Method for applying cementitious compositions comprising kinetic modulators in thick layers

Abstract

The invention relates to a method for applying a cementitious composition (2) in a thick layer (3), in particular for repair, grouting, joining, leveling, priming, anchoring, additive manufacturing or casting of building elements, said cementitious composition comprising a kinetic modulator selected from the group consisting of hydroxycarboxylic acids and derivatives thereof, in particular esters of hydroxycarboxylic acids.

Description

Technical Field

[0001] The present invention relates to a method for applying a cement-based composition comprising a dynamics modifier in thick layers. Background of the Invention

[0003] It is a well-known phenomenon that cement-based compositions generate and release heat upon hydration. In particular, the hydration reaction of cement is exothermic and releases a large amount of energy, generally referred to as the heat of hydration, upon hydration of cement.

[0004] Especially when cementitious compositions are applied in thick layers, heat release can be significant, and a typical phenomenon is a significant temperature difference between the inner and outer layers. Another phenomenon related to heat release is dimensional changes due to elongation and contraction. In addition, very high core temperatures may be encountered, for example above 60°C or above 80°C, which may lead to the formation of metastable hydrate phases. As a result, cementitious compositions applied in thick layers have an increased risk of cracking, and strength development may be less predictable and sometimes less than expected. Cementitious compositions that crack have lower durability, and sometimes cracking may even lead to structural failure.

[0005] Known measures to eliminate this problem include using special cements with low heat generation, cooling aggregates, placing cement-based compositions in several subsequent layers, curing with thermal insulation, active cooling, and designing joints and sections to promote heat dissipation. All of these measures require additional steps that can be difficult to implement on the job site and significantly increase the complexity and cost of a given project.

[0006] Retarders for the hydration reaction of cementitious compositions are known. However, known retarders generally inhibit the hydration reaction only for a period of time or they slow down the hydration reaction. Inhibition generally does not balance the heat release, and when hydration finally begins, the entire heat of hydration is released. Slowing the hydration reaction can balance the release of the heat of hydration over a longer period of time, but also prolongs the time to reach the desired degree of cure (usually the desired strength), and thus can slow down the overall construction process.

[0007] What is needed are kinetic modifiers for cementitious compositions that can control or balance heat release during the curing time, as well as methods for applying cementitious compositions containing such kinetic modifiers. Ideally, such kinetic modifiers do not significantly inhibit the onset of cement hydration, i.e., do not delay the initial chemical reaction between cement particles and water in the concrete. In addition, such kinetic modifiers do not excessively prolong the curing of the cementitious material. Preferably, they do not increase the open time by more than 50%, preferably by no more than 20%, and most preferably by no more than 5%, compared to samples without the added kinetic modifier. SUMMARY OF THE INVENTION

[0009] An object of the present invention is to provide a method for applying a cementitious composition, wherein the cementitious composition is applied in a thick layer. A particular object of the present invention is to provide a method for applying a thick layer of cement mortar. In particular, the method is used for repairing, grouting, joining, leveling, rendering, anchoring, additive manufacturing or casting of building elements.

[0010] Surprisingly, the object of the invention is achieved by a method according to claim 1 .

[0011] It has been found that kinetic regulators selected from hydroxycarboxylic acids and derivatives thereof, in particular esters of hydroxycarboxylic acids, in particular citric acid, citrate, tartrate, lactate, gluconate, malate, glycolate and / or mandelate can control or balance the heat release during the curing of cementitious compositions. Thus, for example, the peak or maximum heat flow of a cementitious composition comprising the kinetic regulator can be reduced by 10-90% compared to the same cementitious composition without the kinetic regulator. In particular, the temperature of a cementitious composition applied in a thick layer can be controlled to no more than 65°C or lower. This control or balancing of heat release enables the application of cementitious compositions in thick layers. In particular, elevated temperatures in the core of a cementitious composition applied in a thick layer, and / or temperature differences between internal and external components, are avoided. This significantly reduces the risk of cracking and / or the risk of lower strength development.

[0012] Further objects of the invention are the subject matter of the other independent claims. Advantageous embodiments are the subject matter of the dependent claims.

[0013] Modes for Carrying Out the Invention

[0014] In a first aspect, the present invention relates to a method of applying a cement-based composition, said method comprising the steps of:

[0015] (i) providing a dry cement-based composition comprising at least one binder,

[0016] (ii) providing a kinetic regulator selected from hydroxycarboxylic acids and derivatives thereof, in particular esters of hydroxycarboxylic acids,

[0017] (iii) providing mixing water,

[0018] (iv) mixing the dry cementitious composition, the dynamics modifier and water to obtain a wet cementitious composition,

[0019] or mixing the dry cementitious composition and the dynamics modifier to prepare a dry dry mix, and mixing the dry dry mix with water to obtain a wet cementitious composition,

[0020] (v) applying the wet cementitious composition to the surface in an amount sufficient to produce a layer having a thickness of at least 5 cm, preferably at least 7.5 cm, more preferably at least 8 cm, even more preferably at least 10 cm, even more preferably at least 15 cm, especially at least 20 cm, and

[0021] (vi) optionally curing the applied wet cementitious composition.

[0022] In particular, the present invention relates to a method for applying a cement-based composition wherein exotherm is dissipated.

[0023] In particular, the method of the present invention is a method for repairing, grouting, joining, leveling, rendering, anchoring, additive manufacturing, or casting of a building element. A building element herein can be any element that forms part of a construction project, such as a building. For example, a building element can be a wall, a screed, a putty, a patch, a joint, a decorative element, a filling, or a foundation.

[0024] The dry cementitious composition or dry premix is ​​substantially free of water. Substantially free of water means that the water content does not exceed 5 wt. %, preferably does not exceed 1 wt. %, in particular does not exceed 0.1 wt. % relative to the total weight of the dry cementitious composition.

[0025] The at least one binder is selected from hydraulic cements, pozzolans, and / or latent hydraulic materials. The hydraulic cements may in particular be cements of the CEM I, CEM II, CEM III, CEM IV, and CEM V types as described in standard EN 197-1, cements of type CEM VI as described in standard DIN EN 197-5, calcium aluminate cements as described in standard EN 14647, and / or calcium sulfoaluminate cements. The pozzolans and latent hydraulic materials are preferably selected from slags, in particular blast furnace slag or basic oxygen furnace slag, clays, calcined clays, in particular metakaolin, kiln dust, microsilica, fly ash, pyrogenic silica, precipitated silica, silica fume, zeolites, rice husk ash, burned oil shale, and natural pozzolans such as pumice, volcanic ash, and finely ground limestone.

[0026] The dry cementitious composition provided in the method of the present invention may preferably comprise Portland cement. In particular, the dry cementitious composition comprises a binder in an amount of at least 5% by weight, preferably at least 20% by weight, more preferably at least 35% by weight, still more preferably at least 65% by weight, in particular at least 80% by weight, in particular at least 95% by weight of ordinary Portland clinker, relative to the total weight of the binder.

[0027] The kinetic regulator is selected from hydroxycarboxylic acids and their derivatives, in particular esters of hydroxycarboxylic acids.

[0028] Particularly preferably, the kinetic regulator is selected from citric acid, citrate esters, tartrate esters, lactates, gluconates, malates, glycolates and / or mandelates.

[0029] According to an embodiment, the kinetic regulator is a citric acid ester. In particular, the kinetic regulator is an ester of citric acid and a polyol. Further preferred is a mixed ester of citric acid and a fatty acid and a polyol.

[0030] In the context of the present invention, citric acid is also meant to include isocitric acid.

[0031] According to an embodiment, the kinetic modulator is a citrate ester according to the following general structure (I):

[0032]

[0033] wherein each R is independently H, or a branched or unbranched C2-C30 alkyl chain, or a branched or unbranched C3-C30 alkenyl chain, where the alkenyl chain may contain 1 to 6 double bonds, or a cyclohexyl group, or an aromatic group having 5 to 10 C atoms, with the proviso that at least one R is not H.

[0034] It has been found that kinetic regulators of the general structure (I) and having at least one hydrophobic portion R are particularly suitable in the context of the present invention. Suitable kinetic regulators of the general formula (I) are monobutyl citrate, dibutyl citrate, tributyl citrate, monopentyl citrate, dipentyl citrate, tripentyl citrate, monohexyl citrate, dihexyl citrate, trihexyl citrate, monooleyl citrate, dioleyl citrate, trioleyl citrate, monostearyl citrate, distearyl citrate, tristearyl citrate, monolauryl citrate, dilauryl citrate, trilauryl citrate, monoisopentenyl citrate, diisopentenyl citrate, triisopentenyl citrate, monocyclohexyl citrate, dicyclohexyl citrate, tricyclohexyl citrate, monophenyl citrate, diphenyl citrate, triphenyl citrate.

[0035] According to a further embodiment, the kinetic modifier is an ester of citric acid and a polyol. Such an ester has the following general formula (II):

[0036]

[0037] wherein q is an integer between 0 and 4, preferably 1 or 2, and

[0038] R' is independently H or C(O)-R"", or a portion of the general structure (III), provided that at least one R' is a portion of the general structure (III), wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and wherein the general structure (III) is:

[0039]

[0040] wherein each M is independently H or an alkali metal or alkaline earth metal ion.

[0041] Suitable kinetic modifiers of formula (II) are esters of citric acid with ethylene glycol, glycerol or erythritol. Such esters may be monoesters, diesters or triesters of citric acid. Such esters may be monomers, oligomers or polymers.

[0042] In this context, the esters of citric acid and polyhydric alcohols may contain additional ester groups formed from acids other than citric acid. These acids are particularly acetic acid, propionic acid, and fatty acids. Therefore, suitable kinetic modifiers of general structure (II) also include co-esters of ethylene glycol, glycerol, or erythritol with citric acid and at least one selected from acetic acid, propionic acid, and fatty acids.

[0043] According to a particularly preferred embodiment, the kinetic modifier is selected from monoglycerides and / or diglycerides of citric acid. The monoglycerides and / or diglycerides of citric acid have the chemical structure of the following general formula (IV). Therefore, according to a preferred embodiment, the kinetic modifier of the present invention has the general structure (IV):

[0044]

[0045] in

[0046] Each R" is independently H or C(O)-R"", provided that at least one R" is not H,

[0047] wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and

[0048] Each R'' is independently OM, wherein M is H or an alkali metal or alkaline earth metal ion, or a portion of the following general structure (V),

[0049]

[0050] in

[0051] Each R" is independently H or C(O)-R", wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds.

[0052] The kinetic modifier of the present invention can be a monoglyceride of citric acid or a mixture of different monoglycerides of citric acid. The kinetic modifier of the present invention can be a diglyceride of citric acid or a mixture of different diglycerides of citric acid. The kinetic modifier of the present invention can also be a mixture of one or more monoglycerides of citric acid and one or more diglycerides of citric acid. Preferably, the kinetic modifier of the present invention is a mixture of monoglycerides and diglycerides of citric acid.

[0053] Such monoglycerides and / or diglycerides of citric acid are also known as Citrem. They are commercially available and are commonly used in the food industry.

[0054] The moiety C(O)-R"" in the above general structures (IV) and (V) is preferably derived from a fatty acid. Preferred fatty acids present as esters in the general structures (IV) and (V) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

[0055] According to an embodiment, the kinetic modifier is a tartaric acid ester. In particular, the kinetic modifier is an ester of tartaric acid and a polyol. Further preferred are mixed esters of tartaric acid and fatty acids with a polyol.

[0056] According to an embodiment, the kinetic modulator is an ester of tartaric acid according to the following general structure (VI):

[0057]

[0058] wherein each R is independently H, or a branched or unbranched C2-C30 alkyl chain, or a branched or unbranched C3-C30 alkenyl chain, where the alkenyl chain may contain 1 to 6 double bonds, or a cyclohexyl group, or an aromatic group having 5 to 10 C atoms, with the proviso that at least one R is not H.

[0059] It has been found that kinetic regulators of the general structure (VI) and having at least one hydrophobic group R are particularly suitable in this context. Suitable kinetic regulators of the general structure (VI) are monobutyl tartrate, dibutyl tartrate, monopentyl tartrate, dipentyl tartrate, monohexyl tartrate, dihexyl tartrate, monooleyl tartrate, dioleyl tartrate, monostearyl tartrate, distearyl tartrate, monolauryl tartrate, dilauryl tartrate, monoisopentenyl tartrate, diisopentenyl tartrate, monocyclohexyl tartrate, dicyclohexyl tartrate, monophenyl tartrate, diphenyl tartrate.

[0060] According to a further embodiment, the kinetic modifier is an ester of tartaric acid and a polyol. This ester has the following general structure (VII):

[0061]

[0062] wherein q is an integer between 0 and 4, preferably 1 or 2, and

[0063] R' is independently H or C(O)-R"", or a portion of the general structure (VIII), provided that at least one R' is a portion of the general structure (VIII), wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and wherein the general structure (VIII) is:

[0064]

[0065] wherein each M is independently H or an alkali metal or alkaline earth metal ion.

[0066] Suitable kinetic modifiers of general structure (VII) are esters of tartaric acid with ethylene glycol, glycerol or erythritol. Such esters can be monoesters or diesters of tartaric acid. Such esters can be monomers, oligomers or polymers.

[0067] In this article, the esters of tartaric acid and polyhydric alcohols may contain additional ester groups formed with acids different from tartaric acid. These acids are particularly acetic acid, propionic acid and fatty acids. Therefore, suitable kinetic modifiers of general structure (VII) also include co-esters of ethylene glycol, glycerol or erythritol with tartaric acid and at least one selected from acetic acid, propionic acid and fatty acids.

[0068] According to a particularly preferred embodiment, the kinetic modifier is selected from tartaric acid monoglycerides and / or diglycerides. Tartaric acid monoglycerides and / or diglycerides have the chemical structure of the following general formula (IX). Therefore, according to a preferred embodiment, the kinetic modifier of the present invention has the general formula (IX):

[0069]

[0070] in

[0071] Each R" is independently H or C(O)-R"", provided that at least one R" is not H,

[0072] wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and

[0073] Each R'' is independently OM, wherein M is H or an alkali metal or alkaline earth metal ion, or a portion of the following general structure (X),

[0074]

[0075] in

[0076] Each R" is independently H or C(O)-R", wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds.

[0077] The kinetics regulator of the present invention can be tartaric acid monoglyceride or a mixture of different tartaric acid monoglycerides. The kinetics regulator of the present invention can be tartaric acid diglyceride or a mixture of different tartaric acid diglycerides. The kinetics regulator of the present invention can also be a mixture of one or more tartaric acid monoglycerides and one or more tartaric acid diglycerides. Preferably, the kinetics regulator of the present invention is a mixture of tartaric acid monoglyceride and tartaric acid diglyceride.

[0078] The C(O)-R"" moiety in the general structures (IX) and (X) above is preferably derived from a fatty acid. Preferred fatty acids present as esters in the general structures (IX) and (X) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, elaidic acid, linolenic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0079] Examples of preferred kinetic modifiers are diacetylated mono- and diglycerides of tartaric acid.

[0080] According to an embodiment, the kinetic regulator is a lactic acid ester. In particular, the kinetic regulator is an ester of lactic acid with a polyol. Further preferred are mixed esters of lactic acid and fatty acids with a polyol.

[0081] According to an embodiment, the kinetic modulator is an ester of lactic acid according to the following general structure (XI)

[0082]

[0083] wherein R is a branched or unbranched C2-C30 alkyl chain, or a branched or unbranched C3-C30 alkenyl chain, where the alkenyl chain may contain 1 to 6 double bonds, or a cyclohexyl group, or an aromatic group having 5 to 10 C atoms.

[0084] Suitable kinetic regulators of the general structure (XI) are butyl lactate, amyl lactate, hexyl lactate, oleyl lactate, stearyl lactate, lauryl lactate, isoprene lactate, cyclohexyl lactate, phenyl lactate.

[0085] According to a further embodiment, the kinetic modifier is an ester of lactic acid and a polyol. Such esters have the following general structure (XII):

[0086]

[0087] wherein q is an integer between 0 and 4, preferably 1 or 2, and

[0088] R' is independently H or C(O)-R"", or a moiety of the general structure (XIII), provided that at least one R' is a moiety of the general structure (XIII), wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and wherein the general structure (XIII) is:

[0089]

[0090] Suitable kinetic regulators of general structure (XII) are esters of lactic acid with ethylene glycol, glycerol or erythritol.

[0091] In this context, esters of lactic acid with polyols contain additional ester groups formed with acids other than lactic acid. Such acids are particularly acetic acid, propionic acid, and fatty acids. Therefore, suitable kinetic modifiers of general structure (XII) also include co-esters of ethylene glycol, glycerol, or erythritol with lactic acid and at least one selected from acetic acid, propionic acid, and fatty acids.

[0092] According to a particularly preferred embodiment, the kinetic modifier is selected from glycerol monoesters of lactic acid. The glycerol monoesters of lactic acid have the chemical structure of the following general formula (XIV). Therefore, according to a preferred embodiment, the kinetic modifier of the present invention has the general formula (XIV):

[0093]

[0094] in

[0095] Each R" is independently H or C(O)-R"", provided that at least one R" is not H,

[0096] wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds.

[0097] The kinetic modifier of the present invention may be a glycerol monoester of lactic acid or a mixture of different glycerol monoesters of lactic acid.

[0098] The moiety C(O)-R"" in the above general structure (XIV) is preferably derived from a fatty acid. Preferred fatty acids present as esters in the general structure (XIV) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, elaidic acid, linolenic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

[0099] According to an embodiment, the kinetic regulator is a gluconate ester. In particular, the kinetic regulator is an ester of gluconic acid with a polyol. Further preferred are mixed esters of gluconic acid and fatty acids with a polyol.

[0100] According to an embodiment, the kinetic modulator is a gluconate ester according to the following general structure (XV):

[0101]

[0102] wherein R is a branched or unbranched C2-C30 alkyl chain, or a branched or unbranched C3-C30 alkenyl chain, where the alkenyl chain may contain 1-6 double bonds, or a cyclohexyl group, or an aromatic group having 5-10 C atoms.

[0103] Suitable kinetic regulators of general structure (XV) are butyl gluconate, pentyl gluconate, hexyl gluconate, oleyl gluconate, stearyl gluconate, lauryl gluconate, isoprenyl gluconate, cyclohexyl gluconate, phenyl gluconate.

[0104] According to a further embodiment, the kinetic modifier is an ester of gluconic acid and a polyol. Such esters have the following general structure (XVI):

[0105]

[0106] wherein q is an integer between 0 and 4, preferably 1 or 2, and

[0107] R' is independently H or C(O)-R"", or a portion of the general structure (XVII), provided that at least one R' is a portion of the general structure (XVII), wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and wherein the general structure (XVII) is:

[0108]

[0109] Suitable kinetic regulators of general structure (XVI) are esters of gluconic acid with ethylene glycol, glycerol or erythritol.

[0110] In this context, the esters of gluconic acid with polyols contain additional ester groups formed with acids other than gluconic acid. Such acids are in particular acetic acid, propionic acid, and fatty acids. Therefore, suitable kinetic modifiers of general formula (XVI) also include co-esters of ethylene glycol, glycerol, or erythritol with gluconic acid and at least one selected from acetic acid, propionic acid, and fatty acids.

[0111] According to a particularly preferred embodiment, the kinetic modulator is selected from gluconoglyceride. Gluconoglyceride has the chemical structure of the following general structure (XVIII). Therefore, according to a preferred embodiment, the kinetic modulator of the present invention has the general structure (XVIII):

[0112]

[0113] in

[0114] Each R" is independently H or C(O)-R"", provided that at least one R" is not H,

[0115] wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds.

[0116] The kinetic modifier of the present invention may be a gluconoglyceride monoester or a mixture of different gluconoglycerides monoesters.

[0117] The moiety C(O)-R"" in the above general structure (XVIII) is preferably derived from a fatty acid. Preferred fatty acids present as esters in general formula (XVIII) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, elaidic acid, linolenic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

[0118] According to an embodiment, the kinetic regulator is a malate. In particular, the kinetic regulator is an ester of malic acid with a polyol. Further preferred are mixed esters of malic acid and fatty acids with a polyol.

[0119] According to an embodiment, the kinetic modulator is a malate ester according to the following general structure (IXX):

[0120]

[0121] wherein each R is independently H, or a branched or unbranched C2-C30 alkyl chain, or a branched or unbranched C3-C30 alkenyl chain, where the alkenyl chain may contain 1 to 6 double bonds, or a cyclohexyl group, or an aromatic group having 5 to 10 C atoms, with the proviso that at least one R is not H.

[0122] It has been found that kinetic modulators having the general structure (IXX) and at least one hydrophobic portion R are particularly suitable for the present invention. Suitable kinetic modulators of the general structure (IXX) are monobutyl malate, dibutyl malate, monopentyl malate, dipentyl malate, monohexyl malate, dihexyl malate, monooleyl malate, dioleyl malate, monostearyl malate, distearyl malate, monolauryl malate, dilauryl malate, monoisopentenyl malate, diisopentenyl malate, monocyclohexyl malate, dicyclohexyl malate, monophenyl malate, diphenyl malate.

[0123] According to a further embodiment, the kinetic modifier is an ester of maleic acid and a polyol. Such esters have the following general structure (XX):

[0124]

[0125] wherein q is an integer between 0 and 4, preferably 1 or 2, and

[0126] R' is independently H or C(O)-R"", or a portion of the general structure (XXIa) or (XXIb), provided that at least one R' is a portion of the general structure (XXIa) or (XXIb), wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and wherein the general structures (XXIa) and (XXIb) are:

[0127]

[0128] wherein each M is independently H or an alkali metal or alkaline earth metal ion.

[0129] Suitable kinetic modifiers of general structure (XX) are esters of malic acid with ethylene glycol, glycerol or erythritol. Such esters can be monoesters or diesters of malic acid. Such esters can be monomers, oligomers or polymers.

[0130] In this article, the esters of maleic acid and polyols may contain additional ester groups formed with acids other than maleic acid. Such acids are particularly acetic acid, propionic acid, and fatty acids. Therefore, suitable kinetic modifiers of general structure (XX) also include co-esters of ethylene glycol, glycerol, or erythritol with malic acid and at least one selected from acetic acid, propionic acid, and fatty acids.

[0131] According to a particularly preferred embodiment, the kinetic modulator is selected from monoglycerides and / or diglycerides of malic acid. The monoglycerides and / or diglycerides of malic acid have the following chemical structure of formula (XXIIa) or (XXIIb). Therefore, according to a preferred embodiment, the kinetic modulator of the present invention has the general structure (XXIIa) or (XXIIb):

[0132]

[0133] in

[0134] Each R" is independently H or C(O)-R"", provided that at least one R" is not H,

[0135] wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and

[0136] Each R'' is independently OM, wherein M is H or an alkali metal or alkaline earth metal ion, or a moiety of the following general structure (XXIII),

[0137]

[0138] in

[0139] Each R" is independently H or C(O)-R", wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds.

[0140] The kinetic modifier of the present invention can be malic acid monoglyceride or a mixture of different malic acid monoglycerides. The kinetic modifier of the present invention can be malic acid diglyceride or a mixture of different malic acid diglycerides. The kinetic modifier of the present invention can also be a mixture of one or more malic acid monoglycerides and one or more malic acid diglycerides. Preferably, the kinetic modifier of the present invention is a mixture of malic acid monoglyceride and malic acid diglyceride.

[0141] The moiety C(O)-R"" in the general structures (XXII) and (XXIII) above is preferably derived from a fatty acid. Preferred fatty acids present as esters in the general structures (XXII) and (XXIII) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, elaidic acid, linolenic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

[0142] According to an embodiment, the kinetic modifier is a glycolate. In particular, the kinetic modifier is an ester of glycolic acid and a polyol. Further preferred are mixed esters of glycolic acid and fatty acids with a polyol.

[0143] According to an embodiment, the kinetic modulator is an ester of glycolic acid according to the following general structure (XXIV):

[0144]

[0145] wherein R is a branched or unbranched C2-C30 alkyl chain, or a branched or unbranched C3-C30 alkenyl chain, where the alkenyl chain may contain 1 to 6 double bonds, or a cyclohexyl group, or an aromatic group having 5 to 10 C atoms.

[0146] Suitable kinetic modifiers of general structure (XXIV) are butyl glycolate, pentyl glycolate, hexyl glycolate, oleyl glycolate, stearyl glycolate, lauryl glycolate, isoprenyl glycolate, cyclohexyl glycolate, phenyl glycolate.

[0147] According to a further embodiment, the kinetic modifier is an ester of glycolic acid and a polyol. Such esters have the following general structure (XXV):

[0148]

[0149] wherein q is an integer between 0 and 4, preferably 1 or 2, and

[0150] R' is independently H or C(O)-R"", or a moiety of the general structure (XXVI), provided that at least one R' is a moiety of the general structure (XXVI), wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and wherein the general structure (XXVI) is:

[0151]

[0152] Suitable kinetic modulators of general structure (XXV) are esters of glycolic acid with ethylene glycol, glycerol or erythritol.

[0153] In this context, esters of glycolic acid with polyols contain additional ester groups with acids other than glycolic acid. Such acids include, in particular, acetic acid, propionic acid, and fatty acids. Thus, suitable kinetic modifiers of general structure (XXV) also include co-esters of ethylene glycol, glycerol, or erythritol with glycolic acid and at least one of acetic acid, propionic acid, and fatty acids.

[0154] According to a particularly preferred embodiment, the kinetic modulator is selected from glycolic acid monoglyceride. Glycolic acid monoglyceride has the chemical structure of the following general formula (XXVII). Therefore, according to a preferred embodiment, the kinetic modulator of the present invention has the general structure (XXVII):

[0155]

[0156] in

[0157] Each R" is independently H or C(O)-R"", provided that at least one R" is not H,

[0158] wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds.

[0159] The kinetic modulator of the present invention may be glycolic acid monoglyceride or a mixture of different glycolic acid monoglycerides.

[0160] The moiety C(O)-R"" in the above general structure (XXVII) is preferably derived from a fatty acid. Preferred fatty acids present as esters in the general formula (XXVII) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, elaidic acid, linolenic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

[0161] According to an embodiment, the dynamics regulator is a mandelic acid ester. In particular, the dynamics regulator is an ester of mandelic acid and a polyol. Further preferred are mixed esters of mandelic acid and fatty acids with polyols.

[0162] According to an embodiment, the kinetic modulator is a mandelate ester according to the following general structure (XXVIII):

[0163]

[0164] wherein R is a branched or unbranched C2-C30 alkyl chain, or a branched or unbranched C3-C30 alkenyl chain, where the alkenyl chain may contain 1 to 6 double bonds, or a cyclohexyl group, or an aromatic group having 5 to 10 C atoms.

[0165] Suitable kinetic regulators of the general structure (XXVIII) are butyl mandelate, pentyl mandelate, hexyl mandelate, oleyl mandelate, stearyl mandelate, lauryl mandelate, isoprenyl mandelate, cyclohexyl mandelate, phenyl mandelate.

[0166] According to a further embodiment, the kinetic modifier is an ester of mandelic acid and a polyol. Such esters have the following general structure (XXIX):

[0167]

[0168] wherein q is an integer between 0 and 4, preferably 1 or 2, and

[0169] R' is independently H or C(O)-R"", or a portion of the general structure (XXX), provided that at least one R' is a portion of the general structure (XXX), wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds, and wherein the general structure (XXX) is:

[0170]

[0171] Suitable kinetic modulators of general structure (XXIX) are esters of mandelic acid with ethylene glycol, glycerol or erythritol.

[0172] In this article, the esters of mandelic acid and polyols contain additional ester groups formed with acids different from mandelic acid. Such acids are especially acetic acid, propionic acid and fatty acids. Therefore, suitable kinetic modifiers of general structure (XXIX) also include co-esters of ethylene glycol, glycerol or erythritol with mandelic acid and at least one selected from acetic acid, propionic acid and fatty acids.

[0173] According to a particularly preferred embodiment, the kinetic modulator is selected from glyceryl mandelate. Glyceryl mandelate has the chemical structure of the following general formula (XXXI). Therefore, according to a preferred embodiment, the kinetic modulator of the present invention has the general structure (XXXI):

[0174]

[0175] in

[0176] Each R" is independently H or C(O)-R"", provided that at least one R" is not H,

[0177] wherein R"" is an unbranched C2-C30 alkyl chain or an unbranched C2-C30 alkenyl chain, wherein the alkenyl chain may contain 1 to 6 double bonds.

[0178] The kinetic modulator of the present invention may be mandelic acid monoglyceride or a mixture of different mandelic acid monoglycerides.

[0179] The moiety C(O)-R"" in the above general structure (XXXI) is preferably derived from a fatty acid. Preferred fatty acids present as esters in general formula (XXXI) are caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, elaidic acid, linolenic acid, linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

[0180] According to an embodiment, the kinetic modulator of the present invention can also be a mixture of two or more of citrate, tartrate, lactate, gluconate, malate, glycolate and / or mandelate. Mixtures of two or more can also be applied to esters of the same acid but chemically different.

[0181] The kinetic modifier of the present invention is preferably a solid. According to an embodiment, the kinetic modifier of the present invention is a solid having a particle size of 0-2000 μm, preferably 250-1000 μm, and more preferably 250-500 μm. It has been found that when a kinetic modifier with too low a particle size is used, the setting time, i.e., the open time of the mineral binder composition, may be excessively prolonged. It has also been found that a kinetic modifier with a particle size greater than 2000 μm may result in incomplete reaction of the kinetic modifier within the mineral binder composition, resulting in lower efficiency.

[0182] Particle size can be measured by sieve analysis according to standard ASTM C136 / C136M. This method separates fine particles from coarse particles by passing the material through a plurality of sieves of different mesh sizes. The material to be analyzed is vibrated through a series of successively smaller sieves using a single or combined horizontal, vertical or rotational motion. As a result, the mass percentage of particles passing through the sieve of a given size is obtained. In this document, for a given particle size range, the lower number refers to the mesh size at which >90%, preferably >99%, of the particles are retained, while the higher number refers to the mesh size at which >90%, preferably >99%, of the particles can still pass.

[0183] Therefore, it is preferred that the kinetic modifier present in the admixture of the present invention has a particle size of 0-2000 μm, preferably 250-1000 μm, more preferably 250-500 μm, measured according to ASTM C136 / C136M.

[0184] Without wishing to be bound by theory, it is believed that the esters of hydroxycarboxylic acids slowly hydrolyze in the alkaline environment of the mineral binder mixed with water. The hydroxycarboxylic acid is slowly released and acts as a retarder for the hydration, hardening and / or drying of the mineral binder.

[0185] According to an embodiment, the kinetic modifier is contained in the wet cementitious composition in an amount of 0.01-10 wt%, preferably 0.05-5 wt%, more preferably 0.1-2 wt%, still more preferably 0.25-1.5 wt%, relative to the total weight of the binder.

[0186] In particular, the citrate is contained in the wet cementitious composition in an amount of 0.01-10 wt%, preferably 0.05-5 wt%, more preferably 0.1-2 wt%, still more preferably 0.25-1.5 wt%, even more preferably 0.50-1.5 wt% relative to the total weight of the binder.

[0187] In particular, the tartaric acid ester is contained in the wet cementitious composition in an amount of 0.01-10 wt.-%, preferably 0.05-5 wt.-%, more preferably 0.1-2 wt.-%, still more preferably 0.25-1.5 wt.-%, even more preferably 0.50-1.5 wt.-% relative to the total weight of the binder.

[0188] According to an embodiment, the binder is present in the dry cementitious composition in an amount of 5-95% by weight, preferably 10-60% by weight, relative to the total weight of the dry cementitious composition, and the dynamic modifier is used in an amount of 0.01-10% by weight, preferably 0.05-5% by weight, more preferably 0.1-2% by weight, still more preferably 0.25-1.5% by weight, relative to the total weight of the binder.

[0189] Can mix dry cement-based composition and dynamics regulator of the present invention to prepare dry premix, and further described dry premix is ​​mixed with water to obtain wet cement-based composition.Therefore, dynamics regulator can be mixed with dry cement-based composition to prepare dry mixture.Especially, dynamics regulator is added in dry cement-based composition during preparation described dry cement-based composition.Very preferably, dry premix itself is dry cement-based composition.Mixing can be carried out by the method that is generally applied to dry or wet mixed mortar and concrete.According to preferred embodiment, dry cement-based composition and dynamics regulator are premixed to prepare dry premix, subsequently this dry premix is ​​bagged, stored and transported to construction site, and this dry premix is ​​mixed with water to prepare wet cement-based composition at construction site.

[0190] The kinetic modifier can be inter-ground with a binder selected from hydraulic cement, pozzolan, and / or latent hydraulic material. Thus, the kinetic modifier and binder are mixed with the other components of the dry cement-based composition. Inter-grinding can be performed using methods commonly used for dry grinding of cement, in particular using a ball mill or roller mill.

[0191] According to an embodiment, the dry cementitious composition comprises cement interground with a kinetic modifier.

[0192] Can mix dry cement-based composition and dynamics regulator of the present invention and water to prepare wet cement-based composition equally.Especially, in this case, dynamics regulator is not a part of dry cement-based composition.Mixing can be carried out especially at construction site.In this case, dynamics regulator is particularly preferably added to dry cement-based composition together with mixing water, preferably adds in the form of aqueous solution or dispersion.Dynamics regulator can be added additionally or alternatively before mixing water and / or soon afterwards.

[0193] The dry cementitious composition according to the invention may additionally comprise at least one accelerator. The at least one accelerator may also be added on site, in particular together with the mixing water.

[0194] According to an embodiment, in the method according to the invention, the dry cementitious composition additionally comprises at least one accelerator or at least one accelerator is additionally added together with the mixing water, wherein the at least one accelerator is selected from alkali metal or alkaline earth metal hydroxides, nitrates, nitrites, thiocyanates, chlorides, carbonates, bicarbonates or silicates, or aluminum salts, preferably sodium silicate, sodium thiocyanate, sodium carbonate, sodium bicarbonate, calcium hydroxide, calcium chloride, calcium nitrate, calcium nitrite or aluminum sulfate.

[0195] According to an embodiment, the at least one accelerator is present in an amount of 0.01-5 wt. %, preferably 0.1-4 wt. %, more preferably 0.2-3 wt. %, relative to the total weight of the binder.

[0196] The combination of a kinetic modifier and an accelerator as described above is particularly useful for controlling or balancing heat flow from a cementitious composition while increasing early strength, particularly early flexural strength.

[0197] A particularly suitable dry cementitious composition comprises cement, especially Portland cement, a kinetic modifier which is a mixture of mono- and diglycerides of citric acid, and an accelerator which is calcium nitrate.

[0198] A particularly suitable dry cementitious composition comprises cement, especially Portland cement, a kinetic modifier which is citric acid and an accelerator which is calcium nitrate.

[0199] The dry cementitious composition may further comprise aggregates, fillers and / or admixtures which are chemically different from the kinetic modifiers and accelerators as defined above.

[0200] Aggregate can be any aggregate commonly used in building materials. Typical aggregates are, for example, rock, crushed stone (e.g., crushed limestone), gravel, sand (in particular, quartz sand), river sand, and / or manufactured sand. Aggregate can also be a bio-based aggregate, such as hemp fiber. Suitable crushed stone and / or sand in this context can have a particle size of between 0.063 and 4 mm. Suitable gravel can have a particle size of between 8 and 32 mm. However, other particle sizes are also possible. The particle size can be measured by sieve analysis according to standard DIN EN 933-1:2012-03. Suitable aggregates are described, for example, in standard EN 12620:2013. Of course, mixtures of aggregates are possible.

[0201] The dry cementitious composition of the present invention is particularly preferably a dry mortar. In particular, the dry cementitious composition is not concrete. The mortar contains aggregates having a smaller particle size than concrete. According to an embodiment, the dry cementitious composition of the present invention contains aggregates, and at least 90% by weight, preferably at least 98% by weight, in particular 100% by weight of all the aggregates contained have a maximum particle size of 4 mm, preferably 3 mm, and in particular 2 mm. In particular, the maximum particle size of the aggregates is determined according to DIN EN 933-1:2012-03.

[0202] The admixture chemically different from the kinetic regulator and accelerator as defined above can be any admixture commonly used in mortar and concrete industry.Especially, the admixture can be selected from plasticizer, superplasticizer, shrinkage reducing agent, air entraining agent, degassing agent, stabilizer, viscosity modifier, thickener, water reducer, retarder, waterproofing agent, fiber, foaming agent, defoamer, redispersible polymer powder, dust remover, chromate reducing agent, pigment, biocide, corrosion inhibitor and steel passivator, under the condition that these admixtures are chemically different from the kinetic regulator and accelerator as defined above.Certainly, the mixture of two or more of these additives is also possible.

[0203] Dry cement-based composition and kinetics regulator or dry premix are mixed with water to obtain the mode of wet cement-based composition without particular restriction.For example, dry cement-based composition can be provided to mixed aggregate, add kinetics regulator and water, and mix until obtaining uniform wet cement-based composition.Suitable mixed aggregate includes but not limited to hand mixer, Hobart agitator, portable concrete mixer, truck mixer, mixing drum, paddle stirrer, jet stirrer, screw agitator, spiral mixer, horizontal single shaft agitator, twin shaft paddle stirrer, vertical shaft agitator, ribbon agitator, orbital agitator, change tank agitator, tumble container, vertical stirring chamber or air agitation operation.Mixing can be continuous, semi-continuous or in batches.

[0204] The amount of water added can vary widely. For example, the amount of water added can be such that the mass ratio of water to dry cementitious composition or dry premix is ​​0.1 to 1.0. Higher amounts of water result in a more fluid mixture, while lower amounts result in a more viscous mixture.

[0205] Applying the wet cementitious composition in the method of the invention can be carried out, for example, by brushing, rolling, troweling, spraying, pouring or dispensing.

[0206] In particular, in additive manufacturing methods, the wet cement-based composition can be applied by dispensing from an automated dispenser such as a 3D printer.

[0207] The term "layer thickness" is the thickness of a continuous layer of a wet cementitious composition. The layer thickness is the length measured at right angles and in a straight line from the surface to which the wet cementitious composition is applied to the interface between the wet cementitious composition and any other material (e.g., air, brick, cured concrete, sealing sheet, coating). In the event that there is more than one possible method to measure the layer thickness, the layer thickness always relates to the highest length measured.

[0208] In the case of a wet cementitious composition being applied wet-in-wet in several layers, the layer thickness refers to the total thickness of all layers. In other words, in the case of a wet cementitious composition being applied wet-in-wet to more than one layer, the layer thickness refers to the sum of the thicknesses of the individual layers. The term "wet-in-wet" refers to a situation in which a second layer is applied on top of a first layer, while the first layer has not yet reached its setting time endpoint. In the case of a wet cementitious composition, the setting time can be measured according to standard EN 196-3:2017-03 or ASTM C191-21.

[0209] Preferably, the layer thickness is not higher than 80cm, especially not higher than 50cm or not higher than 30cm. According to an embodiment, the layer thickness can be between 5-80cm, preferably 7.5-50cm, more preferably 8-50cm, still more preferably 10-50cm, still more preferably 15-50cm, especially 20-50cm.

[0210] The method of the invention is particularly suitable for applying layers having a thickness of at least 30 mm, preferably at least 50 mm, since at lower thicknesses there is less need to control the heat release since the heat dissipates freely.

[0211] The surface to which the wet cementitious composition is applied is not particularly limited. The surface may be porous or non-porous. The surface may be dry or wet. Preferably, the surface is capable of withstanding the load of the applied wet cementitious composition. Preferably, the surface is a building material. In the case of a reactive building material, the surface is at least partially cured, preferably substantially completely cured. The surface may be, for example, cured concrete, brickwork, screed, cured gypsum, gypsum board, cardboard, wood, asphalt, or soil.

[0212] In a second aspect, the present invention relates to a kit of parts consisting of:

[0213] (a) a cement-based composition comprising

[0214] (a1) at least one cement,

[0215] (a2) at least one kinetic regulator selected from hydroxycarboxylic acids and their derivatives, in particular esters of hydroxycarboxylic acids,

[0216] (a3) Aggregates,

[0217] (a4) optional other additives, and

[0218] (a5) optionally water, and

[0219] (b) instructions for use of the cementitious composition for application in a layer thickness of at least 5 cm, preferably at least 7.5 cm, more preferably at least 8 cm, even more preferably at least 10 cm, even more preferably at least 15 cm, in particular at least 20 cm of the cementitious composition.

[0220] Likewise, the present invention relates to a kit of parts consisting of:

[0221] (a) a cement-based composition comprising

[0222] (a1) at least one cement,

[0223] (a3) Aggregates,

[0224] (a4) optional other additives, and

[0225] (a5) optionally water,

[0226] (b) at least one kinetic regulator selected from hydroxycarboxylic acids and their derivatives, in particular esters of hydroxycarboxylic acids, and

[0227] (c) instructions for use of the cementitious composition for application in a layer thickness of at least 5 cm, preferably at least 7.5 cm, more preferably at least 8 cm, even more preferably at least 10 cm, even more preferably at least 15 cm, in particular at least 20 cm of the cementitious composition.

[0228] All features and embodiments described above also apply to this aspect.

[0229] According to an embodiment, the at least one cement is applied at a rate of 50-1200 kg / m 3 , preferably 100-900kg / m 3 , still more preferably 300-900 kg / m 3 The dynamic modifier is present in the cementitious composition of the present invention in an amount of 0.01-10 wt. %, preferably 0.05-5 wt. %, more preferably 0.1-2 wt. %, still more preferably 0.25-1.5 wt. %, in each case relative to the total dry weight of the cement. The aggregate is optionally present in an amount of 500-3500 kg / m 3 , preferably 800-3000kg / m 3 The other additives are optionally present in an amount of 0.1-10 wt % relative to the total dry weight of the cement. Water is optionally present in a water to cement weight ratio of 0.1-1.0, preferably 0.2-0.6, more preferably 0.25-0.5.

[0230] According to a further embodiment, the at least one cement is present in the cementitious composition of the present invention in an amount of 5-95% by weight, preferably 10-60% by weight, relative to the total dry weight of the cementitious composition. The kinetic modifier is present in an amount of 0.01-10% by weight, preferably 0.05-5% by weight, more preferably 0.1-2% by weight, even more preferably 0.25-1.5% by weight, in each case relative to the total dry weight of the cement. Aggregate is present in an amount of 5-85% by weight, preferably 20-80% by weight, relative to the total dry weight of the cementitious composition. Further additives are optionally present in an amount of 0.1-10% by weight relative to the total dry weight of the cement. Water is optionally present in a water to powder weight ratio of 0.1-0.6, preferably 0.2-0.5.

[0231] According to a further embodiment, the at least one cement is present in the cementitious composition of the present invention in an amount of 20-75% by weight, preferably 30-50% by weight, relative to the total dry weight of the cementitious composition. The kinetic modifier is present in an amount of 0.01-10% by weight, preferably 0.05-5% by weight, more preferably 0.1-2% by weight, even more preferably 0.25-1.5% by weight, in each case relative to the total dry weight of the cement. The aggregate is present in an amount of 24-75% by weight, preferably 30-60% by weight, relative to the total dry weight of the cementitious composition. Further additives are optionally present in an amount of 0.1-10% by weight relative to the total dry weight of the cement. Water is optionally present in a water to powder weight ratio of 0.1-0.6, preferably 0.2-0.5.

[0232] The cementitious composition of the present invention can be a dry cementitious composition or a dry dry mixture. A dry cementitious composition or a dry dry mixture means that the amount of water present in such a composition is less than 5% by weight, preferably less than 1% by weight, relative to the total weight. The dry cementitious composition or the dry dry mixture can be cement, dry mortar or dry concrete. The cementitious composition of the present invention can also contain water. Therefore, the cementitious composition can also be a wet cementitious composition. The wet cementitious composition can be mortar, grout, leveling agent, adhesive, leveling compound or concrete. The wet cementitious composition of the present invention is obtained by mixing the dry cementitious composition or the dry dry mixture with water. This mixing is especially carried out before applying the cementitious composition. The curing of the cementitious composition will begin when mixed with water. According to an embodiment, the amount of water added to the dry cementitious composition or the dry dry mixture of the present invention is such that the weight ratio of water to cement is 0.1-1.0, preferably 0.2-0.6, more preferably 0.25-0.5.

[0233] A preferred cement-based composition of the present invention consists of:

[0234] a) at least one cement selected from Portland cement, calcium aluminate cement and / or calcium sulfoaluminate cement, preferably Portland cement,

[0235] b) at least one kinetic regulator selected from mono- and / or diglycerides of citric acid of general structure (IV) in an amount of 0.01-10 wt.-%, preferably 0.05-5 wt.-%, more preferably 0.1-2 wt.-%, still more preferably 0.25-1.5 wt.-%, relative to the total dry weight of the cement, and

[0236] c) optionally, 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, relative to the total dry weight of the cement, of at least one accelerator chosen from alkali metal or alkaline earth metal hydroxides, nitrates, nitrites, thiocyanates, chlorides, carbonates, bicarbonates or silicates, or an aluminum salt, preferably sodium silicate, sodium thiocyanate, sodium carbonate, sodium bicarbonate, calcium hydroxide, calcium chloride, calcium nitrate, calcium nitrite or aluminum sulfate.

[0237] Another preferred cementitious composition of the present invention comprises or consists essentially of:

[0238] a) 5 to 95% by weight, relative to the total dry weight of the cement-based composition, of at least one cement chosen from Portland cement, calcium aluminate cement and / or calcium sulphoaluminate cement, preferably Portland cement,

[0239] b) at least one kinetic regulator selected from mono- and / or diglycerides of citric acid of general structure (IV) in an amount of 0.01-10% by weight, preferably 0.05-5% by weight, more preferably 0.1-2% by weight, still more preferably 0.25-1.5% by weight, relative to the total dry weight of the cement,

[0240] c) optionally, 5 to 95% by weight of sand and / or gravel, relative to the total dry weight of the cementitious composition,

[0241] d1) optionally, 0.01 to 3% by weight, relative to the total dry weight of the cement, of at least one plasticizer or superplasticizer,

[0242] d2) optionally, 0.01 to 5% by weight, preferably 0.1 to 4% by weight, more preferably 0.2 to 3% by weight, relative to the total dry weight of the cement, of at least one accelerator chosen from alkali metal or alkaline earth metal hydroxides, nitrates, nitrites, thiocyanates, chlorides, carbonates, bicarbonates or silicates, or an aluminium salt, preferably sodium silicate, sodium thiocyanate, sodium carbonate, sodium bicarbonate, calcium hydroxide, calcium chloride, calcium nitrate, calcium nitrite or aluminium sulphate, and

[0243] e) optionally water, in a weight ratio of water to cement of 0.1-1.0, preferably 0.2-0.6, more preferably 0.25-0.5. BRIEF DESCRIPTION OF THE DRAWINGS

[0244] Figure 1 The layer thickness (3) is shown in the case where a layer of a wet cement-based composition (2) has been applied to a substrate (1).

[0245] Figure 2 The layer thickness (3) is shown in the case where a layer of a wet cement-based composition (2) has been applied to a substrate (1) and covered with a further material (4), such as a paint.

[0246] Figure 3 The layer thickness (3) is shown in the case of two layers of a wet cement-based composition (2a, 2b) applied wet-on-wet to a substrate (1).

[0247] Figure 4 The layer thickness (3) is shown in the case where a layer of a wet cement-based composition (2) has been applied to a gap in a substrate (1) and anchoring elements (5), such as screws, have additionally been introduced into the gap. Example

[0248] Example 1 - Grouting composition

[0249] By in a mixer bowl, 25 % by weight Portland cement (CEM I52.5.R), 74 % by weight silica sand (0.1-2mm) and 1 % by weight additive (plasticizer, defoamer, shrinkage-reducing agent) are mixed at a low speed until visually evenly preparing the dry cement-based composition for grouting. To add water wherein in an amount realizing a mass ratio of water to cement that is 0.5. The kinetics regulator (with respect to the % by weight of cement) of the corresponding amount as shown in the following table 1 is added together with water. Subsequently, mixing was continued at a high speed for 30 seconds, then the wall of the mixing bowl was scraped off, and then mixing was continued for 90 seconds. So obtain the wet cement-based composition.

[0250] The heat flow curves of the resulting grouting mortars were measured in an isothermal process using the Calmetrix i-CAL 8000 instrument, as described in ASTM C1702-17. The wet cementitious composition was applied to the measuring cell in a layer thickness of 5 cm. The maximum heat flow reported in the table below is the global maximum of the heat flow curve. The heat flow 40 hours after mixing with water is also given in the table below. The open time given in the table below is the time at which the heat flow curve begins to increase. To determine the maximum heat flow and open time, the initial peak in the heat flow encountered within the first approximately 5 minutes after mixing was disregarded, as this heat flow is more relevant to the mixing process.

[0251] After the times indicated in Table 1 below, the flexural strength and the compressive strength were measured according to standard EN 196-1:20 05-05.

[0252] Table 1: Examples 1-1, 1-2 (not according to the present invention) and 1-3 (according to the present invention)

[0253]

[0254] *TKPP: Tetrapotassium pyrophosphate

[0255] **R-1: Citric acid esters of mono- and diglycerides (also known as E472c emulsifier)

[0256] Example 2 - Repair composition

[0257] A dry cement-based composition for repair was prepared by mixing 33% by weight Portland cement (CEM I 42.5.R), 63% by weight silica sand (0.063-2 mm), 2% by weight redispersible polymer powder, and 2% by weight additives (plasticizer, thickener, defoamer, shrinkage reducer) in a mixer bowl at low speed until visually homogeneous. Water was added in an amount to achieve a water-to-cement mass ratio of 0.5. The corresponding amount of kinetic modifier (in % by weight relative to cement) shown in Table 2 below was added along with the water. Mixing was then continued at high speed for 30 seconds, followed by scraping down the sides of the mixing bowl and continuing mixing for an additional 90 seconds.

[0258] The measurements were performed as described in Example 1.

[0259] Table 2: Examples 2-1, 2-2 (not of the present invention) and 2-3, 2-4 (of the present invention)

[0260]

[0261] *TKPP: Tetrapotassium pyrophosphate

[0262] **R-1: Citric acid esters of mono- and diglycerides (also known as E472c emulsifier)

[0263] nm: Not measured.

Claims

1. A method for applying a cement-based composition, the method comprising the steps of: (i) providing a dry cement-based composition comprising at least one binder, (ii) providing a kinetic regulator selected from hydroxycarboxylic acids and derivatives thereof, in particular esters of hydroxycarboxylic acids, (iii) providing mixing water, (iv) mixing the dry cementitious composition, the dynamics modifier and water to obtain a wet cementitious composition, or mixing the dry cementitious composition and the kinetic modifier to prepare a dry mix, and mixing the dry mix with water to obtain a wet cementitious composition, (v) applying the wet cementitious composition to the surface in an amount sufficient to produce a layer having a thickness of at least 5 cm, preferably at least 7.5 cm, more preferably at least 8 cm, even more preferably at least 10 cm, even more preferably at least 15 cm, especially at least 20 cm, and (vi) optionally curing the applied wet cementitious composition.

2. The method of claim 1, wherein in step (iv) the kinetic modifier is added to the dry cementitious composition together with the mixing water, preferably in the form of an aqueous solution or dispersion.

3. The method according to at least one of the preceding claims, characterized in that The kinetic modifier is selected from citric acid, citrate esters, tartrate esters, lactates, gluconates, malates, glycolates and / or mandelates.

4. The method according to at least one of the preceding claims, characterized in that The dynamic modifier is contained in the wet cementitious composition in an amount of 0.01-10 wt%, preferably 0.05-5 wt%, more preferably 0.1-2 wt%, still more preferably 0.25-1.5 wt%, even more preferably 0.50-1.5 wt%, relative to the total weight of the binder.

5. The method according to at least one of the preceding claims, characterized in that The kinetic regulator is a solid having a particle size of 0-2000 μm, preferably 250-1000 μm, more preferably 250-500 μm.

6. The method according to at least one of the preceding claims, characterized in that The binder is selected from hydraulic cement, pozzolan and / or latent hydraulic material.

7. The method according to at least one of the preceding claims, characterized in that The binder is present in the dry cementitious composition in an amount of 5-95 wt.-%, preferably 10-60 wt.-%, relative to the total weight of the dry cementitious composition, and the dynamic modifier is used in an amount of 0.01-10 wt.-%, preferably 0.05-5 wt.-%, more preferably 0.1-2 wt.-%, still more preferably 0.25-1.5 wt.-%, relative to the total weight of the binder.

8. The method according to at least one of the preceding claims, characterized in that The dry cement-based composition comprises Portland cement.

9. The method according to at least one of the preceding claims, characterized in that The dry cementitious composition comprises cement interground with the kinetic modifier.

10. The method according to at least one of the preceding claims, characterized in that The dry cementitious composition additionally comprises at least one accelerator or at least one accelerator is additionally added together with the mixing water, wherein the at least one accelerator is selected from alkali metal or alkaline earth metal hydroxides, nitrates, nitrites, thiocyanates, chlorides, carbonates, bicarbonates or silicates, or aluminum salts, preferably sodium silicate, sodium thiocyanate, sodium carbonate, sodium bicarbonate, calcium hydroxide, calcium chloride, calcium nitrate, calcium nitrite or aluminum sulfate.

11. The method according to claim 10, wherein The at least one accelerator is present in an amount of 0.01-5 wt %, preferably 0.1-4 wt %, more preferably 0.2-3 wt %, relative to the total weight of the binder.

12. The method according to at least one of the preceding claims, characterized in that The dry cementitious composition comprises aggregates, and at least 90% by weight, preferably at least 98% by weight, in particular 100% by weight of all the aggregates comprised have a maximum particle size of 4 mm, preferably 3 mm, especially 2 mm.

13. The method according to at least one of the preceding claims, characterized in that The method is used for repairing, grouting, joining, leveling, rendering, anchoring, additive manufacturing or casting of building elements.

14. A kit of parts consisting of: (a) a cement-based composition comprising (a1) at least one cement, (a2) at least one kinetic regulator selected from hydroxycarboxylic acids and their derivatives, in particular esters of hydroxycarboxylic acids, (a3) Aggregate (a4) optional other additives, and (a5) optionally water, and (b) instructions for use of the cementitious composition for application in a layer thickness of at least 5 cm, preferably at least 7.5 cm, more preferably at least 8 cm, even more preferably at least 10 cm, even more preferably at least 15 cm, in particular at least 20 cm of the cementitious composition.

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