Composition containing semi-ordered calcium silicate hydrate

Description

[0001] The present invention relates to a composition containing calcium silicate hydrate, which is particularly suitable as a hardening accelerator for hydraulic binders, a method for producing the composition and its use.

[0002] During cement hydration, the various cement clinker phases react with water to form essentially the hydrate phases calcium silicate hydrate, ettringite, calcium aluminate ferrite phases, monosulfate (kuzelite) and portlandite.

[0003] From WO 2010 / 026155, it is known to accelerate cement hydration by adding calcium silicate hydrate nuclei to cement. Thus, the strength development of cement can be accelerated by adding such calcium silicate hydrate nuclei. The calcium silicate hydrate nuclei are obtainable by reacting a water-soluble calcium component with a water-soluble silicon component in aqueous solution or by reacting a calcium compound with silicon dioxide, in each case in the presence of a water-soluble comb polymer suitable as a superplasticizer for hydraulic binders. The resulting compositions possess an excellent acceleration effect, but also a relatively high viscosity, which can complicate application, for example, when the composition needs to be pumped or sprayed.Furthermore, the compositions obtained by reacting a water-soluble calcium component with a water-soluble silicon component contain foreign ions, such as chloride and nitrate, which bring application-related disadvantages, such as corrosiveness.

[0004] From WO 95 / 04007 a setting and hardening accelerator for silicate hydraulic binders is known, which is obtained in particular from the hydration of Portland cements, crushed Portland clinker or compound Portland cements or mixtures of the aforementioned starting materials by hydration at <90 °C and subsequent grinding.

[0005] WO 2013 / 017391 describes a process for producing a fast-setting hydraulic binder by milling a cement clinker with 0.1 to 5 wt% of a material containing more than 15 wt% calcium silicate hydrate. Water reducers, which are polyoxyalkylene polycarboxylates, can also be milled along with the clinker. The commercially available, crystalline Circolit® is used as the calcium silicate hydrate-containing material.

[0006] G. Land and D. Stephan, Cement & Concrete Composites 57 (2015) 64-67, describe the use of tobermorite particles (630 nm) and xonotlite particles (420 nm) to accelerate cement hydration by adding an aqueous dispersion of the particles to CEM I white cement. The acceleration effect of the xonotlite particles was found to be greater than that of the tobermorite particles.

[0007] EP 2 243 754 A1 describes a process for producing a belite-containing binder, in which a starting material containing calcium, silicon, and oxygen atoms is mixed with water, hydrothermally treated at a temperature of 120°C to 250°C, and the resulting intermediate is subjected to reaction milling at a temperature of 100°C to 200°C for a period of 5 to 30 minutes. During this process, the belite-containing binder is formed through reaction and dehydration and can be used like Portland cement.

[0008] EP 2 801 557 B9 describes a process for producing a highly reactive binder, in which a starting material is mixed from one or more raw materials containing CaO, MgO, SiO₂, Al₂O₃, and Fe₂O₃ or other compounds of these elements. The mixture, which necessarily contains Mg and Al, is treated hydrothermally at 100 to 300 °C with a residence time of 0.1 to 24 h, and the resulting intermediate is annealed at 350 to 600 °C. The product obtained contains at least one calcium silicate and at least one calcium aluminate.

[0009] EP 2 801 558 A1 describes a similar process, but the process product is used as an accelerator of the stiffening / solidification and / or hardening of Portland cement.

[0010] EP 2 801 559 A1 describes a process for enhancing the latent hydraulic and / or pozzolanic reactivity of materials, such as waste and by-products, wherein a starting material containing a CaO source and a source of SiO₂ and / or Al₂O₃ is mixed with water and treated hydrothermally at 100°C to 300°C for a residence time of 0.1 to 50 h. The resulting product exhibits hydraulic, pozzolanic, or latent hydraulic reactivity.

[0011] WO 2017 / 032719 describes a process for producing a composition suitable as an accelerator for the hardening of cement. The process involves bringing a hydraulic or latent hydraulic binder into contact with a dispersant suitable for dispersing inorganic particles in water.

[0012] TASHIRO et al., 23rd General Meeting of the Cement Association Japan, January 1, 1969, pages 136-141, investigate the influence of synthetic calcium silicate hydrate on the strength of cement paste. The synthetic calcium silicate hydrate was produced at 130 °C for 5 days at 5-10 atms. The X-ray diffraction pattern shows that the synthetic calcium silicate hydrate contains significant amounts of quartz.

[0013] EP2607329 concerns additives for hydraulic binders and systems made from them, such as concrete and mortar. In particular, setting and hardening accelerators for hydraulic binders are proposed, which are obtained by reacting a calcium compound with a silica sol.

[0014] The accelerators known from the prior art based on calcium silicate hydrate either have an unsatisfactory acceleration effect or have disadvantages in terms of application (too high viscosity, corrosiveness), so that the economically viable applications are limited.

[0015] The present invention is therefore based on the objective of providing a calcium silicate hydrate-containing composition which, in particular, has a satisfactory accelerating effect on the hardening of hydraulic or latent hydraulic binders and exhibits improved application-related properties. In particular, the composition should be easy to handle, especially having a viscosity that allows for easy pumping and spraying, and be suitable as a hardening accelerator for hydraulically or latently hydraulically setting binders, thus improving the early strength of hydraulically or latently hydraulically setting binders, especially Portland cement. Furthermore, the composition should be economically producible using inexpensive and readily available raw materials.

[0016] For hydraulically setting binders, early strength is defined here as the compressive strength 6 hours after mixing the hydraulically setting binder with water. For latently hydraulically setting binders, early strength is defined as the compressive strength 7 days after mixing the hydraulically setting binder with water.

[0017] Surprisingly, it was found that this problem is solved by a composition suitable for accelerating the hardening of construction chemical mixtures, containing a hydraulic or latent hydraulic binder, comprising a mineral component and a polymeric water-soluble dispersant, wherein the mineral component is a semi-ordered calcium silicate hydrate with an apparent crystallite size of 1 to 15 nm, which is determined by X-ray diffraction and Rietveld analysis, and less than 35 wt.- %, based on the dry weight of the mineral component, contains crystalline phases that are not a calcium silicate hydrate (CSH) phase, wherein "semi-ordered" means that the calcium silicate hydrate (1) has a lower degree of order than a macroscopic crystalline calcium silicate hydrate and (2) has a higher degree of order than amorphous calcium silicate hydrate, and wherein the principal diffraction peak of the semi-ordered calcium silicate hydrate in the X-ray diffraction diagram has a half-width that is at least 1.25 times the half-width of the corresponding principal diffraction peak of the crystalline form with a crystallite size of 50 nm or larger.

[0018] It was found that the composition according to the invention has a more pronounced accelerating effect on the hardening of hydraulic or latent hydraulic binders than comparable compositions in which the mineral component comprises a calcium silicate hydrate with a higher degree of crystallinity. Furthermore, unlike compositions based on calcium silicate hydrate gels or completely amorphous calcium silicate hydrates, compositions according to the invention remain pumpable even at high solids contents.

[0019] The term "comprehensive" or "encompasses" used here also includes the expressions "essentially consisting of" and "consisting of" without being synonymous with these expressions. Mineral component

[0020] The mineral component of the composition according to the invention preferably comprises at least 95 wt.%, more preferably at least 98 wt.%, based on the dry weight of the mineral component, calcium oxide (CaO) and silicon dioxide (SiO₂). The molar ratio Ca / Si in the mineral component is preferably in the range of 0.5 to 2.5, more preferably 0.8 to 2.2, and particularly preferably 1.0 to 2.0 or 1.6 to 2.0.

[0021] Due to manufacturing-related impurities, the mineral component may contain small amounts of aluminum ions, with the molar ratio of silicon / aluminium in the mineral component being 10000 : 1 to 2 : 1, preferably 1000 : 1 to 5 : 1, and particularly preferably 100 : 1 to 10 : 1.

[0022] The mineral component is essentially free of cement, cement clinker and / or ettringite. "Essentially free" here means less than 10 wt.% or less than 5 wt.%, preferably less than 1 wt.% and particularly 0 wt.%, in each case based on the total weight of the mineral component.

[0023] The mineral component of the composition according to the invention comprises a semi-ordered calcium silicate hydrate. Semi-ordered calcium silicate hydrate exhibits physical properties that differ from both the pure crystalline form and the pure amorphous form.

[0024] X-ray diffraction is a suitable method for determining whether calcium silicate hydrate is semi-ordered. Diffraction patterns of calcium silicate hydrate can be recorded using a commercially available powder diffractometer. The X-ray diffraction pattern of semi-ordered calcium silicate hydrate differs from that of crystalline calcium silicate hydrate. Semi-ordered calcium silicate hydrate exhibits a diffraction pattern in which the reflections, diffraction lines, or "peaks" are broader, less defined, and / or partially absent compared to the diffraction pattern of the crystalline form. In the following, a "peak" is defined as a maximum in the plot of X-ray diffraction intensity versus diffraction angle.The principal diffraction peak of the semi-ordered calcium silicate hydrate has a half-width that is at least 1.25 times, usually at least 2 times or at least 3 times, the half-width of the corresponding principal diffraction peak of the crystalline form with a crystallite size of 50 nm or larger.

[0025] On the other hand, the X-ray diffraction pattern of the semi-ordered calcium silicate hydrate also differs from that of the purely X-ray amorphous form. The X-ray diffraction pattern of the semi-ordered calcium silicate hydrate shows a few broad, phase-specific X-ray diffraction maxima, indicating a certain degree of order within the calcium silicate hydrate, whereas the X-ray amorphous form shows no distinguishable X-ray diffraction maxima. No specific calcium silicate hydrate phase can be unambiguously assigned to the X-ray amorphous form.

[0026] Semi-ordered calcium silicate hydrate exhibits a long-range order of less than 100 repeating units, usually less than 20, of the unit cell in at least one spatial direction. If the coherently scattering regions (crystallites), which correspond to the repeating units of the unit cell, are very small in a sample, the individual crystallites, which are actually in a reflection position, are often slightly tilted relative to each other. Furthermore, the disruption of the structure at the grain boundaries leads to changes in the diffraction behavior. This broadens the angular range in which reflections, and thus a diffraction signal, still occur. An "apparent" crystallite size can be calculated from the half-widths of X-ray diffraction signals according to Scherrer: β = λ / ε cos θ β = Full width at half maximum (FWHM) A = Wavelength ε = apparent crystallite size θ = Bragg angle

[0027] In practice, Hugo Rietveld's "Whole-Pattern-Fitting-Structure-Refinement (PFSR)" ("Rietveld analysis") has proven effective for evaluating diffraction patterns. This software method refines a multitude of measurement parameters, including grating parameters, signal width, and waveform. This allows for the calculation of theoretical diffraction patterns. Once the calculated diffraction pattern is nearly identical to the data of an unknown sample, precise quantitative information about crystallite size and amorphous content can be determined.

[0028] According to the invention, the semi-ordered calcium silicate hydrate has an apparent crystallite size of 1 to 15 nm, or 1 to 10 nm and particularly preferably 1 nm to 5 nm, determined by X-ray diffraction analysis and subsequent Rietveld analysis.

[0029] The unit cells of the ordered regions of the semi-ordered calcium silicate hydrate, whose size is described in the present application based on their apparent crystallite size, are derived from crystalline calcium silicate hydrate phases (CSH). Crystalline calcium silicate hydrate phases include, in particular, foshagite, hillebrandite, xonotlite (Belov), xonotlite (Kudoh), nekoite, clinotobermorite, 9 Å tobermorite (riversiderite), 10 Å tobermorite, 11 Å tobermorite (C / S 0.75 and 0.66), 14 Å tobermorite (plombierite), jennite, metajennite, calcium chondrodite, and afwillite. α - C 2 SH, dellaite, jaffeite, rosenhahnite, killalaite, bultfonteinite, reinhardbraunsite, kilchoanite, C 8 S 5 , ocenite, reyerite, gyrolite, truscottite, K-phase, Z-phase, scawtite, fukalite, tylleite, spurrite and / or suolunite, preferably as xonotlite, 9Å-tobermorite (riversiderite), 11Å - tobermorite, 14 Å - tobermorite (plombierite), jennite, metajennite, afwillite and / or jaffeite.

[0030] The unit cells of the ordered regions are preferably derived from 9Å - tobermorite (riversiderite), 10Å - tobermorite, 11Å - tobermorite (C / S 0.75 and 0.66), 14Å - tobermorite (plombierite), scawtite and / or xonotlite or mixtures.

[0031] For the purposes of this document, it has proven to be a sufficient approximation to use only the unit cell of 14 Å - tobermorite (plombierite) to determine the apparent crystallite size.

[0032] The mineral component contains less than 35 wt%, based on the dry weight of the mineral component, of crystalline phases other than semi-ordered calcium silicate hydrate, i.e., crystalline phases that are not calcium silicate hydrate (CSH) phases (hereinafter also referred to as "crystalline foreign phases"). Crystalline foreign phases include portlandite (Ca(OH)₂), calcite (CaCO₃), aragonite (CaCO₃), vaterite (CaCO₃), and α-Quartz (SiO₂). The content of crystalline impurities can range from 0.1 to less than 35 wt.%, preferably 1 to 25 wt.%, based on the dry weight of the mineral component. The dry weight is determined by drying the mineral component at 105 °C until a constant weight is achieved.

[0033] In the case of impurities with aluminium, the mineral component may also contain aluminium-containing phases such as gibbsite (Al(OH) 3 ).

[0034] Typically, the mineral component contains, in addition to the semi-ordered calcium silicate hydrate (and optionally crystalline impurities), an X-ray amorphous phase. According to one embodiment, the mineral component has at least ≥ 10 wt.%, preferably ≥ 40 wt.%, particularly preferably ≥ 60 wt.%, and especially 10 to 99.9 wt.% or 10 to 80 wt.%, preferably 40 to 80 wt.%, X-ray amorphous phase, based on the dry weight of the mineral component, determined by X-ray diffraction analysis followed by Rietveld analysis.

[0035] The sum of semi-ordered calcium silicate hydrate and X-ray amorphous phase is preferably at least 65 wt.%, e.g. 65 to 99 wt.%, based on the dry weight of the mineral component, determined by X-ray diffraction analysis and subsequent Rietveld analysis.

[0036] Preferably, no or only a very small amount of foreign ions, such as alkali, chloride, or nitrate ions, are introduced into the composition according to the invention via the mineral component. In one embodiment, the composition according to the invention contains 2% by weight or less of alkali metals, based on the dry weight of the mineral component.

[0037] The present invention provides a process for producing a calcium silicate hydrate-containing composition, wherein a mineral component is brought into contact with at least one water-soluble polymeric dispersant in an aqueous medium by introducing kinetic energy, wherein the mineral component is a semi-ordered calcium silicate hydrate with an apparent crystallite size of 1 to 15 nm and less than 35 wt.-%, based on the dry weight of the mineral component, contains crystalline phases that are not calcium silicate hydrate phase (CSH), wherein the mineral component is produced by reacting calcium oxide or calcium hydroxide with silicon dioxide in the presence of water under hydrothermal conditions at a temperature in the range of 100 °C to 400 °C over a period of 5 h to 30 h, wherein the contact of the mineral component with the water-soluble polymeric dispersant is effected by milling.

[0038] The mineral component is obtained as a solid with physically adsorbed water. Apart from optional drying at a temperature up to approximately 105 °C, it is not subjected to any further thermal treatment. The mineral component thus produced contains semi-ordered calcium silicate hydrate, crystalline impurities including unreacted or reaction-formed crystalline impurities such as quartz, portlandite, calcite, etc., as well as X-ray amorphous phases.

[0039] The mineral component is expediently produced in a closed container, such as an autoclave, at a temperature in the range of 100°C to 400°C, particularly 110°C to 300°C, 110°C to 230°C, 130°C to 200°C, 130°C to 180°C, 155°C to 180°C, or 160°C to 180°C, and at the resulting pressure. Calcium oxide or calcium hydroxide can be derived from, for example, quicklime, slaked lime, etc. Suitable silicon dioxide materials include, for example, quartz sand or quartz flour, microsilica, etc. Furthermore, pozzolanic binders such as fly ash, slags (such as blast furnace slag), and / or metakaolins can also be used as starting materials. To facilitate the reaction and shorten the reaction time, the starting materials are generally used with an average particle size of < 1 mm.The silicon dioxide source generally has a particle size d(99 value) in the range of 1 to 100 µm, particularly 1 to 90 µm. The amount of calcium oxide or calcium hydroxide and silicon dioxide is generally selected such that the molar ratio of Ca / Si in the mineral component is in the range of 0.5 to 2.5, preferably 0.8 to 2.2, and particularly preferably 1.0 to 2.0 or 1.6 to 2.0.

[0040] It has proven advantageous to use a foaming agent, in particular aluminium powder or a paste containing metallic aluminium, in the hydrothermal production of the mineral component.

[0041] It has proven advantageous to comminute the mineral component after hydrothermal synthesis. Conventional equipment such as crushers and ball mills are suitable for this purpose. Comminution is carried out until a particle size (d(97) value) of ≤ 5 mm, preferably ≤ 2 mm, and in particular a particle size (d(97) value) in the range of 0.05 mm to 5 mm, preferably 0.1 mm to 2 mm, and in particular 0.3 mm to 1 mm, is achieved. Comminution is carried out at a temperature of ≤ 80 °C, in particular ≤ 60 °C, and preferably ≤ 50 °C.

[0042] The mineral component obtained after hydrothermal synthesis is preferably first subjected to mechanical comminution at a temperature of ≤ 80 °C, in particular ≤ 60 °C, preferably ≤ 50 °C.

[0043] After mechanical comminution, the mineral component has a particle size (d(97) value) of ≤ 5 mm, preferably ≤ 2.5 mm and particularly ≤ 1 mm. For example, the particle size (d(97) value) of the mineral component after mechanical comminution is in the range of 0.05 mm to 5 mm, preferably 0.1 mm to 2 mm, and particularly 0.3 mm to 1 mm.

[0044] Preferably, the mineral component that comes into contact with the polymeric dispersant has a specific BET surface area in the range of 30 to 150 m² / g, preferably 80 to 150, particularly 90 to 150 m² / g, especially preferably 100 to 150 m² / g, determined according to DIN ISO 9277:2003-05. Water-soluble polymeric dispersant

[0045] The term "water-soluble polymeric dispersant" here refers to an organic water-soluble polymeric dispersant, i.e., an organic polymer which has a solubility in water at 20 °C and normal pressure of at least 1 gram per liter, in particular at least 10 grams per liter and particularly preferably at least 100 grams per liter.

[0046] The dispersing agent is in particular a comb polymer with polyether side chains, preferably polyalkylene oxide side chains.

[0047] Preferably, the polymeric dispersant is a copolymer comprising acid functional groups and polyether side chains on the main chain.

[0048] In one embodiment, the polymeric dispersant has at least one structural unit of the general formulas (1a), (1b), (1c) and / or (1d), wherein the structural units (1a), (1b), (1c) and (1d) can be the same or different both within individual polymer molecules and between different polymer molecules. wherein R1< represents H or an unbranched or branched C1-C4 alkyl group, CH2COOH or CH2CO-XR2<, preferably H or CH3; X represents NH-(CnH2n), O(CnH2n) with n = 1, 2, 3 or 4, wherein the nitrogen atom or the oxygen atom is bonded to the CO group, or a chemical bond, preferably X = chemical bond or O(CnH2n); R2< represents OM, PO3M2, O-PO3M2 or SO3M; with the proviso that X represents a chemical bond when R2< represents OM; wherein R 3< stands for H or an unbranched or branched C 1 -C 4 alkyl group, preferably for H or CH 3 ; n stands for 0, 1, 2, 3 or 4, preferably for 0 or 1 ; R 4< stands for PO 3 M 2 , O-PO 3 M 2 or SO 3 M ; wherein R 5< stands for H or an unbranched or branched C 1 -C 4 alkyl group, preferably for H; Z for O or NR 7< , preferably for O; R 7< stands for 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 , (C 6 H 4 )-OPO 3 M 2 , (C n H 2n )-SO 3 M or (C 6 H 4 )-SO 3 M , and n stands for 1, 2, 3 or 4, preferably for 1, 2 or 3; wherein R6< represents H or an unbranched or branched C1-C4 alkyl group, preferably H; Q represents NR7< or O, preferably O; R7< represents H, (CnH2n)-OH, (CnH2n)-PO3M2, (CnH2n)-OPO3M2, (C6H4)-PO3M2, (C6H4)-OPO3M2, (CnH2n)-SO3M or (C6H4)-SO3M, n represents 1, 2, 3 or 4, preferably 1, 2 or 3; and Each M in the above formulas independently represents H or a cation equivalent.

[0049] Preferably, the comb polymer has at least one structural unit of formula (1a), wherein R 1< represents H or CH 3; and / or at least one structural unit of formula (1b), wherein R 3< represents H or CH 3; and / or at least one structural unit of formula (1c), wherein R 5< represents H or CH 3 and Z represents O; and / or at least one structural unit of formula (1d), wherein R 6< represents H and Q represents O.

[0050] Preferably the comb polymer has at least one structural unit of formula (1a) wherein R 1< stands for H or CH 3 and XR 2< stands for OM or X for O(C n H 2n ) with n = 1, 2, 3 or 4, in particular 2, and R 2< stands for O-PO 3 M 2.

[0051] Preferably, the comb polymer has at least one structural unit of the general formulas (IIa), (IIb), (IIc) and / or (IId) as a polyether side chain: wherein R10<, R11< and R12< independently represent H or an unbranched or branched C1-C4 alkyl group; Z represents O or S; E represents an unbranched or branched C1-C6 alkylene group, a cyclohexylene group, CH2-C6H10, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene; G represents O, NH or CO-NH; or E and G together represent a chemical bond; A represents CxH2x with x = 2, 3, 4 or 5 or CH2CH(C6H5), preferably 2 or 3; n represents 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2. a represents an integer from 2 to 350, preferably 5 to 150; R 13< represents H, an unbranched or branched C 1 -C 4 alkyl group, CO-NH 2 and / or COCH 3; wherein R16<, R17< and R18< independently represent H or an unbranched or branched C1-C4 alkyl group; E represents an unbranched or branched C1-C6 alkylene group, a cyclohexylene group, CH2-C6H10, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, or a chemical bond; A represents CxH2x with x = 2, 3, 4 or 5 or CH2CH(C6H5), preferably 2 or 3; n represents 0, 1, 2, 3, 4 and / or 5, preferably 0, 1 or 2; L represents C x H 2x with x = 2, 3, 4 or 5 or CH 2 -CH(C 6 H 5 ), preferably 2 or 3; a represents an integer from 2 to 350, preferably 5 to 150; d represents an integer from 1 to 350, preferably 5 to 150; R 19< represents H or an unbranched or branched C 1 -C 4 alkyl group; R 20< represents H or an unbranched C 1 -C 4 alkyl group; wherein R 21< , R 22< and R 23< independently represent H or an unbranched or branched C 1-C 4 alkyl group; W represents O, NR 25< or N; Y represents 1 when W = O or NR 25< , and 2 when W = N; A represents C x H 2x with x = 2, 3, 4 or 5 or CH 2 CH(C 6 H 5 ), preferably 2 or 3; a represents an integer from 2 to 350, preferably 5 to 150; R 24< represents H or an unbranched or branched C 1-C 4 alkyl group; and R 25< represents H or an unbranched or branched C 1-C 4 alkyl group; wherein R 6< represents H or an unbranched or branched C 1 - C 4 alkyl group; Q represents NR 10<, N or O; V represents 1 when W = O or NR 10< and 2 when W = N; R 10< represents H or an unbranched or branched C 1 - C 4 alkyl group; and A represents C x H 2x with x = 2, 3, 4 or 5, or CH 2 C(C 6 H 5 )H, preferably 2 or 3; R 24< represents H or an unbranched or branched C 1 - C 4 alkyl group; M represents H or a cation equivalent; and a represents an integer from 2 to 350, preferably 5 to 150.

[0052] Particularly preferably, the structural unit according to formula 1a is a methacrylic acid or acrylic acid unit, the structural unit according to formula 1c is a maleic anhydride unit and the structural unit according to formula 1d is a maleic acid or a maleic acid monoester unit.

[0053] Insofar as the monomers (I) are phosphoric acid esters or phosphonic acid esters, they may also include the corresponding diesters and triesters as well as the monoester of diphosphoric acid. These are generally formed during the esterification of organic alcohols with phosphoric acid, polyphosphoric acid, phosphorus oxides, phosphorus halides or phosphorus oxyhalides or the corresponding phosphonic acid compounds, in addition to the monoester in varying proportions, for example 5-30 mol% diesters and 1-15 mol% triesters as well as 2-20 mol% of the monoester of diphosphoric acid.

[0054] Preferably, the comb polymer has the following polyether side chain: (a) at least one structural unit of formula (IIa) wherein R 10< and R 12< represent H, R 11< represents H or CH 3, E and G together represent a chemical bond, A represents C x H 2x with x = 2 and / or 3, a represents 3 to 150, and R 13< represents H or an unbranched or branched C 1 -C 4 alkyl group; and / or (b) at least one structural unit of formula (IIb) wherein R 16< and R 18< represent H, R 17< represents H or CH 3, E represents an unbranched or branched C 1 -C 6 alkylene group, A represents C x H 2x with x = 2 and / or 3, L represents C x H 2x with x = 2 and / or 3, a represents an integer from 2 to 150, d represents an integer from 1 to 150, R 19< represents H or an unbranched or branched C 1 -C 4 alkyl group, and R 20< represents H or an unbranched or branched C 1 -C 4 alkyl group;and / or (c) at least one structural unit of formula (IIc), wherein R 21< and R 23< represent H, R 22< represents H or CH 3, A represents C x H 2x with x = 2 and / or 3, a represents an integer from 2 to 150, and R 24< represents H or an unbranched or branched C 1-C 4 alkyl group; and / or (d) at least one structural unit of formula (IId), wherein R 6< represents H, Q represents O, R 7< represents (C n H 2n )-O-(AO) a -R 9<, n represents 2 and / or 3, A represents C x H 2x with x = 2 and / or 3, a represents an integer from 1 to 150, and R 9< represents H or an unbranched or branched C 1-C 4 alkyl group.

[0055] The structural unit according to formula IIa is particularly preferably an alkoxylated isoprenyl, alkoxylated hydroxybutyl vinyl ether, alkoxylated (meth)allyl alcohol, or a vinylated methyl polyalkylene glycol unit, each preferably with an arithmetic mean of 2 to 350 oxyalkylene groups.

[0056] Preferably the comb polymer comprises at least one structural unit of formula (IIa) and / or (IIc), in particular of formula (IIa).

[0057] In addition to the structural units of formulas (I) and (II), the polymeric dispersant may also contain further structural units derived from radically polymerizable monomers, such as hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, (meth)acrylamide, (C1-C4)-alkyl(meth)acrylates, styrene, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, (meth)allylsulfonic acid, vinylsulfonic acid, vinyl acetate, acrolein, N-vinylformamide, vinylpyrrolidone, (meth)allyl alcohol, isoprenol, 1-butyl vinyl ether, isobutyl vinyl ether, aminopropyl vinyl ether, ethylene glycol monovinyl ether, 4-hydroxybutyl monovinyl ether, (meth)acrolein, crotonaldehyde, dibutyl maleate, dimethyl maleate, diethyl maleate, dipropyl maleate, etc.

[0058] The production of the comb polymers containing structural units (I) and (II) is carried out in the usual manner, for example by radical polymerization. This is described, for example, in EP0894811, EP1851256, EP2463314, EP0753488.

[0059] Preferably, the comb polymer comprises units of formulas (I) and (II), in particular formulas (1a) and (1a).

[0060] Preferably, the comb polymer has structural units of formulas (1a) and (2c).

[0061] Preferably, the comb polymer has structural units of formulas (Ic) and (IIa).

[0062] Preferably, the comb polymer has structural units of formulas (1a), (1c) and (IIa).

[0063] Preferably, the comb polymer is composed of (i) anionic or anionic structural units derived from acrylic acid, methacrylic acid, maleic acid, hydroxyethyl acrylate phosphoric acid ester, and / or hydroxyethyl methacrylate phosphoric acid ester, hydroxyethyl acrylate phosphoric acid diester, and / or hydroxyethyl methacrylate phosphoric acid diester, and (ii) structural units with polyether side chains, wherein the structural units are derived from C1-C4-alkyl polyethylene glycol acrylic esters, polyethylene glycol acrylic esters, C1-C4-alkyl polyethylene glycol methacrylic acid esters, polyethylene glycol methacrylic acid esters, C1-C4-alkyl polyethylene glycol acrylic esters, polyethylene glycol acrylic esters, vinyloxy-C2-C4-alkylene polyethylene glycol, vinyloxy-C2-C4-alkylene polyethylene glycol-C1-C4-alkyl ether, allyloxypolyethylene glycol. Allyloxypolyethylene glycol C 1 -C 4 alkyl ether, methallyloxypolyethylene glycol, methallyloxypolyethylene glycol C 1 -C 4 alkyl ether,Isoprenyloxypolyethylene glycol and / or isoprenyloxypolyethylene glycol-C1-C4 alkyl ether,

[0064] Preferably, the comb polymer is composed of structural units (i) and (ii) derived from (i) Hydroxyethyl acrylate phosphoric acid esters and / or hydroxyethyl methacrylate phosphoric acid esters and (ii) C1-C4-alkyl polyethylene glycol acrylic acid esters and / or C1-C4-alkyl polyethylene glycol methacrylic acid esters; or (i) acrylic acid and / or methacrylic acid and (ii) C1-C4-alkyl polyethylene glycol acrylic acid esters and / or C1-C4-alkyl polyethylene glycol methacrylic acid esters; or (i) acrylic acid, methacrylic acid and / or maleic acid and (ii) vinyloxy-C2-C4-alkylene polyethylene glycol, allyloxy-polyethylene glycol, methallyloxy-polyethylene glycol and / or isoprenyloxy-polyethylene glycol.

[0065] Preferably, the comb polymer is composed of structural units (i) and (ii) derived from (i) Hydroxyethyl methacrylate phosphate ester and (ii) C1-C4-alkyl polyethylene glycol methacrylic acid ester or polyethylene glycol methacrylic acid ester; or (i) methacrylic acid and (ii) C1-C4-alkyl polyethylene glycol methacrylic acid ester or polyethylene glycol methacrylic acid ester; or (i) acrylic acid and maleic acid and (ii) vinyloxy-C2-C4-alkylene polyethylene glycol or (i) acrylic acid and maleic acid and (ii) isoprenyloxy-polyethylene glycol or (i) acrylic acid and (ii) vinyloxy-C2-C4-alkylene polyethylene glycol or (i) acrylic acid and (ii) isoprenyloxy-polyethylene glycol or (i) acrylic acid and (ii) methalyloxy-polyethylene glycol or (i) maleic acid and (ii) isoprenyloxy-polyethylene glycol or (i) maleic acid and (ii) allyloxy-polyethylene glycol or (i) maleic acid and (ii) methalyloxy-polyethylene glycol

[0066] Preferably the molar ratio of the structural units (I) : (II) is 1 : 4 to 15 : 1, in particular 1 : 1 to 10 : 1.

[0067] Preferably the molecular weight of the polyether side chains is >500 g / mol, preferably >3000 g / mol and <8000 g / mol, preferably <6000 g / mol.

[0068] Preferably, the molecular weight of the polyether side chains is in the range of 2000-8000 g / mol, in particular 4000-6000 g / mol.

[0069] In one embodiment, the comb polymer is a polycondensation product comprising structural units (III) and (IV): wherein T represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaromatic group with 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O, and S; n represents 1 or 2; B represents N, NH, or O, with the proviso that n represents 2 when B represents N and that n represents 1 when B represents NH or O; A represents C₆H₂ₓ with x = 2, 3, 4, or 5 or CH₂CH(C₆H₅); a represents an integer from 1 to 300, preferably 5 to 150; R 25< stands for H, a branched or unbranched C 1 - to C 10 alkyl group, C 5 - to C 8 cycloalkyl group, aryl group, or heteroaryl group with 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O and S; where structural unit (IV) is selected from structural units (IVa) and (IVb) wherein D represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted heteroaromatic group with 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O, and S; E represents N, NH, or O, with the proviso that m represents 2 when E represents N and that m represents 1 when E represents NH or O; A represents C₆H₂ₓ with x = 2, 3, 4, or 5 or CH₂CH(C₆H₅); b represents an integer from 1 to 300, preferably 1 to 50; M represents, independently of each other, H, a cation equivalent; and wherein V represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group, wherein V is optionally substituted by one or two groups selected independently from among R< , OH, OR< , (CO)R< , COOM, COOR< , SO3R< , and NO2, preferably OH, ; OC1-C4-alkyl and C1-C4-alkyl; R7 represents COOM, OCH2COOM, SO3M or OPO3M2; M represents H or a cation equivalent; wherein the aforementioned phenyl, naphthyl or heteroaromatic residues are optionally substituted by one or two residues selected from R 8< , OH, OR 8< , (CO)R 8< , COOM, COOR 8< , SO 3 R 8< and NO 2 ; and R 8< stands for C 1 -C 4 alkyl, phenyl, naphthyl, phenyl-C 1 -C 4 alkyl or C 1 -C 4 alkylphenyl.

[0070] In general formula (III), a preferably represents an integer from 1 to 300, and particularly 5 to 150, and in general formula (IV), b preferably represents an integer from 1 to 300, particularly 1 to 50, and particularly preferably 1 to 10. Furthermore, the residues of general formulas (III) or (IV) can each independently have the same chain length, with a and b each being represented by a number. It will generally be advantageous if mixtures with different chain lengths are present, so that the residues of the structural units in the polycondensation product have different numerical values ​​for a and independently for b.

[0071] Preferably in formula III T stands for a substituted or unsubstituted phenyl or naphthyl group, A for C x H 2x with x = 2 and / or 3, a for an integer from 1 to 150, and R 25< for H, or a branched or unbranched C 1 to C 10 alkyl group.

[0072] Preferably in formula IVa, D represents a substituted or unsubstituted phenyl or naphthyl group, E represents NH or O, A represents C x H 2x with x = 2 and / or 3, and b represents an integer from 1 to 150.

[0073] Preferably, T and / or D represent phenyl or naphthyl substituted by 1 or 2 C 1 -C 4 alkyl, hydroxy or 2 C 1 -C 4 alkoxy groups.

[0074] Preferably, V stands for phenyl or naphthyl substituted by 1 or 2 C 1 -C 4 alkyl, OH, OCH 3 or COOM, and R 7< for COOM or OCH 2 COOM.

[0075] The structural units T and D in the general formulas (III) and (IV) of the polycondensation product are preferably derived from phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, naphthyl, 2-hydroxynaphthyl, 4-hydroxynaphthyl, 2-methoxynaphthyl, 4-methoxynaphthyl, phenoxyacetic acid, salicylic acid, preferably from phenyl, wherein T and D can be chosen independently of one another and can also each be derived from a mixture of the aforementioned groups. Groups B and E preferably represent O independently of one another. All structural units A can be the same or different both within individual polyether side chains and between different polyether side chains. In a particularly preferred embodiment, A represents C₂H₄.

[0076] It is advantageous to have a relatively high proportion of structural units (IV) in the polycondensation product, since a relatively high negative charge of the polymers has a positive influence on the stability of the aqueous colloidally dispersed preparation. The molar ratio of structural units (IVa):(IVb), when both are present, is typically 1:10 to 10:1 and preferably 1:3 to 3:1.

[0077] In certain embodiments, the polycondensation product comprises a further structural unit (V) of the formula wherein R 5< and R 6< may be the same or different and for H, CH 3 , COOH or a substituted or unsubstituted phenyl or naphthyl group or for a substituted or unsubstituted heteroaromatic group with 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O and S.

[0078] R5< and R6< can be the same or different and represent H, CH3, or COOH, in particular H or one of the R5< and R6< groups representing H and the other CH3. Typically, R5< and R6< in structural unit (V) are the same or different and represent H, COOH, and / or methyl. H is particularly preferred.

[0079] The polycondensates are typically produced by a process involving the reaction of the compounds underlying structural units (III), (IV), and (V). The production of the polycondensates is described, for example, in WO 2006 / 042709 and WO 2010 / 026155.

[0080] Preferably, the monomer with a keto group is an aldehyde or ketone. Examples of monomers of formula (V) are formaldehyde, acetaldehyde, acetone, glyoxylic acid and / or benzaldehyde. Formaldehyde is preferred.

[0081] In general, the polycondensation product has a weight-average molecular weight of 5,000 g / mol to 200,000 g / mol, preferably 10,000 to 100,000 g / mol and particularly preferably 15,000 to 55,000 g / mol.

[0082] Preferably the molar ratio of the structural units (III) : (IV) is 4 : 1 to 1 : 15, in particular 2 : 1 to 1 : 10.

[0083] Preferably the molar ratio of the structural units (III + IV) : (V) is 2:1 to 1:3, in particular 1:0.8 to 1:2.

[0084] In preferred embodiments, the comb polymer is composed of structural units of formulas (III) and (IV), wherein T and D represent phenyl or naphthyl, the phenyl or naphthyl being optionally substituted by 1 or 2 C1-C4 alkyl, hydroxy or 2 C1-C4 alkoxy groups, B and E represent O, A represents CxH2x with x = 2, a represents 3 to 150, in particular 10 to 150, and b represents 1, 2 or 3.

[0085] In certain embodiments, a homopolymer containing units containing sulfo and / or sulfonate groups or units containing carboxylic acid and / or carboxylate groups, or a copolymer comprising units containing sulfo and / or sulfonate groups and units containing carboxylic acid and / or carboxylate groups, is used as a polymeric dispersant.

[0086] For example, the sulfo- and / or sulfonate group-containing units are vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 4-vinylphenylsulfonic acid units or structural units of formula (VI) , in which R 1< stands for H or CH 3, R 2< , R 3< and R 4< independently stand for H or straight-chain or branched C 1 -C 6 -alkyl or C 6 -C 14 -aryl, M stands for H or a cation, in particular a metal cation, preferably a monovalent or divalent metal cation, or an ammonium cation, a stands for 1 or 1 / valence of the cation, in particular 1 / 2 or 1.

[0087] Preferably, the sulfo- and / or sulfonate group-containing units are vinylsulfonic acid, methallylsulfonic acid and / or 2-acrylamido-2-methylpropylsulfonic acid units, in particular 2-acrylamido-2-methylpropylsulfonic acid units.

[0088] Preferably, the units containing carboxylic acid and / or carboxylate groups are acrylic acid, methacrylic acid, 2-ethylacrylic acid, vinylacetic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and / or citraconic acid units, and in particular acrylic acid and / or methacrylic acid units.

[0089] The molecular weight Mw of the copolymer is preferably in the range of 1,000 to 50,000, determined by aqueous gel permeation chromatography.

[0090] In particularly suitable embodiments, the dispersing agent is selected from: Copolymers comprising structural units of formulas (1a) and (IIa), in particular copolymers comprising structural units derived from acrylic acid and / or methacrylic acid and ethoxylated hydroxyalkyl vinyl ethers, such as ethoxylated hydroxybutyl vinyl ether; copolymers comprising structural units of formulas (1a), (Id) and (1a), in particular copolymers comprising structural units derived from acrylic acid and / or methacrylic acid, maleic acid and ethoxylated hydroxyalkyl vinyl ethers, such as ethoxylated hydroxybutyl vinyl ether; copolymers comprising structural units of formulas (1a) and (IIc), in particular copolymers comprising structural units derived from acrylic acid and / or methacrylic acid and esters of acrylic acid or methacrylic acid with polyethylene glycol or polyethylene glycol end-sealed with C1-C12 alkyl;Polycondensation products comprising structural units (III), (IVa) and (V), in particular condensation products of ethoxylated phenol, phenoxy-C2-C6-alkanol phosphate and formaldehyde; homopolymers comprising units containing sulfo- and / or sulfonate groups or units containing carboxylic acid and / or carboxylate groups; copolymers comprising units containing sulfo- and / or sulfonate groups and units containing carboxylic acid and / or carboxylate groups; and / or polyacrylic acid; and the salts thereof and combinations of two or more of these dispersants.

[0091] In one embodiment, at least one additional dispersing agent is used, which is selected from lignosulfonates, melamine-formaldehyde sulfonate condensates, β-naphthalenesulfonic acid condensates, phenolsulfonic acid condensates and sulfonated ketone-formaldehyde condensates.

[0092] The molar ratio of the structural units (III) : (IV) is typically 4 : 1 to 1 : 15 and preferably 2 : 1 to 1 : 10.

[0093] In a preferred embodiment, the polycondensation product contains a further structural unit (V) which is represented by the following formula: wherein R 5< stands for H, CH 3 , COOH or substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl; R 6< stands for H, CH 3 , COOH or substituted or unsubstituted phenyl or substituted or unsubstituted naphthyl.

[0094] The comb polymer can also be in the form of its salts, such as the sodium, potassium, organic ammonium, ammonium and / or calcium salts, preferably as the sodium and / or calcium salt.

[0095] The molecular weight of the polymeric dispersant, determined by gel chromatography with polystyrene as a standard, is generally in the range of 5,000 to 100,000. The molecular weight of the side chains is generally in the range of 1,000 to 10,000.

[0096] The charge density of the polymers is generally in the range of 500 µeq / g to 1,500 µeq / g.

[0097] Preferred polymeric dispersants are: Copolymers comprising structural units of formulas (1a) and (IIa), in particular copolymers comprising structural units derived from acrylic acid and / or methacrylic acid and ethoxylated hydroxyalkyl vinyl ethers, such as ethoxylated hydroxybutyl vinyl ether; copolymers comprising structural units of formulas (1a), (Id) and (IIa), in particular copolymers comprising structural units derived from acrylic acid and / or methacrylic acid, maleic acid and ethoxylated hydroxyalkyl vinyl ethers, such as ethoxylated hydroxybutyl vinyl ether; copolymers comprising structural units of formulas (1a) and (IIc), in particular copolymers comprising structural units derived from acrylic acid and / or methacrylic acid and esters of acrylic acid or methacrylic acid with polyethylene glycol or polyethylene glycol end-sealed with C1-C12 alkyl;Polycondensation products comprising structural units (III), (IVa) and (V), in particular condensation products of ethoxylated phenol, phenoxy-C2-C6-alkanol phosphate and formaldehyde; homopolymers comprising units containing sulfo- and / or sulfonate groups or units containing carboxylic acid and / or carboxylate groups; copolymers comprising units containing sulfo- and / or sulfonate groups and units containing carboxylic acid and / or carboxylate groups; and / or polyacrylic acid; and the salts thereof and combinations of two or more of these dispersants. Bringing the mineral component into contact with the water-soluble polymeric dispersant

[0098] To produce the composition containing calcium silicate hydrate, the mineral component is brought into contact with at least one water-soluble polymeric dispersant in an aqueous medium.

[0099] For contact with the polymeric dispersant, the mineral component can be used in the form of a suspension or as a dry powder. The polymeric dispersant is then added to the suspension containing the mineral component, either as a solid or as an aqueous solution, either all at once or in two or more portions. Preferably, however, the mineral component is added to an aqueous solution of the polymeric dispersant, either as a solid or as an aqueous suspension, all at once or in two or more portions.

[0100] In one embodiment, the weight ratio of the mineral component (calculated as the dry component) to the polymeric dispersing agent is in the range of 15:1 to 1:2, particularly in the range of 10:1 to 1:1.5, and more preferably in the range of 5:1 to 1:1. In another embodiment, the weight ratio of the mineral component (calculated as the dry component) to water is in the range of 3:1 to 1:20, particularly in the range of 1:1 to 1:10, and more preferably in the range of 2:3 to 1:5.

[0101] The determination of the dry component of the mineral constituent is carried out by drying the material at 105 °C in a laboratory oven until a constant weight is reached and the resulting loss in weight due to drying is determined.

[0102] The water content of the suspension (determined by drying the suspension at 105 °C until constant weight) when the mineral component is brought into contact with the polymeric dispersant is suitably in the range of 25 wt.% to 95 wt.%, particularly in the range of 50 wt.% to 90 wt.%, and especially preferably 60 wt.% to 80 wt.%.

[0103] Optionally, the process can be carried out with the addition of Portland cement, Portland cement clinker, and / or a latent hydraulic binder, wherein the mass fraction of Portland cement, Portland cement clinker, and / or latent hydraulic binder, based on the total amount of mineral component, is between 0.01 and 10 wt.%, preferably between 0.01 and 5 wt.%. The addition can be made before contact with the polymeric dispersant or after mechanical comminution of the mineral component.

[0104] In preferred embodiments, the process is carried out essentially without the addition of other components and in particular essentially without the addition of Portland cement, Portland cement clinker and / or ettringite.

[0105] The contact between the mineral component and the polymeric dispersant is achieved by introducing kinetic energy through grinding. Virtually all equipment known to those skilled in the art is suitable for this purpose.

[0106] In a preferred embodiment, contact is brought into contact by introducing shear energy, wherein more than 50 kWh, in particular more than 200 kWh, preferably more than 400 kWh, in particular 100 to 5,000 kWh, in particular 200 to 3,000 kWh, in particular preferably 300 to 1,000 kWh of shear energy per ton of the composition are introduced.

[0107] Shear energy is defined as the work work WW, which results from the shear power PW expended for grinding and the grinding time t according to the following equation (1): W W = P W ⋅ t

[0108] The shear power acting on the suspension is calculated as the difference between the active power Pp (power input of the device during grinding of the suspension) and the zero power Po (power input of the device at idle without suspension and possibly without grinding balls, e.g., in the case of a bead mill, ball mill, or toothed colloid mill) using the following equation (2): P W = P P − P 0

[0109] The zero power (equation (3a)) and the active power (equation (3b)) result from the active voltage U and the active current I, which is measured on the device during operation using an ammeter: P 0 = U 0 ⋅ I 0 ⋅ cos ϕ ; cos ϕ = 1 P P = U P ⋅ I P ⋅ cos ϕ ; cos ϕ = 1

[0110] The ratio of active power Pp to apparent power Ps of the device is given by cos φ. ϕ described by equation (4): cos ϕ = P P / P S

[0111] Since apparent power is very device-specific and active power can be easily measured (by measuring the active voltage and current), the cos φ is used to simplify the calculation. ϕ = 1 assumed.

[0112] Therefore, processes that introduce high shear energy are preferred. In particular, the introduction of shear energy can be achieved by grinding, as in a toothed colloid mill, bead mill, ball mill, or preferably a stirred ball mill. The stirred ball mill comprises a grinding chamber containing the grinding media, a stator, and a rotor, which are arranged in the grinding chamber. Furthermore, the stirred ball mill preferably includes a material inlet and a material outlet for feeding and discharging material into and out of the grinding chamber, as well as a grinding media separator arranged upstream of the outlet in the grinding chamber. This separator serves to separate any grinding media entrained in the material before the material is discharged from the grinding chamber through the outlet.

[0113] To increase the mechanical grinding power transferred to the material being ground in the grinding chamber, pins are preferably provided on the rotor and / or stator, projecting into the grinding chamber. During operation, the grinding power is thus increased directly through impacts between the material being ground and the pins. A further contribution to the grinding power is made indirectly through impacts between the pins and the grinding media carried within the material being ground, and subsequently through impacts between the material being ground and the grinding media. Finally, shear and tensile forces acting on the material being ground also contribute to the comminution of the suspended particles.

[0114] In one embodiment, contact with the polymeric dispersant is carried out in two stages. In the first stage, contact is maintained until the particle size d(99) of the mineral component is ≤ 300 µm, and in particular is in the range of 0.5 to 300 µm. This can be achieved using a device selected from a grinding device, an ultrasonic device, a rotor-stator mixing system, and a dissolver disc.

[0115] In the second stage, contact is maintained until the mineral component has a d(50) particle size of ≤ 400 nm, preferably ≤ 300 nm, particularly preferably ≤ 200 nm, determined by static light scattering. This is carried out using a grinding device.

[0116] It has proven advantageous to allow the suspension to settle for a period of 0.01 h to 48 h, preferably 4 h to 24 h, and particularly preferably 6 h to 16 h, before introducing kinetic energy. During this period, the suspension rests or is stirred in a stirred tank without exposure to high shear energy (i.e., shear energies of < 50 kWh per ton of suspension) to prevent sedimentation. If contact with the polymeric dispersant is carried out in two stages, the settling period can take place before the first stage or between the two stages.

[0117] An acidic compound with a molecular weight of at most 200 g / mol, particularly 40–100 g / mol, can be added before, during, or after contacting the mineral component with the dispersant. Preferably, the acidic compound is added after contacting the mineral component with the dispersant. The acidic compound is selected, for example, from nitric acid, sulfamic acid, methanesulfonic acid, formic acid, acetic acid, sulfuric acid, and mixtures thereof, preferably sulfamic acid, methanesulfonic acid, acetic acid, and mixtures thereof. The amount of the acidic compound is suitably selected such that, immediately after the addition of the acid (10 to 60 seconds) or after complete homogenization, the pH of the suspension is 11.0–13.0, preferably 11.4–12.5, and particularly preferably 11.8–12.4. building material mixture

[0118] The invention also relates to a building material mixture comprising the composition according to the invention containing calcium silicate hydrate and optionally a hydraulic or latent hydraulic binder, in particular Portland cement, slag, preferably granulated blast furnace slag, fly ash, silica flour, metakaolin, natural pozzolans, calcined oil shale, calcium sulfoaluminate cements and / or calcium aluminate cements.

[0119] The building material mixture according to the invention may also contain further additives that are typically used in the field of construction chemicals, such as other hardening accelerators, dispersants, liquefiers, water-reducing agents, setting retarders, defoamers, air-entraining agents, retarders, shrinkage-reducing agents, redispersible powders, antifreeze agents and / or anti-efflorescence agents.

[0120] Suitable alternative hardening accelerators are alkanolamines, preferably triisopropanolamine and / or tetrahydroxyethylethylenediamine (THEED). The alkanolamines are preferably used in a dosage of 0.01 to 2.5 wt%, based on the weight of the hydraulic binder. When using amines, especially triisopropanolamine and tetrahydroxyethylethylenediamine, synergistic effects on the early strength development of hydraulic binder systems, particularly cementitious systems, can be observed.

[0121] Other suitable hardening accelerators include, for example, calcium chloride, calcium formate, calcium nitrate, inorganic carbonates (such as sodium carbonate, potassium carbonate), 1,3-dioxolan-2-one, and 4-methyl-1,3-dioxolan-2-one. Calcium formate and calcium nitrate are preferably used in a dosage of 0.1 to 4 wt% based on the hydraulic binder.

[0122] Suitable dispersants, liquefiers, and water-reducing agents include, for example: a) sulfonated melamine-formaldehyde condensates, b) lignosulfonates, c) sulfonated ketone-formaldehyde condensates, d) sulfonated naphthalene-formaldehyde condensates (BNS), e) polycarboxylate ethers (PCE), f) non-ionic copolymers for extending the workability of a cementitious mixture containing cement and water, wherein the copolymer comprises units derived from at least the following monomer components: component A, namely an ethylene-unsaturated carboxylic acid ester monomer with a unit hydrolyzable in the cementitious mixture;and component B, namely an ethylene unsaturated carboxylic acid ester monomer or alkenyl ether monomer, comprising at least one poly-C 2-4 oxyalkylene side chain with 1 to 350 oxyalkylene units or g) phosphonate group-containing dispersing agents of the formula R-(OA) n -N-[CH 2 -PO(OM 2 ) 2 ] 2 , wherein R represents H or a saturated or unsaturated hydrocarbon residue, preferably a C 1 to C 15 alkyl residue; A may be the same or different and represents alkylenes with 2 to 18 carbon atoms, preferably ethylene and / or propylene, in particular ethylene; where n represents 5 to 500, preferably 10 to 200, in particular 10 to 100, and M represents H, an alkali metal, 1 / 2 alkaline earth metal and / or an amine, wherein each combination of the aforementioned dispersing agents comprises a) to g).

[0123] Suitable setting retarders include citric acid, tartaric acid, gluconic acid, phosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminotetra(methylenephosphonic)ic acid, and diethylenetriaminopenta(methylenephosphonic)ic acid, each including the respective salts of the acids, pyrophosphates, pentaborates, metaborates, and / or sugars (e.g., glucose, molasses). The advantage of adding setting retarders is that the open time can be controlled and, in particular, extended if necessary. Preferably, the setting retarders are used in a dosage of 0.01% to 0.5% by weight, based on the weight of the hydraulic binder, preferably cement.

[0124] The calcium silicate hydrate-containing composition exhibits a surprisingly strong acceleration effect on the hardening of hydraulic and latent hydraulic binders, particularly Portland cement. Using this composition improves the early strength of hydraulically and latently hydraulically setting binders, especially Portland cement. Furthermore, the composition possesses improved application properties, such as low viscosity in the relevant concentration ranges. It is therefore easy to handle and allows for easy pumping and spraying.

[0125] The invention further relates to the use of the compositions according to the invention for accelerating the hardening of construction chemical mixtures containing a hydraulic or latent hydraulic binder, in particular cement, slag, preferably granulated blast furnace slag, fly ash, silica flour, metakaolin, natural pozzolans, calcined oil shale, calcium sulfoaluminate cements and / or calcium aluminate cements, preferably of construction chemical mixtures which predominantly contain cement as a hydraulic binder.

[0126] The dosage of the compositions according to the invention is preferably from 0.01 wt.% to 15 wt.%, preferably 0.1 wt.% to 10 wt.%, particularly preferably 0.1 wt.% to 5 wt.% of the solid of the compositions, based on the hydraulic or latent hydraulic binder.

[0127] The invention is further illustrated by the accompanying drawings and the following examples.

[0128] Fig. 1 shows X-ray diffraction spectra of samples containing (i) crystalline tobermorite 14 Å (crystallite size 50 nm), (ii) amorphous calcium silicate hydrate (tobermorite 14 Å; crystallite size 0.5 nm) and an X-ray diffraction spectrum of a semi-ordered calcium silicate hydrate (htCSH3) suitable according to the invention after Rietveld analysis.

[0129] Fig. 2 shows X-ray diffraction spectra of a hydrothermal calcium silicate hydrate (htCSH1, comparison) and two semi-ordered calcium silicate hydrates suitable according to the invention (htCSH2 and htCSH3).

[0130] The distinguishable peaks or maxima were assigned to the phases; the abbreviations mean: P - portlandite Cc - calcite Qz - alpha quartz T - tobermorite 14 Å sCSH - semi-ordered calcium silicate hydrate aCSH - amorphous calcium silicate hydrate Xo - xonotlite

[0131] According to Fig. 1Crystalline tobermorite exhibits a well-resolved spectrum with sharp peaks; in the spectrum of amorphous calcium silicate hydrate, no maxima attributable to a crystalline calcium silicate hydrate phase are present. The contribution of amorphous calcium silicate hydrate to the X-ray diffraction spectrum is noticeable by an increased background, particularly in the 2θ region between 25° and 35° (Cu Kα). The semi-ordered calcium silicate hydrate suitable according to the invention shows a broadening and overlapping of the tobermorite maxima by 2θ = 30°; the individual peaks are no longer resolved.

[0132] According to Fig. 2 The hydrothermal calcium silicate hydrate htCSH1 exhibits a well-resolved spectrum with sharp xonotlite peaks. The semi-ordered calcium silicate hydrates htCSH2 and htCSH3 suitable according to the invention show broad maxima around 2θ = 30°. Examples Determination methods

[0133] (i) Particle size of the raw material (mineral component): The particle size of the raw material for wet milling was characterized by static light scattering using the Malvern Mastersizer 2000 instrument. (ii) Determination of the specific surface area according to BET: The specific surface area according to BET of the raw material for wet milling was determined by nitrogen adsorption using the Quantachrome NOVA 4000e Surface Area and Pore Size Analyzer. Samples were pre-dried at 105 °C until constant weight was achieved. (iii) X-ray diffraction (XRD) and Rietveld analysis to determine the X-ray amorphous fraction and crystallite size of the calcium silicate hydrate: The XRDs were performed using a Bruker AXS D4 ENDEAVOR (CuK α - radiation, 40 kV, 40 mA) and the Rietveld measurements were carried out using Bruker's Topas 4.2 software.

[0134] For XRD analysis, the hydrothermal CSH from the autoclave process was crushed to a particle size with a d(95) value of ≤ 1 mm using a jaw crusher and a counter-impact mill. Subsequently, 5 g of the powder were dried in a laboratory oven at 105 °C for 1 h.

[0135] For the XRD analysis, 2 g of the dried powder were ground in an agate mortar until the sample could be completely passed through a sieve with a mesh size of 36 µm.

[0136] The sample used to determine the proportion of the X-ray amorphous phase was a homogeneously mixed powder containing the sample and a known amount of an internal crystalline standard. For these investigations, 15 wt% to 30 wt% fluorite (CaF₂) was homogeneously ground with the sample (particle size < 36 µm) in an agate mortar.

[0137] The homogenized powder, containing fluorite as an internal standard, was then prepared and measured using front loading. A prerequisite for using fluorite as an internal standard is that fluorite is not present in the original sample. A standard with a mass attenuation coefficient (MAC) similar to that of the sample must be selected to minimize X-ray adsorption contrast. The samples have a MAC value for Cu K α Radiation between 75 and 80 cm² / g. Therefore, CaF₂ with a MAC value of 94.96 cm² / g was chosen. According to the scientific literature, approximately 20 wt% of the internal standard is recommended for an amorphous fraction of the sample to be analyzed between 30 and 90% (Scrivener, Snellings, and Lothenbach. "Chapter 4. X-Ray Powder Diffraction Applied to Cement." A Practical Guide to Microstructural Analysis of Cementitious Materials. CRC / Taylor & Francis Group, 2016. 107-176). The samples analyzed contain 10 wt% to 70 wt% of X-ray amorphous or nanocrystalline phases with crystallite sizes < 5 nm, so 15 wt% and 30 wt% of internal standard were used, respectively.

[0138] The X-ray diffraction diagrams (diffractograms) recorded by X-ray diffraction analysis were subsequently evaluated using Rietveld analysis with the Topas 4.0 software. The Rietveld method is a standard procedure for evaluating diffractograms obtained by X-ray diffraction analysis of powder samples. The method is described in detail, for example, in G. Will (2006): Powder Diffraction - The Rietveld method and the two-stage method, Springer Verlag, and R. Young (1995): The Rietveld method, IUCr Monographs on Crystallography, vol. 5, Oxford University Press.

[0139] For the Rietveld analysis of the samples presented here, the following structural data from the Inorganic Crystal Structure Database (ICSD) were used: Tobermorite (mineral of calcium silicate hydrates): ICSD number 152489; Calcite: ICSD number 79674; Quartz: ICSD number 174; Portlandite: ICSD number 15471; Fluorite: ICSD number 60368

[0140] Using Rietveld analysis, the crystallite size of the calcium silicate hydrate phase tobermorite was determined in addition to the phase content of the individual phases. The crystallite size is reflected in the full width at half maximum (FWHM) of the reflections of a phase and is determined during the refinement process of the Rietveld analysis. The relationship between the FWHM of a reflection in the diffractogram and the crystallite size is described, for example, in Chapter 5.4.1 from page 142 in R. Dinnebier, S. Billinge (2008): Powder Diffraction - Theory and Practice, RSC Publishing, as well as on page 113 in G. Will (2006): Powder Diffraction - The Rietveld method and the two-stage method, Springer Verlag, and R. Young (1995): The Rietveld method, IUCr Monographs on Crystallography, vol. 5, Oxford University Press.

[0141] The determination of the proportion of the X-ray amorphous phase using an internal standard serves to quantify the absolute amount of the crystalline and X-ray amorphous phases and was carried out according to the publication by I. Madsen, N. Scarlett, and A. Kern, "Description and survey of methodologies for the determination of amorphous content via X-ray powder diffraction." Zeitschrift für Kristallographie Crystalline Materials 226.12 (2011): 944-955. During the Rietveld refinement, the known proportion of the internal standard is specified, and the other phases are related to it. The difference between the sum of the crystalline phases (tobermorite, calcite, quartz, portlandite, fluorite) and 100 wt% corresponds to the X-ray amorphous content of the sample. (iv) The charge density was determined by titration with poly-DADMAC (poly(diallyldimethylammonium chloride)) or sodium polyethylene sulfonate using a Mettler Toledo DL 28 titrator combined with a BTG Mütek particle charge detector. (v) To determine the viscosity, the suspensions were stored sealed at room temperature for 24 h after milling. The viscosity was then determined on a Brookfield DV-II+ viscometer at 12 rpm with a 62 mm spindle. (vi) The weight-mean molecular weight of the polymeric dispersant was determined by gel permeation chromatography (GPC) (column combinations: OH-Pak SB-G, OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Shodex, Japan; eluent: 80 vol% aqueous solution of HCO₂₂NH₄ (0.05 mol / l) and 20 vol% Acetonitrile; injection volume 100 µl; flow rate 0.5 ml / min). Calibration for determining the mean molar mass was performed using linear poly(ethylene oxide) and polyethylene glycol standards.. Production of polymeric dispersants: Polymers 1, 2 and 7

[0142] In a 1-liter four-necked flask equipped with a thermometer, reflux condenser, and two inlets, 875 g of a 40% aqueous solution of polyethylene glycol hydroxybutyl monovinyl ether and 20% NaOH are placed. Details regarding the molar masses of the respective polyethylene glycol hydroxybutyl monovinyl ethers can be found in Table 2. The solution is then cooled to 20 °C. Acrylic acid (99%) is then slowly added to the polyethylene glycol hydroxybutyl monovinyl ether solution in the receiving flask. The pH decreases to approximately 4–5. Next, 0.5 g of iron(II) sulfate heptahydrate, 5 g of Rongalit, and mercaptoethanol are added. After brief stirring, 3 g of 50% hydrogen peroxide are added. The temperature rises from 20 °C to approximately 30 °C to 65 °C. The solution is then stirred for 10 minutes before being neutralized with sodium hydroxide solution (20%).A light yellow, clear aqueous polymer solution with a solids content of approximately 40 wt% is obtained. The quantities of the chemicals used (NaOH, mercaptoethanol, and acrylic acid), as well as the molar masses of the respective polyethylene glycol-hydroxybutyl monovinyl ether (PEG-HBVE), weight-average molar mass, and charge density of the polymer (number of moles of carboxylate and / or carboxyl groups / total molar mass of the PCE) (mol / (g / mol)) can be found in Tables 1 and 2 below. Table 1: Details on the production of P1, P2 and P7 polymer NaOH (20%) [g] Mercaptoethano l [g] Acrylic acid (99%) [g] P1 40 1,5 30,8 P2 10 1,7 42,4 P7 0 0,9 21,9 Table 2: Overview of the structural parameters of the polymers polymer Charge density (µeq / g) M w (g / mol) Molar mass of PEG-HBVE (g / mol) P1 1110 28537 5800 P2 1488 28659 3000 P7 811 35665 5800 Polymer P3

[0143] Polymer P3 is a comb polymer based on the monomers maleic acid, acrylic acid, and vinyloxybutyl polyethylene glycol (5800). The molar ratio of acrylic acid to maleic acid is 7. The molecular weight (Mw) is 40,000 g / mol and was determined by GPC. The solids content is 45 wt.%. The synthesis is described, for example, in EP 0894811. The charge density is 930 µeq / g. Polymer P4

[0144] Polymer P4 is a condensate of the building blocks phenolPEG5000, phenoxyethanol phosphate, and formaldehyde. Its molecular weight (MW) is 25,730 g / mol. The polymer was prepared according to Polymer 7 of WO 2015 / 091461 (Tables 1 and 2). Polymer P5

[0145] Polymer P5 is a comb polymer polymerized from a hydroxyethyl methacrylate phosphoric acid ester and an ester of methacrylic acid and methyl polyethylene glycol with a molecular weight of 5,000 g / mol. The synthesis was carried out according to the preparation of P1 from WO 2014 / 026938. The molecular weight MW is 3,660 g / mol. The solids content of the polymer solution is 29 wt%. Polymer P6

[0146] Polymer 6 is a commercially available polyacrylate partially neutralized with NaOH (degree of neutralization 80%). Its mean molecular weight (MW) is 5,000–10,000 g / mol. The solids content of the polymer solution is 45 wt%. Hydrothermal calcium silicate hydrate (htCSH)

[0147] htCSH1: Circolit, available from Cirkel GmbH & Co. KG, Haltern am See. htCSH2:

[0148] To produce htCSH2, 153 kg of quartz flour (d(95) < 63 µm, SiO2 content > 95 wt%), 150 kg of quicklime (d(95) < 90 µm, CaO content > 90 wt%), 222 g of aluminum paste (water content = 40%, d(50) = 15 µm), and 340 kg of water were mixed. This suspension was allowed to stand for 3 hours at a temperature of 20 °C. The material was then held in an autoclave at 150 °C (approx. 5 bar) for 8 hours. Afterward, the material was cooled to room temperature and further reduced in size using crushers and ball mills to a particle size of d(95) < 1 mm and d(50) < 500 µm. The moisture content (determined by drying at 105 °C until constant weight) was 36.6 wt.%. htCSH3:

[0149] To produce htCSH3, 100 kg of quartz flour (d(95) < 63 µm, SiO₂ content > 95 wt%), 200 kg of quicklime (d(95) < 90 µm, CaO content > 90 wt%), 222 g of aluminum paste (water content = 40%, d(50) = 15 µm), and 410 kg of water were mixed. This suspension was allowed to stand for 3 h at a temperature of 20 °C. The material was then held in an autoclave at 170 °C (approx. 8 bar) for 12 h. Afterward, the material was cooled to room temperature and further reduced in size using crushers and ball mills to a particle size of d(95) < 1 mm and d(50) < 500 µm. The moisture content (determined by drying at 105 °C until constant weight) was 40.0 wt.%.

[0150] The raw materials used have the following properties (Table 3): Table 3 type htCSH1 htCSH2 htCSH3 Composition (in wt.%) (1) CSH component CSH phase Xonotlit Tobermorit 14Å (based on CSH phase) Tobermorit 14Å (based on CSH phase) 84,5 14,6 23,3 X-ray amorphous component 12,5. 51,1 60,6 Crystalline foreign substance component quartz and 27,3 4,5 Portlandite and 2,6 7,0 Calcite 3,0 2,7 4,6 Characteristics Crystallite size CSH phase 33 nm 3.6 nm 3.6 nm Particle size distribution d(10) in µm 1 7 6 d(50) in µm 7 101 109 d(90) in µm 21 217 227 BET surface 38 cm² / g 113 cm² / g 113 cm² / g molar ratio Ca / Si (3)< 1,09 * 0,89 (2)< 1,77 (2)< nd: not determinable (content is below the detection limit) * determined from product data sheets (1)< From XRD with subsequent Rietveld analysis (2)< Determined by X-ray fluorescence analysis (XRF) (3)< from the total amount of inorganic components of the hydrothermal CSH

[0151] The wet milling of the hydrothermally produced calcium silicate hydrate was carried out using a shaking setup (Fast & Fluid Management SK 300 vibrator). The conditions for the individual wet milling operations are listed in Table 4. For milling, 100 g of the suspension, according to the parameters in Table 4, were placed in 250 ml glass bottles filled with 500 g of ZrO₂ grinding beads with a diameter of 1 mm. Milling took place at stage 3 with an active power I₀ of 1281.1 W. Between the preparation of the suspensions (mixing hydrothermal CSH, water, and water-soluble polymer) and the actual wet milling under high shear energy, the suspensions were allowed to rest for 30 minutes without additional mechanical shearing. After milling, the suspensions were separated from the grinding beads by sieving and partially rinsed with distilled water.The solids content of the suspension was subsequently determined by drying the suspension at 60 °C until a constant weight was achieved.

[0152] For comparison with the state of the art, three suspensions were prepared by precipitation according to WO 2010 / 026155 (pptCSH). These contain amorphous CSH nuclei stabilized by the polymer. Table 4 Example Starting material Hydrothermal CSH content (wt%) polymer Polymer content (solid) in suspension (wt%) Solids content after milling (1) < (wt%) Meal time (min) Shear energy (kWh / t) S1* htCSH1 15 - - 15.26 180 604 S2* htCSH1 15 P4 2.5 17.67 180 604 S3* htCSH1 15 P1 2.5 17.63 180 604 S4* htCSH1 15 P3 2.5 17.69 180 604 S5* htCSH1 15 P6 2.5 17.48 180 604 S6* htCSH1 15 P5 2.5 17.73 180 604 S7 htCSH2 15 P1 2,5 11.22 180 604 S8 htCSH2 15 P1 3,5 12.38 180 604 S9 htCSH2 15 P1 7,5 15.79 180 604 S10 htCSH3 15 P1 2,5 11.56 180 604 S11 htCSH3 15 P1 3,5 12.70 180 604 S12 htCSH3 15 P1 7,5 16.27 180 604 S13 htCSH3 13,91 P7 2,8 15.22 20 67 S14 htCSH3 13,91 P7 2,8 16.72 60 201 S15 htCSH3 13,91 P7 2,8 16.86 120 402 S16* pptCSH -- P7 2,8 17.92 (2)< 20 67 S17* pptCSH -- P7 2,8 18.01 (2)< 60 201 S18* pptCSH -- P7 2,8 18.22 (2)< 120 402 (1) The solids content of the suspension after milling was determined by drying 1 g of suspension at 60 °C in a drying oven until a constant weight was achieved. (2) Before viscosity measurement, the samples were diluted with water to a solids content of 15 wt.%. * Comparative example.

[0153] For comparison with the prior art according to WO 2010 / 026155, 3 suspensions (S16, S17, S18) and 3 suspensions according to the invention (S13, S14, S15) were produced, wherein in examples S13 to S18, 194 g of suspension were ground in the 250 ml bottles with a grinding ball quantity of 500 g.

[0154] For the preparation of S16 to S18, 15.5 g of Ca(OH) 2 (Merck, CAS 1305-62-0, purity > 97%) and 12.1 g of SiO 2 (Silica, fumed; CAS 112945-52-5, Sigma Aldrich, purity > 99.9%) were mixed with water and polymer (see Table 2 above), resulting in a total mass of suspension of 194 g.

[0155] To determine the shear energy, the current in operation of the SK 300 vibrator was measured using a Metrix MX 350 AC multimeter. The current was measured during empty operation I 0 (vibration without grinding beads or material) and during grinding operation IP (vibration with filled glass bottles containing grinding beads and material). The operating voltage was 230 V in both cases.

[0156] The active power I0 resulting from the measured currents was 1281.1 W, while the active power IP during grinding operation for grinding 400 g of suspension was 1361.6 W. This results in a required active power PW of 201.25 W for grinding 1 kg of suspension.

[0157] The polymer content in the suspension always refers to the solids content of the polymer used.

[0158] The suspensions were characterized with regard to acceleration effect using heat flow calorimetry and with regard to viscosity using Brookfield viscometers. Heat flow calorimetry:

[0159] To determine the acceleration performance of the accelerator suspensions, cement pastes containing the accelerator suspensions were prepared, and their hydration kinetics were measured using isothermal heat flow calorimetry. For this purpose, 100 g of Portland cement (CEM I 52.5 R) was mixed with 40 g of water using an overhead stirrer for 90 seconds at 500 rpm. The suspension to be tested was added to the cement along with the mixing water, with the amount of mixing water then adjusted to match the amount of water in the suspension, resulting in a water / cement ratio of 0.4 for each test. The amounts of the suspension to be tested are listed in Table 5.

[0160] Six grams of mortar or cement paste were then placed into the measuring vessel, which was then inserted into the calorimeter. Isothermal heat flow calorimetry was performed using the TAMair calorimeter from TA Instruments at 20 °C.

[0161] The cumulative heat of hydration was determined after 6 hours. Furthermore, for comparison of the samples, the maximum slopes in heat flow between 2 and 8 hours were determined and related to the slope of the reference measurement (cement + water). The determination of the relative slope was carried out according to the publication by L. Nicoleau (2012) (L. Nicoleau: The acceleration of cement hydration by seeding: Influence of the cement mineralogy. Ibausil 18th International Building Materials Conference in Weimar (2012), Proceedings, pages 1-0330 - 1-0337). The results of the calorimetric measurements are summarized in Table 5 below. Table 5 Acceleration suspension Viscosity Suspension (mPas) Amount of suspension added based on cement (wt.%) Amount of CSH starting material added, based on cement HoH after 6 h [J / g cement] Acceleration factor without - 23,25 1,00 S1 >100.000 3,28 0.5% by mass 38,08 1,11 S1 >100.000 6,55 1.0 wt.% 46,89 1,11 S2 85 3,30 0.5% by mass 41,52 1,30 S2 85 6,60 1.0 wt.% 49,83 1,54 S3 30 3,31 0.5% by mass 42,07 1,39 S3 30 6,62 1.0 wt.% 53,18 1,83 S4 20 3,30 0.5% by mass 41,82 1,37 S4 20 6,60 1.0 wt.% 51,87 1,65 S5 3 3,34 0.5% by mass 33,41 1,35 S5 3 6,68 1.0 wt.% 36,38 1,61 S6 7.5 3,29 0.5% by mass 33,83 1,20 S6 7.5 6,58 1.0 wt.% 41,04 1,41 S7 10 5,20 0.5% by mass 48,32 1,85 S7 10 10,40 1.0 wt.% 59,95 2,37 S8 20 4,98 0.5% by mass 44,66 1,87 S8 20 9,96 1.0 wt.% 54,99 2,26 S9 30 4,75 0.5% by mass 33,32 1,50 S9 30 9,50 1.0 wt.% 36,27 1,70 S10 15 5,05 0.5% by mass 57,74 2,13 S10 15 10,09 1.0 wt.% 69,02 2,70 S11 15 4,85 0.5% by mass 55,01 2,22 S11 15 9,71 1.0 wt.% 67,23 2,65 S12 20 4,61 0.5% by mass 41,01 2,26 S12 20 9,22 1.0 wt.% 45,66 2,52 S13 18 9,86 1.25% by mass 51,30 1,42 S14 20 8,97 1.25% by mass 59,42 1,67 S15 35 8,90 1.25% by mass 65,31 1,79 S16 >100.000 8,37 1.25% by mass 64,91 1,65 S17 >100.000 8,33 1.25% by mass 68,95 1,80 S18 >100.000 8,23 1.25% by mass 66,58 1,69 HoH: cumulative heat of hydration after 0.5 h of hydration.

[0162] A viscosity of > 100,000 means that the viscosity was not measurable because a solid gel had formed.

Claims

1. composition suitable for accelerating the hardening of construction chemical mixtures, containing a hydraulic or latent hydraulic binder, comprises a mineral constituent and a polymeric water-soluble dispersant, wherein the mineral constituent is a semi-ordered calcium silicate hydrate with an apparent Kristallitgror.ie of 1 to 15 nm, which is determined by X-ray diffraction and Rietveld analysis and contains less than 35 wt. %, in relation to the dry weight of the mineral component, in crystalline phases that are not calcium silicate hydrate phase (C-S-H), wherein "semi-ordered" is understood to mean that the calcium silicate hydrate (1) has a lower degree of order than a macroscopic crystalline calcium silicate hydrate and (2) a higher degree of order than amorphous calcium silicate hydrate, and where the main diffraction peak of the semi-ordered calcium silicate hydrate in the X-ray diffraction diagram has a half-width that is at least 1.25 times the half-width of the corresponding main diffraction peak of the crystalline form with a Kristallitgror.ie of 50 nm or greater.

2. The composition according to claim 1, wherein the molar ratio of calcium to silicon in the mineral component in the range of 0.5 to 2.5, preferably 0.8 to 2.2, especially preferably 1.0 to 2.0 or 1.6 to 2.0.

3. The composition according to claim 1 or 2, comprising 2% or less alkali metals by weight in relation to the mineral constituent.

4. composition according to any of the preceding claims, wherein the specific BET surface of the mineral component is in the range of 30 to 150 m2 / g, preferably 80 to 150 m2 / g, in particular 90 to 150 m2 / g, especially preferably 100 to 150 m2 / g, determined according to DIN ISO 9277:2003-05.

5. Process for the preparation of a composition containing calcium silicate hydrate, wherein a mineral constituent is brought into contact with at least one water-soluble polymeric dispersant in an aqueous medium by the introduction of kinetic energy, wherein the mineral constituent is a Semi-ordered calcium silicate hydrate with an apparent Kristallitgror.ie of 1 to 15 nm and less than 35 % by weight, based on the dry weight of the mineral constituent, in crystalline phases which are not calcium silicate hydrate phase (C-S-H), wherein the mineral constituent is formed by reaction of calcium oxide or calcium hydroxide with silicon dioxide in the presence of water under hydrothermal conditions at a temperature in the range of 100 °C to 400 °C over a period of 5 h to 30 h, wherein the contact of the mineral component with the water-soluble polymer dispersant by grinding.

6. The method of claim 5, wherein the mineral component is prepared in the presence of a foaming agent.

7. The method of claim 6, wherein grinding up to a Teilchengror.ie d(50) of the mineral constituent of::;; 400 nm, preferred::;; 300 nm, especially preferable ::;; 200 nm, determined by static light scattering.

8. A method of any one of claims 5 to 7, wherein a comb polymer with polyalkylene oxide side chains is used as a polymeric dispersant.

9. Mixture of building materials, comprising the composition according to one of the requirements 1 to 4, as well as a hydraulic or latent hydraulic binder, in particular cement, slag, preferably granulated blast furnace slag, fly ash, silica flour, metakaolin, natural pozzolans, calcined oil shale, calcium sul foaluminate cements and / or calcium aluminate cements.

10. The use of a composition of any one of claims 1 to 4 for accelerating the hardening of construction chemical mixtures comprising a hyd-raulic or latent hydraulic binder, in particular cement, slag, preferably granulated blast furnace slag, fly ash, silica flour, metakaolin, natural pozzolans, calcined oil shale, calcium sulfoaluminate cements and / or calcium aluminate cements, preferably from construction chemical mixtures containing predominantly cement as a hydraulic binder.