortar" or "grout" refers to a cement paste to which fine aggregates, i.e., aggregates with a diameter of 150 μm to 5 mm (e.g., sand), and optionally very fine aggregates are added. Grout is a low-viscosity mixture sufficient to fill voids or gaps. The viscosity of the mortar is high enough to support not only the self-weight of the mortar but also the weight of the masonry placed thereon. The term "concrete" refers to a mortar to which coarse aggregates, i.e., aggregates having a diameter exceeding 5 mm, are added.

[0156] The mixed mortar composition may be provided as a dry mix that is mixed with water on-site to obtain a composition for mixed mortar construction materials.

[0157] The blended mortar composition is obtained by mixing a powder component C containing a cementitious binder (a) and a sulfate source (d) with a liquid aqueous component W, and components (i) and (ii) are included in component C. The calcium salt of the polyol (b) is called and mixed with component C. An optional external aluminate source (c) is preferably included in component C or component W. The dispersant is included in one or both of components C and W.

[0158] The order of addition of any optional component (h) which is a fine material is mainly determined by the water content of component (h). If component (h) is provided in an essentially anhydrous form, it can conveniently be included in component C. Otherwise, more generally, component (h) is premixed with component C and component C is then blended.

[0159] This mixing method prevents the immediate formation of ettringite that occurs when the cementitious binder (a) is exposed to water even if components (i) and (ii) that effectively control the formation of ettringite are not present simultaneously.

[0160] The present invention further relates to an article obtained by the blended mortar composition of the present invention.

[0161] In the context of the present invention, the article is preferably a hardened product.

[0162] The article can be obtained by the following method. The method of preparing the article includes the step of drying the blended mortar composition according to the present invention. The drying step can be an active or passive drying step. When the drying step is an active drying step, the drying is carried out up to 90 °C, preferably 30 °C to 55 °C. When the drying step is a passive step, the blended mortar composition dries by hydration and evaporation of water.

[0163] The present invention is further illustrated by the accompanying drawings and the following examples.

[0164] Method Test Procedure - Setting Time The setting time was determined using a 300 g Vicat needle in accordance with DIN 196-3. The start of setting was reached when the needle stopped 3 mm above the glass plate, and the end of setting was reached when the needle stopped 38 mm above the glass plate. The time is indicated in minutes.

[0165] Test procedure - Overall strength development The adjusted mortar mixture was filled into mortar steel prisms (16 / 4 / 4 cm) respectively, and left to cure at a temperature of 20 °C and a relative humidity of 65% for 3 hours to obtain cured mortar prisms.

[0166] The cured mortar prisms were removed from the mold, and the compressive strength was measured 5 hours, 1 day and 7 days after mixing in accordance with DIN EN 13892-1.

Example

[0167] Substances: For the examples and comparative examples, the following materials were used. Retarder 1: As retarder 1, retarder 7 shown in Table 1 of WO 2019 / 077050 was used. Dispersant 1: The dispersant is a copolymer of polycarboxylic acid ether, more specifically, a copolymer of 4-hydroxybutyl monovinyl ether ethoxylated with an average of 64 moles of ethylene oxide and acrylic acid at a ratio of 1 / 10 (dispersant 1 of WO 2019 / 077050). Cement: CEM I 52.5N (amount of available aluminum, calculated as Al(OH) 4 - : 0.0865 mol / 100 g cement, Blaine surface area: 3401 cm 2 / g, amount of CaSO 4 per 100 g cement: 0.0204 mol)

[0168] Additive package: Defoamer: Vinapor DF 9010F (commercially available from BASF Construction Additive GmbH, Trostberg, Germany) Viscosity modifier: Starvis 3040F, commercially available from BASF Construction Additive GmbH, Trostberg, Germany Calcium glycerolate was prepared as follows.

[0169] 1.5 molar equivalents of glycerol were charged into a container. 1 molar equivalent of Ca(OH) 2 was added. The suspension was mixed and then heated to 80 °C. The solid obtained after 7 hours was cooled, ground into fine powder, and analyzed by IR spectroscopy and XRD. [Table 1]

[0170] Preparation of dry mortar: Glycerol or calcium glycerolate was added to the dry mortar compositions shown in Table 1. The dry mortar was produced by thoroughly mixing the powder additives.

[0171] Comparative Example 1: After spraying 1.145 of liquid glycerol onto the cement, all the components were mixed.

[0172] Comparative Example 2: After spraying 1.145 g of liquid glycerol onto the limestone powder, all the components were mixed.

[0173] Example 1: After adding 1.627 g of calcium glycerolate (molar equivalent to 1.145 g of glycerol) as a powder, all the components were mixed together.

[0174] The dry mortar was used within 2 hours after mixing or stored for 2 days and 15 days. The storage was carried out by filling 1.4 kg of dry mortar into a 1.0 L bucket and then sealing it. These sealed buckets were stored at 21 °C for 2 days and 15 days.

[0175] Manufacture of mortar: To produce the mortar, 190.96 g of water was added to the prepared dry mortar. The mortar was mixed in accordance with DIN EN196-1. Five minutes after mixing the water and the dry mortar components, the flow rate was measured using a Haegermann cone in accordance with DIN EN1015-3. The flow rate values are shown in Table 2 in cm.

Table 2

[0176] It can be shown that the setting time of the experiments of the present invention varies within the experimental error (+ / - 10%) of the Vicat experiment. The shortening of the setting time in the comparative example was significant, and the setting time after 15 days was shortened by about 50%. This significant shortening of the setting time poses an obstacle to the production of dry mortar and limits its applicability.

[0177] Therefore, the dry mortar composition of the present invention in Example 1 exhibits a constant setting time while showing equivalent overall strength.

Claims

1. (a) A cementitious binder comprising one or more calcium silicate mineral phases and one or more calcium aluminate mineral phases, (b) A metal salt of a polyol, wherein the polyol is selected from monosaccharides, oligosaccharides, water-soluble polysaccharides, compounds of general formula (P-I) or dimers or trimers of compounds of general formula (P-I), 【Chemical 1】 In the formula, X is, [Chemical Formula 2] is, R １ is -H, -CH ３ and R ２ is -H, -CH ３ and R ３ is -CH ２ OH, -NH ２ and is R ４ is -H, -(CH ２ ) ｐ CH ２ OH, -(CH ２ ) ｓ CH(OH)CH ３ and m is an integer from 1 to 4, n is an integer from 1 to 8, p is an integer from 1 to 4, s is an integer from 1 to 4, A metal salt of a polyol, (c) Optionally, an external alumina source, (d) A sulfate source, A dry mortar composition comprising, wherein the composition comprises, (e) Al(OH) from calcium aluminate mineral phases and optional external aluminate sources ４ － Cementitious binder a) per 100 g, available aluminates with a total amount of at least 0.05 mol, calculated as, the molar ratio of all available aluminates to sulfates being 0.4 to 2.0, available aluminates comprising, and the composition further comprises, (f) An ettringite formation controller comprising (i) glyoxylic acid, glyoxylate, hydroxycarboxylic acid or its derivative or salt and / or glyoxylic acid derivative and its salt, and / or a mixture thereof, and (ii) a carbonate source, wherein the carbonate source is preferably an inorganic carbonate, an organic carbonate, and a mixture thereof having a water solubility of 0.1 g·L －１ or more at 25 °C, and an ettringite formation controller selected from the group consisting of the above-mentioned substances A dry mortar composition comprising.

2. The composition according to claim 1, further comprising a co-retarder (g) selected from (g-1) phosphonic acids and their salts, (g-2) polycarboxylic acids and their salts, and mixtures thereof.

3. The composition according to claim 1 or 2, wherein the composition is selected from (h) an alkali-activated binder, rock powder and inorganic pigments or mixtures thereof, has a Dv90 of less than 200 μm, preferably less than 150 μm, and is in a total amount of 20 to 200 parts by weight based on 100 parts by weight of the cementitious binder (a). The composition further comprises a fine material.

4. The composition according to any one of claims 1 to 3, wherein the metal salt (b) of the polyol is present in an amount of 0.15 to 2.5% by weight based on the amount of the cementitious binder (a).

5. The composition according to any one of claims 1 to 4, wherein the metal salt (b) of the polyol is present in a crystalline or amorphous form.

6. The composition according to any one of claims 1 to 5, wherein the metal salt (b) of the polyol is a calcium salt of a compound of general formula (P-I) or a dimer or trimer of a compound of general formula (P-I), preferably a calcium salt of a compound of general formula (P-Ia), more preferably calcium glycerolate or a calcium salt of triethanolamine, and particularly preferably calcium glycerolate.

7. The binder (a) is present in an amount of 180 to 900 kg, preferably 180 to 600 kg, per 1 m of the newly mixed mortar composition ３ per, and / or ３ is present in an amount of 180 to 600 kg per The Blaine surface area of the binder (a) is at least 3800 cm ２ / g, preferably at least 4500 cm ２ / g, The composition according to any one of claims 1 to 6.

8. From the calcium aluminate mineral phase and an optional external aluminate source, the available aluminate calculated as Al(OH) ４ － The composition according to any one of claims 1 to 7, wherein the total amount of available aluminate is 0.2 mol or less per 100 g of the cementitious binder a).

9. The composition according to any one of claims 1 to 8, wherein the calcium aluminate mineral phase is selected from C3A, C4AF, and C12A7, particularly C3A and C4AF.

10. The composition according to any one of claims 1 to 9, wherein the cementitious binder (a) is Portland cement, particularly ordinary Portland cement (OPC).

11. The composition according to any one of claims 1 to 10, wherein the sulfate source (d) is a calcium sulfate source, preferably anhydrous calcium sulfate.

12. The composition according to any one of claims 1 to 11, wherein the inorganic carbonate is selected from potassium carbonate, sodium carbonate, sodium hydrogen carbonate, lithium carbonate and magnesium carbonate, and the organic carbonate is selected from ethylene carbonate, propylene carbonate and glycerol carbonate.

13. The composition according to any one of claims 1 to 12, wherein the external aluminate source (c) is selected from non-calcareous aluminate sources such as aluminum (III) salts, aluminum (III) complexes, crystalline aluminum hydroxide, amorphous aluminum hydroxide, and calcareous aluminate sources such as high alumina cement, sulfoaluminate cement or synthetic calcium aluminate mineral phases.

14. A mixed mortar composition comprising the dry mortar composition according to any one of claims 1 to 13 and water, wherein the ratio (w / c) of water to the cementitious binder is 0.2 to 1.5, preferably 0.3 to 1.

15. An article obtained by the mixed mortar composition according to claim 14.

Images