process for preparing a hardening accelerator composition, hardening accelerator composition, buildi

专利摘要:
PROCESS FOR THE PREPARATION OF AN ACCELERATING HARDENING COMPOSITION, ACCELERATING HARDENING COMPOSITION, USE OF THE SAME AND BUILDING MATERIAL MIXTURES CONTAINING AN ACCELERATING HARDENING COMPOSITION The invention relates to a process for the preparation of a hardening accelerating composition for reaction to a source of calcium, selected from calcium hydroxide or calcium oxide with a water-soluble silicate compound in the presence of at least one water-soluble polymeric dispersing agent and the setting accelerator composition obtainable by said process. The composition has a low content of anions and alkaline cations and is therefore widely applicable in building material mixtures.
公开号:BR112015012662B1
申请号:R112015012662-6
申请日:2014-01-27
公开日:2021-05-25
发明作者:Christoph Hesse；Luc Nicoleau
申请人:Basf Se；
IPC主号:

专利说明:

[0001] The present invention relates to a process for the preparation of a hardening accelerator composition, the hardening accelerator composition and the use of the hardening accelerator composition.
[0002] It is known that admixtures in the form of dispersants are often added to aqueous slurries of powdery organic or inorganic substances, such as clays, silicate powder, chalks, carbon blacks, rock powder and hydraulic binders, to improve their workability, ie kneading ability, spreadability, sprayability, pumpability or fluidity. Such mixtures are capable of breaking solid agglomerates, dispersing the formed particles and thus improving fluidity. This effect is also used in an oriented way in particular in the preparation of building material mixtures which contain hydraulic binders, such as cement, lime, gypsum, calcium sulfate hemihydrate (bassanite), anhydrous calcium sulfate (anhydrite) or binders latent hydraulics such as fly ash, blast furnace slag or pozzolans.
[0003] To convert these building material mixtures based on said binders into a viable ready-to-use form, as a rule substantially more mixing water is required than would be required for the subsequent hardening and hydration process. The proportion of cavities which are formed in the concrete body by excess water which subsequently evaporates leads to significantly poorer durability and mechanical strength.
[0004] In order to reduce this proportion of excess water at a predetermined processing consistency and/or to improve workability at a predetermined water/binder ratio, adjuvants, which are generally referred to as water reducing compositions or plasticizers are used. In particular, copolymers which are prepared by free radical copolymerization of acidic monomers with polyether Macro monomers are used in practice as such compositions.
[0005] In addition, admixtures for building material mixtures comprising hydraulic binders usually also contain hardening accelerators which shorten the setting time of the hydraulic binder. According to WO 02/070425, calcium silicate hydrate in particular present in dispersed form (finely or particularly finely dispersed), can be used as such hardening accelerator. However, commercially available calcium silicate hydrate or corresponding calcium silicate hydrate dispersions can only be considered as accelerators which have little hardening effect.
[0006] Another method for producing a CSH-based hardening accelerator is described in 2010 WO/026155, which discloses a process for preparing a hardening accelerator composition by reacting a water-soluble silicate compound with a water soluble calcium silicate compound, the reaction of the water soluble calcium compound with the water soluble silicate compound being carried out in the presence of an aqueous solution which contains a suitable water soluble honeycomb polymer as a plasticizer for hydraulic binders. The water-soluble calcium compound in particular is calcium chloride or calcium nitrate. As water-soluble glass water-soluble silicate compound having a low modulus is preferably used. In one embodiment, calcium hydroxide is reacted with silicon dioxide under alkaline conditions.
[0007] Known hardening accelerators have disadvantages, in particular due to the remaining ions in the product. Hardening accelerators based on C-S-H which are prepared using said calcium compounds as a source of calcium release a part of its activity after drying. The use of calcium chloride results in corrosive mixtures and the use of calcium nitrate together with organic compounds is a critical safety aspect. Calcium acetate based products are hygroscopic, whereas calcium sulfate can result in solubility issues. The presence of a high amount of alkaline ions is disadvantageous from an environmental aspect.
[0008] For these disadvantages, known hardening accelerators can be used only under certain conditions. As water is disadvantageous for dry binders, in particular cement, the known hardening accelerator suspension cannot be used for dry binders.
[0009] The object of the present invention is, therefore, to provide a hardening accelerator composition which is widely applicable. A further object of the present invention is to provide a setting accelerator composition which has a low content of anions, in particular chloride and nitrate, and a low content of alkaline cations. A further object of the present invention is to provide a setting accelerator composition, which can be prepared in powder form, so that it can be used for dry binders.
[0010] This object is achieved by a process for the preparation of a hardening accelerator composition based on calcium silicate hydrate (CSH) by reacting to a calcium source which is selected from calcium hydroxide or calcium oxide calcium with a water-soluble silicate compound in the presence of at least one water-soluble polymeric dispersing agent which includes anionic and/or aniogenic groups and polyether side chains. MODALITIES OF THE INVENTION: 1. Process for preparing a setting accelerator composition for reacting a calcium source selected from calcium hydroxide or calcium oxide with a water-soluble silicate compound in the presence of at least one dispersing agent water-soluble polymeric, which includes anionic and/or aniogenic groups and polyether side chains. 2. Process according to Embodiment 1, wherein the calcium source and the water-soluble silicate compound are added to an aqueous solution of the water-soluble polymeric dispersing agent. 3. Process according to Embodiment 1, wherein a solution or suspension of the calcium source and a solution of a water-soluble silicate compound are added to an aqueous solution of the water-soluble dispersing agent. 4. Process according to Modality 3, wherein the solution or suspension of the calcium source containing the water-soluble dispersing agent and the solution of the water-soluble silicate compound optionally containing the water-soluble dispersing agent are mixed or the calcium source solution/suspension optionally containing the water soluble dispersing agent and the water soluble silicate compound solution containing the water soluble dispersing agent are mixed. 5. Process according to Modality 3, wherein the aqueous solution containing the water-soluble dispersing agent and the calcium source are mixed with a solution of water-soluble silicate compound or aqueous solution containing the water-soluble dispersing agent and a water-soluble silicate compound is mixed with a solution or suspension of the calcium source. 6. Process, according to either Modality 2 or 5, the calcium source is used in solid form. 7. Process according to any one of Modalities 1 or 6, wherein the components are used in the following ratios: i) 0.01 to 75, preferably from 0.01 to 51, more preferably 0.01 to 15% by weight of calcium hydroxide or calcium oxide, ii) 0.01 to 75, preferably 0.01 to 55, more preferably 0.01 to 10% by weight of the water-soluble silicate compounds, iii) 0.001 to 60, preferably of 0.1 to 30, more preferably 0.1 to 10% by weight of water-soluble dispersing agent, iv) 24 to 99, preferably from 50 to 99, most preferably 70 to 99% by weight of water. 8. Process according to any one of Modalities 1 to 7, wherein the aqueous solution further contains dissolved aluminum and/or magnesium ions. 9. Process according to any one of Modalities 1 to 8, wherein calcium hydroxide or calcium oxide is used together with a water-soluble calcium salt selected from calcium chloride, calcium nitrate, formate calcium, calcium acetate, calcium bicarbonate, calcium bromide, calcium carbonate, calcium citrate, calcium chlorate, calcium fluoride, calcium gluconate, calcium hypochlorite, calcium iodate, calcium iodide, calcium lactate , calcium nitrite, calcium oxalate, calcium phosphate, calcium propionate, calcium silicate, calcium stearate, calcium sulfamate, calcium sulfate, calcium sulfate hydrochloride, calcium sulfate dihydrate, calcium sulfide, calcium tartrate, calcium aluminate, tricalcium silicate, dicalcium silicate and mixtures of two or more thereof. 10. Process according to Modality 9, wherein the water-soluble calcium compound is selected from calcium sulfamate, calcium acetate, calcium chloride, calcium formate, calcium sulfate and mixtures of two or more of the same. 11. Process according to any one of Modalities 1 to 10, wherein the water-soluble silicate compound is selected from sodium silicate, potassium silicate, water glass, aluminum silicate, tricalcium silicate, dicalcium silicate, calcium silicate, silicic acid, potassium metasilicate, sodium metasilicate and mixtures of two or more thereof. 12. Process according to any Embodiment 11, wherein the water-soluble silicate compound is selected from an alkali metal silicate with the formula m SiO 2 , n M 2 O, wherein M is Li, Na, K and NH 4 , preferably Na or K or mixtures thereof, m and m are molar numbers and the m:n ratio is from about 0.9 to about 4. 13. Process, according to Modality 12, in which m:n ratio is from about 0.9 to about 3.8, in particular from about 0.9 to about 3.6. 14. Process according to Modality 12, wherein the ratio of m:n is from about 2.5 to about 3.8, in particular from about 3 to about 3.6. 15. Process according to any one of Embodiments 12 to 14, wherein the water-soluble silicate compound is water-soluble glass powder. 16. Process according to any one of Modalities 1 to 15, in which the water-soluble dispersing agent is a copolymer which is produced by free radical polymerization in the presence of acid monomer, preferably carboxylic acid monomer and macro monomer of polyether, so that completely at least 45% by mol, preferably at least 80% by mol, of all structural units of the copolymer are produced by incorporating acid monomer, preferably carboxylic acid monomer and polyether macro monomer in the form of polymerized units. 17. Process according to any one of Modalities 1 to 16, in which the dispersing agent is a copolymer which includes at least one structural unit, having the general formula (Ia), (Ib), (Ic) and/or (Id):
wherein: R1 is H or branched or unbranched C1 - C4 alkyl, CH2COOH or CH2CO-X-R3, preferably H or CH3; X is -NH (CnH2n) or O-(CnH2n), where n = 1, 2, 3 or 4, where the nitrogen atom or the oxygen atom is bonded to the CO group, or X is a chemical bond, preferably a chemical bond or O-(CnH2n); R2 is OM, PO3M2, or O-PO3M2; with the proviso that X is a chemical bond, if R2 is OM; R3 is PO3M2, or O-PO3M2;
wherein: R3 is H or branched or unbranched C1-C4 alkyl, preferably H or CH3; n = 0, 1, 2, 3 or 4, preferably 0 or 1; R4 is PO3M2, O-PO3M2;
wherein: R5 is H or C1-C4 alkyl branched or unbranched, preferably H or CH3; Z is O or NR7, preferably O; R7 is H, (CnH2n)-OH, (CnH2n)-PO3M2, (CnH2n)-OPO3M2, (C6H4)-PO3M2, or (C6H4)-OPO3M2; n is 1, 2, 3 or 4, preferably 1, 2 or 3; (Id) H R6
wherein: R6 is H or branched or unbranched C1-C4 alkyl, preferably H; Q is O or NR7, preferably O; R7 is H, (CnH2n)-OH, (CnH2n)-PO3M2, (CnH2n)-OPO3M2, (C6H4)-PO3M2, or (C6H4)-OPO3M2; n is 1, 2, 3 or 4, preferably 1, 2 or 3; and where each M independently is H or an equivalent cation. 18. Process according to Modality 17, wherein the dispersing agent includes as anionic or anionogenic groups at least one structural unit of formula (Ia), wherein R1 is H or CH3; and/or at least one structural unit of formula (Ib), where R3 is H or CH3; and/or at least one structural unit of formula (Ic), wherein R5 is H or CH3 and Z is O; and/or at least one structural unit of formula (Id), where R6 is H and Q is O. 19. Process, according to Modality 17 or 18, in which the dispersing agent includes as anionic or anionogenic groups at least a structural unit of formula (Ia), wherein R1 is H or CH3 and XR2 is OM or X is O (CnH2n) with n = 1, 2, 3 or 4, in particular 2 and R2 is O-PO3M2. 20. Process according to any one of Modalities 1 to 19, in which the dispersing agent is a copolymer which comprises at least one structural unit, having the general formula (IIa), (IIb), (IIc) and/or (IId): (IIa)
where: R10, R11 and R1. are independently of one another, H C1 -C4 alkyl branched or unbranched; E is C1-C6-branched or unbranched alkylene, cyclohexylene, CH.-C6H1010, 1,.-phenylene, 1,3-phenylene or 1,4-phenylene; G is O, NH or CO-NH, or E and G together form a bond A is CxH2 x where x = 2, 3, 4 or 5 (preferably x = 2 or 3) or CH2CH(C6H5); N is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2; a is an integer from 2 to 350 (preferably 5 to 150); R13 is H, C1 - C4 alkyl, branched or unbranched, CO-NH2 or COCH3;
wherein: R14 is H or C 1 -C 4 alkyl branched or unbranched; E is C1-C6-branched or unbranched alkylene, cyclohexylene, CH2-C6H1010, 1,2-phenylene, 1,3-phenylene or 1,4-phenylene; A is CxH2x where x = 2, 3, 4 or 5 preferably 2 or 3 or CH2CH(C6H5); L is CxH2 x with x = 2, 3, 4 or 5 preferably x = 2 or 3 or CH2CH(C6H5); a is an integer from 2 to 350 preferably 5 to 150; d is an integer from 1 to 350 preferably 5 to 150; R19 is H or C1-C4 alkyl branched or unbranched; R20 is H or C1 -C4 alkyl branched or unbranched; and n is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2;
wherein: R21, R22 and R23 independently of one another are H or C1-C4 alkyl branched or unbranched; W is O, NR25 or N; Y is 1 if W = O or NR25, and is 2 if W = N; A is CxH2x with x = 2, 3, 4 or 5 preferably 2 or 3 or CH2CH(C6H5); a is an integer from 2 to 350 preferably 5 to 150; R24 is H or branched or unbranched C1-C4 alkyl; R25 is H or branched or unbranched C1-C4 alkyl;
wherein R6 is H or branched or unbranched C1-C4 alkyl; Q is NR10, N or O; Y is 1 if W = O or NR25, and is 2 if W = N; R10 is H or C1-C4 alkyl branched or unbranched; A is CxH2 x with x = 2, 3, 4 or 5 preferably 2 or 3 or CH2CH(C6H5; and a is an integer from 2 to 350 preferably 5 to 150; 21. Process according to modality 20 , wherein the polyether side chain of the dispersing agent comprises (a) at least one structural unit (IIa), wherein R10 and R12 are H, R11 is H or CH3, E and G together form a chemical bond, A is CxH2 x with x = 2 or 3, a is 3 to 150 , and R13 is H or C1-C4 alkyl branched or unbranched; and/or (b) at least one structural unit (IIb), wherein R16 and R18 are H, R17 is H or CH3, E is C1-C4 alkylene-branched or unbranched, A is CxH2x with x = 2 or 3, L is CxH2x with x = 2 or 3, a is an integer from 2 to 150, d is an integer from 1 to 150, R19 is H or branched or unbranched C1-C4 alkyl; and R20 is H or branched or unbranched C1-C4 alkyl; and/or (c) at least one structural unit (IIc ), where R21 and R23 are H, R22 is H or CH3, A is CxH2 x with x = 2 and/or 3, a is an integer a from 2 to 150, and R24 is H or branched or unbranched C1-C4 alkyl; and/or (d) at least one structural unit (IId), where R6 is H, Q is O, R7 is (CnH2n)-O-(AO)α-R9, n is 2 and/or 3, A for CxH2 x with x = 2 or 3, a is an integer from 1 to 150, and R9 is H or C1-C4 alkyl-branched or unbranched. 22. Process according to Modality 20 or 21, wherein the dispersing agent comprises at least one structural unit of formula (IIa) and/or (IIc). 23. Process according to any one of Modalities 1 to 15, in which the dispersing agent is a polycondensation product comprising structural units (III) and (IV):
wherein T is substituted or unsubstituted phenyl or naphthyl or substituted or unsubstituted, heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S; no 1 or 2; B is N, NH or O, with the proviso that n is 2 if B is N and with the proviso that n is 1 if B is NH or O; A is CxH2x with x = 2, 3, 4 or 5 preferably x = 2 or 3 or CH2CH(C6H5; a is an integer from 1 to 300, preferably 5 to 150; R25 is H or branched C1-C10 alkyl or unbranched, cycloalkyl, C5-C8 aryl or heteroaryl with 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S, and preferably H; in which structural unit (IV) is selected from structural units (IVa) and (IVb):
wherein D is substituted or unsubstituted phenyl, or naphthyl or substituted or unsubstituted, heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S; E is N, NH or O, with the proviso that n is 2 if E is N and with the proviso that n is 1 if E is NH or O; A is CxH2x with x = 2, 3, 4 or 5 preferably x = 2 or 3 or CH2CH(C6H5; b is an integer from 1 to 300, preferably 5 to 150; M is independently is H or an equivalent cation ;
wherein V is substituted or unsubstituted phenyl or naphthyl or naphthyl which is optionally substituted by one or two groups selected from R8, OH, OR8, (CO)R8, COOM, COOR8, SO3R8 and NO2, preferably, alkyl OH, OC1-C4 and C1-C4 alkyl; R7 is COOM, OCH2COOM, SO3M or OPO3M2; M is H or an equivalent cation; and R8 is C-alkyl, phenyl, naphthyl, phenyl C1-C4, C1-C4 alkyl, or C1-C4 alkylphenyl. 24. Process according to Modality 23, wherein the dispersing agent includes a polycondensation product comprising structural units (III) and (IV), wherein T is substituted phenyl or unsubstituted naphthyl, E is NH or O, A is CxH2 x with x = 2 and/or 3, a is an integer from 1 to 150, and R25 is H or C1-C10 alkyl branched or unbranched. 25. Process according to Modality 23, wherein D is substituted phenyl or unsubstituted naphthyl, E is NH or O, A is CxH2 x with x = 2 and/or 3, and b is an integer from 1 to 150 26. A process according to any one of embodiments 22 to 25, wherein T and/or D is phenyl or naphthyl which is substituted by 1 or 2 C 1 -C 4 alkyl, hydroxy or 2 C 1 -C 4 alkoxy. 27. Process according to Modality 23, wherein V is phenyl or naphthyl which is substituted by 1 or 2 C 1 -C 4 alkyl, OH, OCH 3 or COOM, and R 7 is COOM or OCH 2 COOM. 28. Process according to any one of Embodiments 22 to 27, wherein the polycondensation product comprises an additional structural unit (V) of the formula
wherein R5 and R6 may be the same or different and are H, CH3, COOH or substituted or unsubstituted phenyl or naphthyl or substituted or unsubstituted heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S. 29. Process, according to Modality 28, wherein R5 and R6 in structural unit (V) may be the same or different and are preferably H, CH3, or COOH, in particular H or one of R5 r R6 is H and the other is CH3. 30. Process according to any one of Embodiments 1 to 27, wherein the polymeric dispersing agent comprises structural units of formulas (I) and (II), in particular of formulas (Ia) and (IIa). 31. Process according to any one of Embodiments 30, wherein the polymeric dispersing agent comprises structural units (Ia) and (IIc). 32. Process according to Embodiment 30, wherein the polymeric dispersing agent comprises structural units of formulas (Ic) and (IIa). 33. Process according to any one of Embodiments 30, wherein the polymeric dispersing agent comprises structural units (Ia), (Ic) and (IIa). 34. Process, according to Modality 30, in which the polymeric dispersing agent is formed from (i) anionic or anionogenic structural units derived from monomers selected from: acrylic acid, methacrylic acid, maleic acid, acid ester phosphoric hydroxyethylacrylate, and/or phosphoric acid ester Hydroxyethylmethacrylate, phosphoric acid diester of hydroxyethylacrylate, and/or phosphoric acid diester of hydroxyethylacrylate and (ii) polyether side chain structural units derived from acrylic acid ester polyethylene glycol C1-C4 alkyl , polyethylene glycol acrylic acid ester, C 1 -C 4 alkyl polyethylene glycol methacrylic acid ester, polyethylene glycol methacrylic acid ester, C 1 -C 4 alkyl polyethylene glycol acrylic acid ester, polyethylene glycol acrylic acid ester, C 2 -vinyloxy C4-alkylene-polyethylene glycol vinyloxy-C2-C4alkylene-polyethylene glycol-C1-C4-alkyl ether, allyloxy-polyethylene glycol, allyloxy-po polyethylene glycol-C1-C4-alkyl ether, methyloxy-polyethylene glycol, methyloxy-polyethylene glycol-C1-C4-alkyl ether, isoprenyloxy-polyethylene glycol, isoprenyloxy-polyethylene glycol-C1-C4-alkyl ether and mixtures of two or more thereof. 35. Process according to embodiment 30, wherein the polymeric dispersing agent is formed from structural units (i) and (ii) which are derived from the following monomers (i) Phosphoric acid ester hydroxyethyl acrylate and/or hydroxymethyl acrylate phosphoric acid ester and (ii) C 1 -C 4 alkyl polyethylene glycol acrylic acid ester and/or C 1 -C 4 alkyl polyethylene glycol methacrylic acid ester; or (i) acrylic acid and/or methacrylic acid and (ii) polyethylene glycol C1-C4 alkyl acrylic acid ester and/or polyethylene glycol C1-C4 alkyl methacrylic acid ester; or (i) acrylic acid, methacrylic acid and/or maleic acid and (ii) vinyloxy-C2 -C4 -alkylene-polyethylene glycol, allyloxy-polyethylene glycol, methyloxy-polyethylene glycol or isoprenyloxy-polyethylene glycol. 36. Process according to Modality 35, in which the polymeric dispersing agent is formed of structural units (i) and (ii) which are derived from the following monomers (i) Phosphoric acid ester hydroxyethyl methacrylate and (ii) acid of C 1 -C 4 -alkyl polyethylene glycol methacrylic ester or polyethylene glycol methacrylic acid ester; or (i) acrylic acid and (ii) polyethylene glycol C1-C4 alkyl 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) methyloxy-polyethylene glycol or (i) maleic acid and (ii) isoprenyloxy-polyethylene glycol or (i) maleic acid and (ii) allyloxy-polyethylene glycol or (1) maleic acid and (ii) methyloxy-polyethylene glycol or 37. Process according to any one of Embodiments 17 to 22, wherein the molar ratio of structural units (I) : (II) is from 1:4 to 15:1, in particular from 1:1 to 10:1. 38. Process according to any one of Modalities 23 to 29, wherein the molar ratio of structural units (III):(IV) is 4:1 to 1:15, in particular 2:1 to 1:10. 39. Process according to any one of Modalities 23 to 30, wherein the molar ratio of structural units (III + IV): (V) 2:1 to 1:3, in particular 1:0.8 to 1: two. 40. Process according to any one of Embodiments 23 to 30, 38 or 39, wherein the polymeric dispersing agent is formed from structural units of formulas (III) and (IV) wherein T and D are phenyl or naphthyl , wherein the phenyl or naphthyl is optionally substituted by 1 or 2 C 1 -C 4 alkyl, hydroxy or 2 C 1 -C 4 alkoxy, B and E are O, A is C x H 2 x with x = 2, a is from 3 to 150, in special from 10 to 150, and b is 1, 2 or 3. 41. Process according to any of the above Modalities, wherein the molar ratio of calcium to silicon in the calcium silicate hydrate particles is 0.6 to 2 , preferably 0.8 to 1.8, more preferably 0.9 to 1.6 and in particular 1.0 to 1.5. 42. Process according to any of the above Modalities, wherein the molar ratio of calcium to water in the calcium silicate hydrate particles is from 0.6 to 6, preferably from 0.6 to 4 and in particular from 0 .8 to 2. 43. Process, according to any of the previous Modalities, in which the reaction is carried out completely or partially in the presence of a viscosity-enhancing polymer, selected from the group of polysaccharide derivatives and/or (co ) polymers, with an average molecular weight Mw greater than 500,000 g/mol, more preferably greater than 1,000,000 g/mol, the (co)polymers containing structural units derived (preferably by free radical polymerization) from (meth) monomer derivatives )non-ionic acrylamide and/or sulfonic acid monomer derivatives. 44. Process, according to Modality 43, in which the viscosity-enhancing polymer is a polysaccharide derivative selected from the group of methylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose (MHPC) and/or (co)polymers with an average molecular weight Mw greater than 500,000 g/mol, more preferably greater than 1,000,000 g/mol, the (co)polymers containing structural units derived (preferably by free radical polymerization) from of nonionic (meth)acrylamide monomer derivatives selected from the group of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-cyclohexylacrylamide, N -benzylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminoethylacrylamide and/or N-tert-butylacrylamide, preferably acrylamide, and/or sulfonic acid monomer derivatives selected alongside tir from the group of 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, and/or 2-acrylamide-2, 4,4-trimethylpentanesulfonic acid or the salts of the mentioned acids. 45. Process according to any of the above Modalities, in which the reaction is carried out completely or partially in the presence of an aqueous solution containing hardening accelerators, selected from the group of alkanolamines, preferably triisopropanolamine and/or tetrahydroxyethyl ethylene diamine. 46. Process according to any of the above Modalities in which the reaction is carried out completely or partially in the presence of a configuration retarder selected from the group of citric acid, tartaric acid, gluconic acid, phosphonic acid, amino-trimethylenephosphonic acid , ethylenediaminetetra(methylenephosphonic acid), diethylentriaminepenta(methylenephosphonic acid), in each case, including the respective salts to acids, pyrophosphates, pentaborates, metaborates and/or sugars. 47. Process according to any of the above Modalities, followed by a process step in which the setting accelerator composition is dried, preferably by a spray drying or drum drying process. 48. Process according to Modality 47, wherein the powder has a water content of less than 10% by weight, as determined by weight loss after heating at 100°C for 3 h. A setting accelerator composition obtainable by the process according to any one of Modalities 1 to 48. Composition according to claim 49, preferably an aqueous setting accelerating suspension, containing calcium silicate hydrate particles with a particle diameter of less than 500 nm, preferably less than 300 nm, more preferably less than 200 nm, the particle size of the calcium silicate hydrate being measured by analytical ultracentrifugation. 51. Composition according to Modality 50, in which the calcium silicate hydrate is phosagite, hylebrandite, xonotlite, necoite, clinotobermorite, 9A - tobermorite (riversiderite), 11A - tobermorite, 14 CA - tobermorite (plombierite), jenite, metajenite, calcium chondrodite, afwilite, α-2SH, delaita, jafeita, rosenhanite, quilalaite or suolunite. 52. Composition, according to Modality 51, in which the calcium silicate hydrate is xonotlite, 9A - tobermorite (riversiderite), 11A - tobermorite, 14 CA - tobermorite (plombierite), jenite, metajenite, afwilite, and/or jafeita. 53. Use of a hardening accelerator composition, according to any one of Modalities 49 to 52, in building material mixtures containing cement, gypsum, anhydrite, slag, preferably blast furnace slag, preferably granulated soil, fly ash, powder of silica, metakaolin, natural pozzolans, calcined bituminous shale, calcium sulfoaluminate cement and/or calcium aluminate cement, preferably in building material mixtures which substantially contain cement as a hydraulic binder. 54. Construction material mixtures containing a hardening accelerating composition according to any one of Modalities 49 to 52 and cement, gypsum, anhydrite, slag, preferably blast furnace slag preferably granulated soil, fly ash, silica powder, metakaolin, pozzolans natural, calcined oil shale, calcium sulfoaluminate cement and/or calcium aluminate cement. 55. The use of the cement setting accelerating composition according to any one of Modalities 49 to 52 as a grinding agent in the preparation of cement (portland), slag, fly ash, lime, puzzolan or a mixture thereof, in particular cement (Portland). 56. The use of the hardening accelerator composition according to any one of Modalities 49 to 52 in oil and gas drilling, in particular in the exploration, development and completion of underground oil and gas reservoirs, as well as deep drilling. 57. The use of a hardening accelerator composition in accordance with any one of Modalities 49 to 52 for accelerating the settlement of cement slurries in the cementation of oil and gas well boreholes.
[0011] In the context of the present invention, the dispersing agent, in general, is a comb polymer suitable as a plasticizer for hydraulic binders. Comb polymers are to be understood as polymers which have relatively long side chains (with a molecular weight in each case of at least 200 g/mol, particularly preferably of at least 400 g/mol) on a linear main chain at more or more intervals. less regular. The lengths of these side chains are often approximately equal, but they can also differ considerably from one another (eg when Macro polyether monomers with side chains of different length are incorporated as polymerized units). Such polymers can be obtained for example by a radical polymerization of acid monomers and polyether Macro monomers. Esterification and/or amidation of poly(meth)acrylic acid and similar (co)polymers thereof, such as for example acrylic/maleic acid copolymers with appropriate monohydroxy functional, respectively monoamino functional polyalkylene glycols, preferably alkyl Polyethylene glycols is an alternative route for such comb polymers. Comb polymers obtainable by esterification and/or amidation of poly(meth)acrylic acid are described for example in EP1138697B1, the disclosure of which is incorporated by reference.
[0012] Preferably the average molecular weight Mw as determined by gel permeation chromatography (GPC) of the water soluble comb polymer suitable as a plasticizer for hydraulic binders is from 5,000 to 200,000 g/mol, more preferably from 10,000 to 80,000 g/ mol, more preferably from 20,000 to 70,000 g/mol. Polymers were analyzed by means of exclusion chromatography for average molar mass and conversion (column combination: OH-Pak SB-G, OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Shodex, Japan; Eluent: 80% by volume of aqueous solution of HCO2NH4 (0.05 mol/l) and 20% by volume of acetonitrile; injection volume of 100 μ l; flow rate of 0.5 ml/min). Calibration to determine mean molar mass was performed using polyethylene glycol and linear poly(ethylene oxide) standards. As a measure of conversion, the peak of the copolymer is standardized to a relative height of 1 and the peak height of the macromonomer/PEG containing oligomer is used as a measure of the residual monomer content.
[0013] Preferably the water-soluble comb polymer suitable as a plasticizer for hydraulic binders fulfills the requirements of industry standard EN 934-2 (February 2002).
[0014] In principle, the accelerator contains an inorganic component and an organic component. The inorganic component can be considered as modified, finely dispersed calcium silicate hydrate, which may contain foreign ions such as aluminum and magnesium. Calcium silicate hydrate is prepared in the presence of comb polymer plasticizer (organic component). Typically, a suspension containing calcium silicate hydrate in finely dispersed form is obtained, which suspension effectively accelerates the hardening process of hydraulic binders and can act as a plasticizer. The suspension may be dried in a conventional manner, for example by spray drying or drum drying to result in a powder having an accelerating activity which is comparable to the activity of the suspension product.
[0015] The inorganic component can in most cases be described with regard to its composition by the following empirical formula: a CaO, SiO2, b Al2O3, c H2O, d X, and WX is an alkali metal W is an alkaline earth metal 0 ,1 < a < 2 preferably 0.66 < a < 1.8 0 < b < 1 1 < c < 6 0 < d < 1 preferably preferably 0 < b < 0.1 1 < c < 6.0 0 < d < 0.4 or 0.2 0 < and < 2 preferably 0 < and < 0.1
[0016] In a preferred embodiment, the aqueous solution also contains, in addition to silicate and calcium ions, additionally dissolved ions which are preferably provided in the form of dissolved aluminum salts and/or dissolved magnesium salts. As aluminum salts, preferably aluminum halides, aluminum nitrate, aluminum hydroxide and/or aluminum sulfate can be used. Most preferred within the group of aluminum halides is aluminum chloride. Magnesium salts can preferably be magnesium nitrate, magnesium chloride and/or magnesium sulphate.
[0017] Aluminum salts and magnesium salts have the advantage that defects in the calcium silicate hydrate can be created through the introduction of ions other than calcium and silicon. This leads to a better hardening acceleration effect. Preferably the molar ratio of aluminum or magnesium to calcium and silicon is small. More preferably, the molar ratios are selected so that in the above empirical formula the preferred ranges for a, b and e are met (0.66 < a < 1.8; 0 < b < 0.1; 0 < e < 0.1).
[0018] In a preferred embodiment of the invention, in a first step, the calcium source is mixed with the aqueous solution which contains a water-soluble comb polymer suitable as a plasticizer for hydraulic binders. To the obtained mixture, water-soluble silicate compound is added in a subsequent second step. The water-soluble silicate compound of the second stage may also contain the water-soluble comb polymer.
[0019] The aqueous solution may also contain one or more additional solvents (eg alcohols such as ethanol and/or isopropanol) in addition to water. Preferably, the proportion by weight of solvent, excluding water to the sum of water and additional solvent (alcohol, for example) is up to 20% by weight, more preferably less than 10% by weight and most preferably less than 5% by weight. However most preferred are aqueous systems without any solvent.
[0020] The temperature range in which the process is carried out is not particularly limited. However, certain limits are imposed by the physical state of the system. It is preferred to work in the range of 0 to 100 °C, more preferred 5 to 80 °C and most preferred 15 to 35 °C. High temperatures can be reached, especially when a grinding process is applied. It is preferred not to exceed 80 °C.
[0021] Also the process can be carried out at different pressures, preferably in a range of 1 to 5 bars.
[0022] The pH value depends on the amount of reactants (source of calcium and water-soluble silicate) and the solubility of the precipitated calcium silicate hydrate. It is preferred that the pH value is greater than 8 at the end of the synthesis, preferably in a range between 8 and 13.5.
[0023] In a preferred embodiment, the aqueous solution containing the comb polymer contains the calcium source and the water-soluble compound silicate. This means that the reaction of calcium hydroxide and the water-soluble silicate compound to precipitate calcium silicate hydrate takes place in the presence of an aqueous solution which contains a water-soluble comb polymer suitable as a plasticizer for hydraulic binders.
[0024] In a preferred embodiment, a solution or suspension of the calcium source and a solution of a water-soluble silicate compound are added, preferably separately and simultaneously, to the aqueous solution containing a suitable water-soluble comb polymer as a plasticizer for hydraulic binders. The advantage of this preparation method is its good practicability and the relatively small particle sizes of the C-S-H obtained.
[0025] In a further preferred embodiment of the invention, the solution or suspension of the calcium source and/or the solution of a water-soluble silicate compound contains the water-soluble comb polymer. In this case, the person skilled in the art will understand that the water-soluble comb polymer is dispensed into at least two or three solutions or suspensions. It is advantageous that 1 to 50%, preferably 10 to 25% of the total water-soluble comb polymer is contained in the suspension or solution of calcium source and/or silicate compound solution.
[0026] In a further embodiment, the addition of the calcium source and the water-soluble silicate compound to the aqueous solution containing a water-soluble comb polymer is carried out in a semi-batch cyclic process with a first and a second reactor in series. The second reactor initially contains an aqueous solution of the water-soluble comb polymer. The first reactor is fed with the water-soluble silicate compound solution and the calcium source solution/suspension and the contents of the second reactor. The output from the first reactor is added to the second reactor. This means that the contents of the second reactor are circulated through the first reactor.
[0027] Alternatively, said addition is carried out in a continuous process in which the calcium source, the water-soluble silicate compound and the aqueous solution which contains the water-soluble comb polymer are mixed in the first reactor and the flow The resultant is fed into a mixed-flow reactor or a plug-flow reactor.
[0028] Preferably the ratio of the volumes of the first and second reactor is from 1/10 to 1/2000. Preferably the mass flow rate of the water soluble calcium and water soluble silicate compounds is small compared to the mass flow leaving the second and entering the first reactor, preferably the ratio is 1/5 to 1/1000 . Usually the first reactor can be a dynamic or static mixing unit, preferably mixing in the first reactor must be effective.
[0029] In general, the components are used in the following ratios: i) 0.01 to 75, preferably 0.01 to 51, more preferably 0.01 to 15% by weight of calcium source, 58. 0.01 to 75 , preferably from 0.01 to 55, more preferably 0.01 to 10% by weight of the water-soluble silicate compound, 111. 0.001 to 60, preferably from 0.1 to 30, more preferably 0.1 to 10%, by weight of water-soluble comb polymers suitable as a plasticizer for hydraulic binders, 112, 24 to 99, preferably from 50 to 99, more preferably 70 to 99% by weight of water. Preferably the setting accelerator composition is dosed at 0.01 to 10% by weight, more preferably at 0.1 to 2% by weight solids content with respect to hydraulic binder, preferably cement. The solids content is determined in an oven at 60 °C until reaching a constant sample weight.
[0030] The calcium source can be used in conjunction with a water-soluble calcium compound selected from calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, calcium bromide, carbonate calcium, calcium citrate, calcium chlorate, calcium fluoride, calcium gluconate, calcium hypochlorite, calcium iodate, calcium iodide, calcium lactate, calcium nitrite, calcium oxalate, calcium phosphate, calcium propionate , calcium silicate, calcium stearate, calcium sulfamate, calcium sulfate, calcium sulfate hydrochloride, calcium sulfate dihydrate, calcium sulfide, calcium tartrate, calcium aluminate, tricalcium silicate and/or dicalcium silicate. Preferably, the water-soluble calcium compound is not a calcium silicate. Calcium silicate silicate, dicalcium silicate and/or tricalcium silicate is less preferred because of low solubility (especially in the case of calcium silicate) and for economic reasons (price) (especially in the case of dicalcium silicate and tricalcium silicate).
[0031] The water-soluble calcium compound is preferably present as calcium sulfamate, calcium acetate, calcium chloride, calcium formate and/or calcium sulfate. Advantage of these calcium compounds is their non-corrosiveness.
[0032] The weight ratio of calcium hydroxide or calcium oxide to water-soluble calcium compound is generally in the range of 1:0.01 to 1:0. 5, in particular 1:0.1 to 1:0. 3.
[0033] In general, the water-soluble silicate compound is selected from an alkali metal silicate with the formula m SiO2 • n M2O, wherein M is Li, Na, K and NH4, preferably Na or K or its mixtures, m and m are molar numbers and the m:n ratio is from about 0.9 to about 4. Preferably, the m:n ratio is from about 0.9 to about 3.8, in particular from about 3.8. from about 0.9 to about 3.6. in a more preferred embodiment, the ratio is from about 2.5 to about 3.8, in particular from about 3 to about 3.6. Preferably, the water-soluble silicate compound is water-soluble glass which can be used as an aqueous solution or as a powder.
[0034] Water soluble alkali metal ions (eg lithium, sodium, potassium ions) can be removed from the hardening accelerator composition by water soluble cation and/or nitrate and/or chloride ions exchangers can be removed from the hardening accelerator composition by anion exchangers. Preferably the removal of said cations and/or said anions is carried out in a second stage of the process after the preparation of the setting accelerator composition. For example, acid ion exchangers suitable as cation exchangers are based on sodium polystyrene sulfonate or poly-2-acrylamido-2-propane sulfonic acid (poly AMPS). Basic ion exchangers for example are based on amino acid groups, such as poly(acrylamide-N-propyltrimethylammonium chloride) (polyAPTAC).
[0035] In a preferred embodiment, the water-soluble comb polymer suitable as a plasticizer for hydraulic binders is a copolymer which contains, in the main chain, side chains having ether functions and anionic and/or anionogenic groups. Anionic groups are deprotonated acid groups in the polymeric dispersing agent. Anionogenic groups are the acidic groups on the polymeric dispersing agent. It is also possible that the polymeric dispersing agent contains anionic and anionogenic groups simultaneously, for example partially deprotonated acid groups which are at least dibasic.
[0036] In a preferred embodiment, the water-soluble comb polymer suitable as a plasticizer for hydraulic binders is a copolymer which is produced by free radical polymerization in the presence of acid monomer, preferably carboxylic acid monomer and polyether macro monomer , so that completely at least 45% by mol, preferably at least 80% by mol, of all the structural units of the copolymer are produced by incorporating acidic monomer, preferably carboxylic acid monomer and polyether macro monomer in the form of polymerized units . Acid monomer is to be understood as meaning monomers which are capable of free radical copolymerization, have at least one carbon double bond, contain at least one acidic function, preferably a carboxylic acid function, and react with an acid in an aqueous medium. Furthermore, acidic monomer is also to be understood as meaning monomers which are capable of free radical copolymerization, have at least one carbon double bond, form at least one acidic function, preferably a carboxylic acid function, in an aqueous medium , as a result of a hydrolysis reaction and reacts as an acid in an aqueous medium (example: maleic anhydride or hydrolysable (meth)acrylic acid esters).
[0037] In the context of the present invention, polyether macro monomers which are compounds capable of free radical copolymerization, have at least one carbon double bond and have at least two ether oxygen atoms, with the proviso that the units Polyether macromonomer backbones present in the copolymer have side chains which contain at least two ether oxygen atoms, preferably at least 4 ether oxygen atoms, more preferably at least 8 ether oxygen atoms, more preferably at least 15 ether atoms. oxygen ether.
[0038] Structural units which do not constitute an acidic monomer or a polyether macromonomer can be for example styrene and styrene derivatives (for example substituted methyl derivatives), vinyl acetate, vinyl pyrrolidone, butadiene, vinyl propionate, hydrocarbons unsaturated such as (iso)butylene, ethylene and/or propylene. Monomers are preferred with no more than one double-bonded carbon.
[0039] In a preferred embodiment of the invention the water-soluble comb polymer suitable as a plasticizer for hydraulic binders is a copolymer of styrene and a half maleic acid ester with a monofunctional polyalkalene glycol. Preferably, such copolymers can be produced by the free radical polymerization of styrene monomers and maleic anhydride (or maleic acid) in a first step. In the second step, polyalkalene glycols, preferably alkyl polyalkalene glycols (preferably alkyl polyethylene glycols, more preferably methyl polyethylene glycol) are reacted with the copolymer of styrene and maleic anhydride to achieve an esterification of the acid groups. Styrene can be completely or partially substituted by styrene derivatives, for example methyl substituted derivatives. Copolymers of this preferred embodiment are described in US 5,158,996, the disclosure of which is incorporated in this patent application.
[0040] In one embodiment, the polymeric dispersing agent is a copolymer comprising at least one structural unit, having the general formula (Ia), (Ib), (Ic) and/or (Id) (said units may be the same or different within a polymer molecule and within different polymer molecules)
wherein: R1 is H or branched or unbranched C1 - C4 alkyl, CH2COOH or CH2CO-X-R3, preferably H or CH3; X is -NH (CnH2n) or O-(CnH2n), where n = 1, 2, 3 or 4, where the nitrogen atom or the oxygen atom is bonded to the CO group, or X is a chemical bond, preferably a chemical bond or O-(CnH2n); R2 is OM, PO3M2, or O-PO3M2; with the proviso that X is a chemical bond, if R2 is OM; R3 is PO3M2, or O-PO3M2;
wherein: R3 is H or branched or unbranched C1-C4 alkyl, preferably H or CH3; n = 0, 1, 2, 3 or 4, preferably 0 or 1; R4 is PO3M2, O-PO3M2;
wherein: R5 is H or C1-C4 alkyl branched or unbranched, preferably H or CH3 Z is O or NR7, preferably O; R7 is H, (CnH2n)-OH, (CnH2n)-PO3M2, (CnH2n)-OPO3M2, (C6H4)-PO3M2, or (C6H4)-OPO3M2, n is 1, 2, 3 or 4, preferably 1, 2 or 3; (Id)
wherein: R6 is H or branched or unbranched C1-C4 alkyl, preferably H; Q is O or NR7, preferably O; R7 is H, (CnH2n)-OH, (CnH2n)-PO3M2, (CnH2n)-OPO3M2, (C6H4)-PO3M2, or (C6H4)-OPO3M2, n is 1, 2, 3 or 4, preferably 1, 2 or 3; and where each M independently is H or an equivalent cation.
[0041] Preferably, the polymer includes as anionic or anionogenic groups at least one structural unit of formula (Ia), wherein R1 is H or CH3; and/or at least one structural unit of formula (Ib), where R3 is H or CH3; and/or at least one structural unit of formula (Ic), wherein R5 is H or CH3 and Z is O; and/or at least one structural unit of formula (Id), wherein R6 is H and Q is O.
[0042] The polymer includes as an especially preferred anionic or anionogenic group at least one structural unit of formula (Ia), wherein R1 is H or CH3 and XR2 is OM or X is O (CnH2n) with n = 1, 2 , 3 or 4, in particular 2 and R2 is O-PO3M2.
[0043] The side chains of the polymeric dispersing agent comprise at least one structural unit, having the general formulas (IIa), (IIb), (IIc) and/or (IId)
R10 R11 4HP R12 (CnH2^)-^^^(AO)a-R13 wherein: R10, R11 and R12 are, independently of one another, H C1 -C4 alkyl branched or unbranched; E is C1-C6-branched or unbranched alkylene, cyclohexylene, CH2-C6H1010, 1,2-phenylene, 1,3-phenylene or 1,4-phenylene; G is O, NH or CO-NH, or E and G together form a chemical bond; A is CxH2x where x = 2, 3, 4 or 5 (preferably x = 2 or 3) or CH2CH(C6H5); n is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2; a is an integer from 2 to 350 (preferably 5 to 150); R13 is H, C1 - C4 alkyl, branched or unbranched, CO-NH2 or COCH3;
wherein: R14 is H or C 1 -C 4 alkyl branched or unbranched; E is C1-C6-branched or unbranched alkylene, cyclohexylene, CH2-C6H1010, 1,2-phenylene, 1,3-phenylene or 1,4-phenylene; A is CxH2x where x = 2, 3, 4 or 5 preferably 2 or 3 or CH2CH(C6H5); L is CxH2 x with x = 2, 3, 4 or 5 preferably x = 2 or 3 or CH2CH(C6H5); a is an integer from 2 to 350 preferably 5 to 150; d is an integer from 1 to 350 preferably 5 to 150; R19 is H or C1-C4 alkyl branched or unbranched; R20 is H or C1 -C4 alkyl branched or unbranched; and n is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2;
wherein: R21, R22 and R23 independently of one another are H or C1-C4 alkyl branched or unbranched; W is O, NR25 or N; Y is 1 if W = O or NR25, and is 2 if W = N; A is CxH2x with x = 2, 3, 4 or 5 preferably 2 or 3 or CH2CH(C6H5); a is an integer from 2 to 350 preferably 5 to 150; R24 is H or branched or unbranched C1-C4 alkyl; R25 is H or branched or unbranched C1-C4 alkyl;
wherein R6 is H or branched or unbranched C1-C4 alkyl; Q is NR10, N or O; Y is 1 if W = O or NR25, and is 2 if W = N; R10 is H or C1-C4 alkyl branched or unbranched; A is CxH2x with x = 2, 3, 4 or 5 preferably 2 or 3 or CH2CH(C6H5; and a is an integer from 2 to 350 preferably 5 to 150;
[0044] Preferably, the polymer comprises polyether side chains formed from (a) at least one structural unit (IIa), wherein R10 and R12 are H, R11 is H or CH3, E and G together form a bond chemistry, A is CxH2 x with x = 2 or 3, a is 3 to 150, and R13 is H or C1-C4 alkyl branched or unbranched; and/or (b) at least one structural unit (IIb), wherein R16 and R18 are H, R17 is H or CH3, E is C1-C4 alkylene-branched or unbranched, A is CxH2x with x = 2 or 3 , L is CxH2x with x = 2 or 3, a is an integer from 2 to 150, d is an integer from 1 to 150, R19 is H or branched or unbranched C1-C4 alkyl; and R20 is H or C1-C4 alkyl branched or unbranched; and/or (c) at least one structural unit (IIc), wherein R21 and R23 are H, R22 is H or CH3, A is CxH2 x with x = 2 and/or 3, a is an integer from 2 to 150, and R24 is H or C 1 -C 4 branched or unbranched alkyl; and/or (d) at least one structural unit (IId), where R6 is H, Q is O, R7 is (CnH2n)-O-(AO)α-R9, n is 2 and/or 3, A for CxH2 x with x = 2 or 3, a is an integer from 1 to 150, and R9 is H or C1-C4 alkyl-branched or unbranched.
[0045] Especially preferred, the polymer comprises at least one structural unit of formula (IIa) and/or (CII).
[0046] According to a further modality, the polymeric dispersing agent is a polycondensate, comprising at least one aromatic or heteroaromatic structural unit with a side chain of at least one polyether side chain and or aromatic or heteroaromatic structural unit with at least one group of phosphoric acid or a salt thereof.
[0047] Preferably, the polymer includes a polycondensation product comprising structural units (III) and (IV):
wherein T is substituted or unsubstituted phenyl or naphthyl or substituted or unsubstituted, heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S; no 1 or 2; B is N, NH or O, with the proviso that n is 2 if B is N and with the proviso that n is 1 if B is NH or O; A is CxH2x with x = 2, 3, 4 or 5 preferably x = 2 or 3 or CH2CH(C6H5; a is an integer from 1 to 300, preferably 5 to 150; R25 is H or branched C1-C10 alkyl or unbranched, cycloalkyl, C5-C8 aryl or heteroaryl with 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S; wherein structural unit (IV) is selected from structural units (IVa) and (IVb):
wherein D is substituted or unsubstituted phenyl, or naphthyl or substituted or unsubstituted, heteroaryl having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S; E is N, NH or O, with the proviso that n is 2 if E is N and with the proviso that n is 1 if E is NH or O; A is CxH2x with x = 2, 3, 4 or 5 preferably x = 2 or 3 or CH2CH(C6H5; b is an integer from 1 to 300, preferably 5 to 150; M is independently is H or an equivalent cation ;
wherein V is substituted or unsubstituted phenyl or naphthyl or naphthyl which is optionally substituted by one or two groups selected from R8, OH, OR8, (CO)R8, COOM, COOR8, SO3R8 and NO2, preferably, alkyl OH, OC1-C4 and C1-C4 alkyl; R7 is COOM, OCH2COOM, SO3M or OPO3M2; M is H or an equivalent cation; and R8 is C-alkyl, phenyl, naphthyl, phenyl C1-C4, C1-C4 alkyl, or C1-C4 alkylphenyl.
[0048] Preferably, the polymer includes a polycondensation product comprising structural units (III) and (IV), wherein T is substituted phenyl or unsubstituted naphthyl, E is NH or O, A is CxH2 x with x = 2 and /or 3, a is an integer from 1 to 150, and R25 is H or C1-C10 alkyl branched or unbranched.
[0049] Preferably, the polymer includes a polycondensation product comprising structural units (III) and (IV), wherein D is substituted or unsubstituted phenyl or naphthyl, E is NH or O, A is CxH2 x with x = 2 or 3, and b is an integer from 1 to 150.
[0050] Especially preferred, the polymer includes a polycondensation product comprising structural units (III) and (IV), where T and/or D is phenyl or naphthyl which is substituted by 1 or 2 C1-C4 alkyl, hydroxy or C 21-C4 alkoxy.
[0051] The polycondensation product may comprise structural units (IVb), wherein V is phenyl or naphthyl which is substituted by 1 or 2 C1-C4 alkyl, OH, OCH3 or COOM, and R7 is COOM or OCH2COOM.
[0052] The polycondensation product may comprise at least one additional structural unit (V) of the formula
on what
[0053] R5 and R6 may be the same or different and are H, CH3, COOH or substituted or unsubstituted phenyl or naphthyl or substituted or unsubstituted heteroaryl with 5 to 10 ring atoms, of which 1 or 2 atoms are hetero atoms, which are selected from N, O and S.
[0054] R5 and R6 in structural unit (V) may be the same or different and are preferably H, CH3, or COOH, in particular H or one of R5 and R6 is H and the other is CH3.
The structural units (III) are preferably derived from amino-added or hydroxy-alkoxylated aromatic or heteroaromatic compounds, for example alkoxylated phenoxyethanol, phenoxypropanol, 2-alkoxyphenoxyethanols, 4-alkoxyphenoxyethanols, 2-alkylphenoxyethanols and 4-alkylphenoxyethanols, N, N -(amylamine)aniline, N-(hydroxyethyl)aniline, N,N-(dihydroxypropyl)aniline and N-(hydroxypropyl)aniline. Especially preferred are alkoxylated phenol derivatives (for example phenoxyethanol or phenoxypropanol), in particular alkoxylated phenol derivatives, especially phenol derivatives having an average molecular weight from 300 g/mol to 10,000 g/mol (for example polyethylene glycol monophenylether).
The structural units (IV) are preferably derived from amino-functionalized or hydroxy alkoxylated aromatic or heteroaromatic compounds, for example phenoxyethanol phosphate, polyethylene glycol monophenylether phosphates, N,N-(dihydroxyethyl)-anilindiphosphate, N,N-(dihydroxyethyl) anilinephosphate, N-(hydroxypropyl)anilinephosphate), which have at least one phosphoric acid ester group and/or a salt of the phosphoric acid ester group (for example by esterification with phosphoric acid and, optionally, addition of bases). Especially preferred are alkoxylated phenols with at least one phosphoric acid ester group and/or a salt of the phosphoric acid ester group (for example polyethylene glycol monophenyl ether phosphates with less than 25 ethylene glycol units) and especially preferred alkoxylated phenols having a molecular weight average from 200 g/mol to 600 g/mol (for example phenoxyethanol phosphate, polyethylene glycol monophenyl ether phosphates with 2 to 10 ethylene glycol units), the alkoxylated phenols having at least one phosphoric acid ester group and/or a salt of the ester group of phosphoric acid (eg by esterification with phosphoric acid and optionally addition of bases).
[0057] Structural units (IV) preferably are derived from formaldehyde, acetaldehyde, acetone, glyoxylic acid, and/or benzaldehyde. Formaldehyde is preferred.
[0058] In one embodiment the polymer comprises structural units of formulas (I) and (II), in particular of formulas (Ia) and (IIa).
[0059] In a further embodiment, the polymer comprises structural units of formulas (I) and (II), in particular of formulas (Ia) and (CII).
[0060] In a further embodiment the polymer comprises structural units of formulas (I) and (II), in particular of formulas (Ia) and (IIa).
[0061] In a further modality the polymer comprises structural units of formulas (I) and (II), in particular of formulas (Ia) and (IIa).
[0062] The polymer can be formed from (i) anionic or anionogenic structural units derived from acrylic acid, methacrylic acid, maleic acid, hydroxyethyl acrylate phosphoric acid ester, and/or hydroxyethyl methacrylate phosphoric acid ester, phosphoric acid diester of hydroxyethylacrylate and/or hydroxyethylmethacrylate of phosphoric acid diester and (ii) polyether side chain structural units derived from C1-C4-alkyl-polyethyleneglycol acrylic acid ester, polyethyleneglycol acrylic acid ester, C1-C4-methacrylic acid ester alkyl polyethylene glycol, methacrylic acid ester of polyethylene glycol, acrylic acid C1-C4-alkyl polyethylene glycol ester, acrylic acid polyethylene glycol ester, vinyloxy-C2-C4-alkylene-polyethylene glycol, vinyloxy-C2-C4-alkylene-polyethylene glycol- C1-C4-alkyl ether, allyloxy-polyethylene glycol, allyloxy-polyethylene glycol-C1-C4-alkyl ether, methyloxy-polyethylene glycol, methyloxy-polyethylene glycol-C1-C4- alkyl ether, isoprenyloxy-polyethylene glycol and/or isoprenyloxy-polyethylene glycol-C1-C4-alkyl ether.
[0063] Preferably, the polymer is formed from structural units (i) and (ii) which are derived from (i) phosphoric acid ester hydroxyethyl acrylate and/or phosphoric acid ester hydroxymethyl acrylate and (ii) phosphoric acid ester. C 1 -C 4 -alkyl polyethylene glycol acrylic acid and/or C 1 -C 4 -alkyl polyethylene glycol methacrylic acid ester; or (i) acrylic acid and/or methacrylic acid and (ii) polyethylene glycol C1-C4 alkyl acrylic acid ester and/or polyethylene glycol C1-C4 alkyl methacrylic acid ester; or (i) acrylic acid, methacrylic acid and/or maleic acid and (ii) vinyloxy-C2 -C4 -alkylene-polyethylene glycol, allyloxy-polyethylene glycol, methyloxy-polyethylene glycol or isoprenyloxy-polyethylene glycol. Especially preferred, the polymer is formed from structural units (i) and (ii) derived from (i) phosphoric acid ester hydroxyethyl methacrylate and (ii) C1-C4 alkyl polyethylene glycol methacrylic ester acid or acid ester polyethylene glycol methacrylic; or (i) acrylic acid and (ii) polyethylene glycol C1-C4 alkyl 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) methyloxy-polyethylene glycol or (1) maleic acid and (ii) isoprenyloxy-polyethylene glycol or (2) maleic acid and (ii) allyloxy-polyethylene glycol or (1) maleic acid and (ii) methyloxy-polyethylene glycol or
[0064] In one embodiment, the molar ratio of structural units (I): (II) is from 1:4 to 15:1, in particular from 1:1 to 10:1.
[0065] In another embodiment, the molar ratio of structural units (III):(IV) 4:1 to 1:15, in particular 2:1 to 1:10.
[0066] In one embodiment, the molar ratio of structural units (III + IV): (V) 2:1 to 1:3, in particular 1:0.8 to 1:2.
[0067] In an especially preferred embodiment, the polymer comprises a polycondensation product formed from structural units of the formulas (III) and (IV) wherein T and D are phenyl or naphthyl, wherein the phenyl or naphthyl optionally is substituted by 1 or 2 C1-C4 alkyl, hydroxy or 2C1-C4 alkoxy, B and E are O, A is CxH2 x with x = 2, a is from 3 to 150, especially from 10 to 150, and b is 1 , 2 or 3.
[0068] The preparation of polymeric dispersing agents containing structural units (I) and (II) takes place in a conventional manner, for example by free radical polymerization which is described for example in EP 894 811, EP 1 851 256, EP 2463314, EP 753488, incorporated herein in its entirety.
[0069] The preparation of polymeric dispersing agents containing structural units (III), (IV) and (V) usually occurs according to a process in which the compounds corresponding to structural units (III), (IV) and (V) ) are reacted. The preparation of polycondensates is described in US 2008/0108732, WO 2006/042709, and WO 2010/026155 incorporated herein in its entirety.
[0070] Alkoxylated isoprenol and/or alkoxylated hydroxybutyl vinyl ether and/or alkoxylated (meth)allyl alcohol and/or vinylated methylpolyalkylene glycol having, preferably, in each case, an arithmetic mean number of 4 to 340 oxyalkylene groups is preferably used as the polyether macro monomer. Methacrylic acid, acrylic acid, maleic acid, maleic anhydride, a maleic acid monoester or a mixture of a plurality of these components is preferably used as the acid monomer.
[0071] The accelerator composition as obtained after the reaction is a suspension. Preferably it is dried and used in powder form. Alternatively, it can be used as a suspension. In this case, the process, according to this invention, can be carried out at a concrete production site (for example a ready-mix concrete, prefabricated concrete plant or any other plant where the mortar, concrete or any other cementitious products are produced). So it is preferable to use the suspension as lots of water. Batch treatment water in this context is water, which is used in the production of concrete or production of similar cementitious materials. Usually the batch water treatment is mixed with cement and for examples aggregated in a ready-mixed concrete plant or ready-mixed concrete plant or any other construction site or any other place where concrete or other cementitious materials are produced. Typically batch water treatment can contain a wide range of additives, such as plasticizers, hardening accelerators, retarders, shrinkage reduction additives, air solubilizing additive and/or defoamers. It is advantageous to produce the hardening accelerators according to this invention in water in batch treatment intended for the production of concrete materials or the like, because there is no need to transport the respective inlets.
[0072] In an additionally preferred embodiment of the invention, preferably performed at a concrete production site (for example a ready-mix concrete, concrete or precast cement plant) the weight ratio of the sum of calcium source, composite of water soluble silicate and comb polymer to water, preferably batch treatment water, is between 1/1000 and 1/10, more preferably between 1/500 and 1/100.
[0073] The aqueous solution in which the reaction is carried out may contain in addition to the comb polymer a second polymer. The second polymer is a condensed poly, as described in the prior text of this embodiment and following embodiments. Preferably the comb polymer used together with the condensed poly is obtained by radical polymerization.
[0074] In a further embodiment of the invention, the reaction is carried out completely or partially in the presence of an aqueous solution containing a viscosity-enhancing polymer, selected from the group of polysaccharide derivatives and/or (co)polymers, with a weight molecular average Mw greater than 500,000 g/mol, more preferably greater than 1,000,000 g/mol, the (co)polymers containing structural units derived (preferably by free radical polymerization) from non-ionic (meth)acrylamide monomer derivatives and/ or sulfonic acid monomer derivatives. It is possible that the viscosity enhancer polymer is added at the beginning, during the process or at the end of the process. For example, it can be added to the aqueous solution of the comb polymer for the calcium compound and/or the silicate compound. The viscosity enhancing polymer can also be used during the process of preparing a setting accelerator composition by reacting a calcium compound, preferably a calcium salt, more preferably a water-soluble calcium salt with a silicon dioxide, containing component. Preferably the viscosity enhancing polymer is added at the end of the reaction (at the end of the addition of reactants) to prevent the particles from being destabilized and to maintain the best stability. The viscosity enhancer has a stabilizing function whereby segregation (aggregation and sedimentation) of eg calcium silicate hydrate) can be prevented. Preferably the viscosity enhancers are used in a dosage of from 0.001 to 10% by weight, more preferably from 0.001 to 1% by weight relative to the weight of the setting accelerating suspension. The viscosity enhancer polymer should preferably be dosed so that a plastic viscosity of the hardening accelerator suspensions greater than 80 mPa•s is obtained.
[0075] Preference is given for polysaccharide derivatives to cellulose ethers, for example, alkylcelluloses such as methylcellulose, ethylcellulose, propylcellulose and methylethylcellulose, hydroxyalkylcelluloses such as hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC) and hydroxyethylhydroxypropylcellulose, alkylhydroxyalkylcelluloses, such as methylhydroxyethylcellulose (MHEC) , methylhydroxypropylcellulose (MHPC) and propylhydroxypropylcellulose. Preference is given to methylcellulose derived from cellulose ether (MC), hydroxypropylcellulose (HPC), hydroxyethylcellulose (HEC) and ethylhydroxyethylcellulose (EHEC), and special preference is given to methylhydroxyethylcellulose (MHEC) and methylhydroxypropylcellulose (MHPC). The above-mentioned cellulose ether derivatives, which can in each case be obtained by appropriate alkylation or alkoxylation of cellulose, are preferably present as non-ionic structures, however, it would be possible to use, for example, also carboxymethylcellulose (CMC) . In addition, preference is also given to using nonionic starch ether derivatives such as hydroxypropyl starch, hydroxyethyl starch and methylhydroxypropyl starch. Preference is given to hydroxypropyl starch. Preferred are polysaccharides also bacterially produced such as gellan gum and/or xanthans and natural polysaccharides such as alginates, carrageenan and galactomannan. These can be obtained from suitable natural products by extraction processes, for example in the case of alginates and carrageenans from algae, in the case of galactomannan from locust bean seeds.
[0076] Viscosity enhancing (co)polymers with a molecular weight Mw greater than 500,000 g/mole, more preferably greater than 1,000,000 g/mole can be produced (preferably by free radical polymerization) from monomer derivatives of nonionic (meth)acrylamide and/or sulfonic acid monomer derivatives. The respective monomers can be selected, for example, from the group of acrylamide, preferably from acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-cyclohexylacrylamide, N,N -benzylacrylamide, N-dimethylaminopropylacrylamide, N,N-dimethylaminoethylacrylamide and/or N-tert-butylacrylamide and/or sulfonic acid monomer derivatives selected from the group of styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid 2 -methacrylamide-2-methylpropanesulfonic acid, 2-acrylamidebutanesulfonic acid, 2-acrylamide-2, 4,4-trimethylpentanesulfonic acid and/or the salts of the mentioned acids. It is preferred that the viscosity enhancer contains more than 50 mol%, more preferably more than 70 mol% of structural units derived from nonionic (meth)acrylamide monomer derivatives and/or sulfonic acid monomer derivatives. Other structural units preferably being contained in the copolymers can be derived for example from (meth)acrylic acid monomers, (meth)acrylic acid esters with C1 to C10 branched or unbranched alcohols, vinyl acetate, vinyl propionate and/or styrene.
[0077] In a further embodiment of the invention, the viscosity enhancer polymer is a polysaccharide derivative selected from the group of methylcellulose, hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), methylhydroxyethylcellulose (MHEC), methylhydroxypropylcellulose (MHPC) and/ or
[0078] (co)polymers with an average molecular weight Mw greater than 500,000 g/mol, more preferably greater than 1,000,000 g/mol, the (co)polymers containing structural units derived (preferably by free radical polymerization) from of nonionic (meth)acrylamide monomer derivatives selected from the group of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-cyclohexylacrylamide, N - benzylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminoethylacrylamide and/or N-tert-butylacrylamide, preferably acrylamide, and/or sulfonic acid monomer derivatives selected from the group of 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, and/or 2-acrylamide-2, 4,4-trimethylpentanesulfonic acid or the salts of the mentioned acids.
Within the group preferably of nonionic (meth)acrylamide monomer derivatives is given to methylacrylamide, N,N-dimethylacrylamide and/or methacrylamide, and particular preference is given to acrylamide. Within the group of acidic monomers, 2-acrylamide-2-methylpropanesulfonic acid (AMPS) and its salts are preferred. Viscosity enhancing polymers can be added at the start of the process or at any other time.
[0080] In a further embodiment of the invention the reaction is carried out completely or partially in the presence of an aqueous solution containing hardening accelerators, selected from the group of alkanolamines, preferably triisopropanolamine and / or tetrahydroxyethyl ethylene diamine (THEED). Hardening accelerators are generally added in the form of an aqueous solution. Preferably the alkanolamines are used in a dosage of 0.01 to 2.5% by weight relative to the weight of hydraulic binder, preferably cement. Synergistic effects can be found when using amines, especially triisopropanolamine and tetrahydroxyethyl ethylene diamine, with regard to the early strength development of hydraulic binder systems, especially cementitious systems. Preferably, the amine is added at the end of the reaction.
[0081] In another modality, the reaction is performed completely or partially in the presence of settling retarders selected from the group of citric acid, tartaric acid, gluconic acid, phosphonic acid, amino-trimethylenephosphonic acid, ethylenediaminetetra(methylenephosphonic) acid, diethylentriaminepenta-(methylenephosphonic acid), in each case, including the respective salts to acids, pyrophosphates, pentaborates, metaborates and/or sugars (eg glucose, molasses). Settling retarders are generally added in the form of an aqueous solution. The advantage of adding setting retarders is that the opening moment can be controlled, and in particular, if necessary, extended. The term "opening time" is understood by the person skilled in the art as the time interval after preparing the hydraulic binder mixture to the point of time at which the fluidity is considered to be not sufficient to allow adequate workability and placement of the hydraulic binder mixture. Opening time depends on the specific requirements on the job site and the type of application. As a rule, the precast industry requires between 30 and 45 minutes and the ready-mixed concrete industry requires about 90 minutes of opening time. Preferably the flame retardants are used in a dosage of 0.01 to 0.5% by weight relative to the weight of hydraulic binder, preferably cement. Retardants can be added at the beginning of the process or at any other time.
[0082] In a preferred embodiment, the setting accelerator composition obtained according to any of the aforementioned embodiments is dried, preferably by a spray drying or drum drying process. The drying method is not particularly limited, another possible drying method is for example the use of a fluid bed dryer. It is generally known that water, even if only in small amounts, is harmful to many binders, particularly cement, due to unwanted early hydration processes. Powdered products with their normally very low water content are advantageous compared to aqueous systems because it is possible to mix them in cement and/or other binders such as calcium sulphate semi-hydrated gypsum (bassanite), anhydrous calcium sulphate, slag, preferably granulated soil blast furnace slag, fly ash, silica powder, metakaolin, natural pozzolan, calcined shale, calcium sulfoaluminate cement and/or calcium aluminate cement.
[0083] The invention, on the other hand, relates to a hardening accelerator composition which is obtained by the process described above.
[0084] According to another aspect of the invention, the accelerator composition contains particles with a particle diameter below 500 nm, preferably below 300 nm, more preferably below 200 nm. The particle diameter measurement is made at a temperature of 25 °C by Beckman ultra centrifugal analysis model Optima XLI from Beckman Coulter GmbH, as described in H. Colfen, 'Analytical Ultracentrifugation of Nanoparticles', in Encyclopedia of Nanoscience andNanotechnology, (American Scientific Publishers, 2004), pp. 67-88.
[0085] Preferably, the accelerator composition is free of hydraulic binders, especially free of cement. "Free" means less than 10%, preferably less than 5%, especially less than 1% by weight and especially 0%.
[0086] Preferably the composition contains i) 0.1 to 75, preferably 0.1 to 50, more preferably 0.1 to 10% by weight of calcium silicate hydrate, ii) 0.001 to 60, preferably 0.1 to 30 , more preferably 0.1 to 10% by weight of water-soluble comb polymers suitable as a plasticizer for hydraulic binders, iii) 24 to 99, more preferably 50 to 99, more preferably 70 to 99% by weight of Water.
[0087] Typically, the calcium silicate hydrate in the composition, preferably aqueous hardening accelerator suspension is phosagite, hylebrandite, xonotlite, necoite, clinotobermorite, 9Â - tobermorite (riversiderite), 11Â - tobermorite, 14 CÂ - tobermorite (plombierite) , jenite, metajenite, calcium chondrodite, afwilite, D-C2SH, delaita, jafeita, rosenhanite, quilalaite or suolunite.
[0088] More preferably, the calcium silicate hydrate in the composition, preferably aqueous hardening accelerator suspension, is xonotlite, 9Â - tobermorite (riversiderite), 11Â - tobermorite, 14Â - tobermorite (plombierite), jenite, metajenite, afwilite or jafeita.
[0089] In a preferred embodiment of the invention, the molar ratio of calcium to silicon in the calcium silicate hydrate in the composition, preferably aqueous hardening accelerator suspension, is from 0.6 to 2, preferably from 0.8 to 1.8 , more preferably 0.9 to 1.5.
[0090] In a further preferred embodiment of the invention, the molar ratio of calcium to water in the calcium silicate hydrate is from 0.6 to 6, preferably from 0.6 to 2, more preferably 0.8 to 2. Said ranges are similar to those found for example in the calcium silicate hydrate phases, which are formed during the hydration of cement. Advantage is good acceleration effect for hydraulic binders.
[0091] It is particularly advantageous to use the hardening accelerators according to this invention in combination with cements containing a relatively high content of soluble sulfates (from 0.1 to 5% by weight relative to the cement). Such cements are commercially available or the water-soluble sulfate salt can be added to the cement. Said cement is preferably rich in anhydrous aluminate phases. Preferably the water-soluble sulphate is selected from sodium and/or potassium sulphate. Combining the soluble sulfates and setting accelerators according to this invention results in a synergistic cement setting accelerating effect.
[0092] The composition preferably contains settling retardants selected from the group of citric acid, tartaric acid, gluconic acid, phosphonic acid, amino-trimethylenephosphonic acid, ethylenediaminetetra(methylenephosphonic acid), diethylentriaminepenta-(methylenephosphonic) acid in each including their acid salts, pyrophosphates, pentaborates, metaborates and/or sugars (eg glucose, molasses). The advantage of adding setting retarders is that the opening time can be controlled, and in particular, if necessary, extended. Preferably the flame retardants are used in a dosage of 0.01 to 0.5% by weight relative to the weight of hydraulic binder, preferably cement.
[0093] The compositions may also contain any formulation component typically used in the field of construction chemicals, preferably defoamers, air solubilizing additive, retarders, shrinkage reducers, redispersible powders, other hardening accelerators, antifreeze agents and/or agents anti-efflorescents.
[0094] The invention also relates to a hardening accelerator composition, which is in powder form. The powdered product can be obtained from the aqueous product as described above, for example by spray drying or drying in a fluid bed dryer.
[0095] The invention comprises the use of a setting accelerator composition obtainable according to any of the processes of the present invention or a composition according to this invention in building material mixtures containing cement, gypsum, anhydrite, slag, preferably Blast furnace slag preferably from granulated soil, fly ash, silica powder, Metakaolin, natural pozzolans, calcined oil shale, calcium sulfoaluminate cement and/or calcium aluminate cement, preferably in building material mixtures which contain substantially of cement as a hydraulic binder.
[0096] The invention further comprises the use of the curing accelerator composition of the present invention as a grinding agent in the preparation of cement (portland), slag, fly ash, lime, puzzolan or a mixture thereof, in particular cement (portland) .
[0097] The invention further comprises the use of the hardening accelerator composition of the present invention in oil and gas drilling, in particular in the exploration, development and completion of underground oil and gas reservoirs, as well as deep drilling. The compositions are useful as settling accelerators for inorganic binders, namely to accelerate the settling of cement slurries in the cementation of oil and gas well boreholes.
[0098] Suitable inorganic binders are, inter alia, Portland cements, calcium aluminate cements, gypsum, anhydrite, blast furnace slag, granulated soil blast furnace slag, fly ash, fume silica, metakaolin, natural and artificial puzzolans, and /or calcined oil shale, preferably Portland cements.
[0099] The use of accelerating hardening compositions preferably occurs in conjunction with other additives useful in well drilling cementation, such as water reducing agents, water retention agents and/or rheological agents.
[00100] Plaster comprises in this context all possible calcium sulphate carriers with different amounts of crystal water molecules, such as for example also calcium sulphate hemidrate.
[00101] The invention also relates to building material mixtures, which contain a composition, preferably an aqueous hardening accelerator suspension according to the invention and cement, gypsum, anhydrite, slag, preferably blast furnace slag, preferably soil granulate, fly ash, silica powder, metakaolin, natural pozzolans, calcined bituminous shale, calcium sulfoaluminate cement and/or calcium aluminate cement. Preferably, the building material mixtures substantially contain cement as a hydraulic binder. The setting accelerator composition is contained in the building material mixture preferably at a dosage of 0.05% by weight to 5% by weight relative to the weight of clinker.
[00102] For illustration, the term building material mixtures can mean mixtures in dry form or in aqueous form and in hardened or plastic state. Dry building material mixtures can be, for example, mixtures of said binders, preferably cement and the setting accelerator compositions (preferably in powder form) according to this invention. Mixtures in aqueous form, usually in the form of slurry, glue, fresh mortar or fresh concrete are produced by adding water to the binder component(s) of the hardening accelerator composition, they then transform from the plastic to the hardened state. EXAMPLES STARTING MATERIALS: Source of Si: Soluble glass Na - module SiO2/Na2O = 3.4 (solids content: 36% by weight) Sources of Ca: - Ca(OH)2 (purity 97%) - CaAcetat (purity 99 .9%) - CaFormiat (99.9%) purity POLYMERS: POLYMER 1:
[00103] Polymer 1 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. MW = 40,000 g/mol as determined by GPC. The solids content is 45% by weight. The synthesis is, for example, disclosed in EP0894811. The charge density is 930 µeq/g. POLYMER 2:
[00104] Polymer 2 is a comb polymer that is a condensate of the components PhenolPEG5000 and phenoxyethanol phosphate. The molecular weight is 23,000 g/mol. The synthesis is, for example, disclosed in DE102004050395. The solids content is 31%. The charge density is 745 µeq/g. POLYMER 3:
[00105] Polymer 3 is a comb polymer, based on acrylic acid monomers and vinyloxybutylpolyethylene glycol-3000 monomers. MW = 40,000 g/mol as determined by GPC. The solids content is 52% by weight. The charge density is 1410 µeq/g. PREPARATION PROCEDURE: a. The polymer was mixed with water and loaded into a reactor; B. The calcium source was prepared by mixing calcium hydroxide and optionally another calcium source with water and optionally a polymer; ç. The silicate solution was prepared by mixing a sodium soluble glass with water; d. The aqueous solution of polymer (a) was disclosed through a 20 ml cell mixer equipped with a Turrax Ultra Ika provided with a Rotor-stator mixing tool at 8000 rpm; and. The silicate source (c) and the calcium source (b) were introduced to the shear zone of the cell mixer; Synthesis duration: 20 min.
[00106] The components used and their quantities are given in table 1. TABLE 1:

CHARACTERIZATION OF ACCELERATOR SUSPENSIONS
[00107] The effect of accelerator suspensions on the hardening of cement (CEM I Miike 52.5 R) was tested by measuring heat release using heat flux calorimetry. The results are shown in Figure 1 which shows the influence of different hardening accelerator compositions on the hardening of Portland cement. The heat flux (HF) over time (t) of pure cement is reflected by line A. H1 shows influence of a reference accelerator while H10 and H11 represent, in the influence of accelerators according to this invention (calorimetry of heat flux for H1, H10 and H11 suspensions compared to pure cement). The suspensions were mixed with the treatment water in batch and the obtained suspension was mixed with 20 g of cement. The water/cement ratio was adjusted to 0.32. The acceleration suspension dosage was selected in such a way that always 0.3% by weight of actives was dosed into the cement. An effective hardening acceleration (as defined in HFW Taylor (1997): Cement Chemistry, 2nd ed., page 212 et seq.) was observed. The results are shown in table 2. TABLE 2:

权利要求:
Claims (13)
[0001]
1. PROCESS FOR THE PREPARATION OF AN ACCELERATING HARDENING COMPOSITION, comprising: reacting, in water, a calcium source selected from the group consisting of calcium hydroxide and calcium oxide with a water-soluble silicate compound in the presence of at least one water-soluble polymeric dispersing agent, wherein the at least one water-soluble dispersing agent comprises a copolymer, and further comprises a polyether side chain, and characterized in that the water-soluble silicate compound is of the formula m SiO2 • nM2O; M is selected from the group consisting of Li, Na, K and NH4; m and n are molar numbers; and an m:n ratio is from 2.5 to 4.
[0002]
Process according to claim 1, characterized in that the calcium source and the water-soluble silicate compound are added to an aqueous solution of the water-soluble polymeric dispersing agent.
[0003]
Process according to claim 1, characterized in that: i) the source of calcium is present in an amount of 0.01 to 75% by weight of calcium hydroxide or calcium oxide, ii) the soluble silicate compound in water is present in an amount of 0.01 to 75% by weight, iii) the water-soluble dispersing agent is present in an amount of 0.001 to 60% by weight, and iv) the water is present in an amount of 24 to 99% by weight of water.
[0004]
4. Process according to claim 1, characterized in that the ratio of m:n is from 2.5 to 3.8.
[0005]
5. Process according to claim 1, characterized in that the water-soluble silicate compound is used in powder form.
[0006]
6. Process according to claim 1, characterized in that the dispersing agent is a copolymer which includes at least one structural unit, having a formula selected from the group consisting of formulas (Ia), (Ib), (Ic) and (Id):
[0007]
Process according to claim 1, characterized in that the dispersing agent is a copolymer which comprises at least one structural unit of a formula selected from the group consisting of formulas (IIa), (IIb), (IIc) and (IId):
[0008]
8. Process according to claim 1, characterized in that the dispersing agent is a polycondensation product comprising structural units (III) and (IV):
[0009]
Process according to claim 8, characterized in that the polycondensation product comprises an additional structural unit (V) of the formula
[0010]
Process according to claim 1, characterized in that it additionally comprises a subsequent step of drying the setting accelerator composition.
[0011]
11. ACCELERATING HARDENING COMPOSITION, characterized by being obtained by the process, as defined in claim 1.
[0012]
12. BUILDING MATERIAL MIXTURE, characterized in that it comprises a hardening accelerator composition, as defined in claim 11, and a building material component selected from the group consisting of cement, gypsum, anhydrite, slag, fly ash, powder of silica, metakaolin, natural pozzolans, calcined bituminous shale, calcium sulfoaluminate cement and calcium aluminate cement.
[0013]
13. A process, which comprises preparing the building material mixture as defined by claim 12, characterized by the step of mixing the hardening accelerator composition with the building material component to form the building material mixture.

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-06| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2021-03-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/01/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP13152685.7|2013-01-25|

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EP13152685|2013-01-25|

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PCT/EP2014/051485|WO2014114782A1|2013-01-25|2014-01-27|Hardening accelerator composition|

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