additive for compositions, process for preparing an additive, uses of an additive and building mater

专利摘要:
ADDITIVE FOR HYDRAULICLY SETTLED COMPOSITIONS, PROCESS FOR PREPARING AN ADDITIVE, USE OF AN ADDITIVE AND BUILDING MATERIAL MIXTURE. The invention relates to an additive which can be used as a setting accelerator for hydraulically settling compositions, comprising a) at least one polymeric dispersant composed of structural units having anionic or anionogenic groups and structural units having polyether side chains, b ) at least one sulfonic acid compound of formula (I) I wherein A1 is NH2, NH Me, NMe2, N(CHrCHrOH)2, CH3, C2Hs, CHrCHrOH, phenyl, or p-CH3-phenyl and Kn+ is a cation alkali metal, or an equivalent of a cation selected from Ca2+, Mg2+, sr2+, Ba2+, Zn2+, Fe2+, Fe3+, Al3+ Mn2+, or Cu2+ and c) calcium silicate hydrate particles.
公开号:BR112015016877B1
申请号:R112015016877-9
申请日:2014-01-27
公开日:2021-05-18
发明作者:Christoph Hesse；Manfred Bichler；Alexander Kraus；Luc Nicoleau；Torben Gãdt；Martin Winklbauer
申请人:Basf Se；
IPC主号:

专利说明:

[0001] The present invention relates to an additive for hydraulically settling compositions, a process for the preparation of the additive and the use of the additive.
[0002] It is known that additives are often added to aqueous slurries of organic or inorganic substances in powder form, such as clays, silicate ground into small particles, chalk, carbon black, stones ground into small particles and hydraulic binders, with the purpose of improving its processing properties - ie, kneading, spreading, spraying, pumping or flowability. Certain additives, comprising hardening accelerators, have an ability to shorten the curing process. This property is also deliberately exploited in connection, in particular, with the production of production material mixtures that compose hydraulic binders, such as cement, lime, gypsum, calcium sulfate hemihydrates (bassanite), or anhydrous (anhydrite) sulfate of calcium or latent hydraulic binders such as fly ash, furnace slag or pozzolans.
[0003] According to WO 02/070425, calcium silicate hydrate (C-S-H), more particularly in dispersed form (finely or very finely dispersed), can be used as such hardening accelerator. WO 2010/026155 discloses a composition comprising a water-soluble comb polymer, which is suitable as a plasticizer for hydraulic binders, and also comprises calcium silicate hydrate particles having a particle diameter < 500 nm. Calcium sources used by the prior art for the production of C-S-H particles include calcium formate, calcium chloride, calcium nitrate, calcium acetate and calcium sulfate.
[0004] WO 2012/025567 describes a method for producing a hardening and setting accelerator for hydraulic binders through the reaction of a calcium compound, which, among others, can be calcium sulfamate, with a silicone compound, accompanied by the addition of a phosphonic acid derivative comprising a polyalkalene oxide chain. The phosphonic acid derivative is prepared by esterifying or amidating a phosphonic acid compound with one or more polyalkalene oxide compounds. The derivative therefore has a terminal phosphonic acid group. Consequently, it is not a polymeric dispersant composed of structural units having anionic or anionogenic groups and structural units having polyether side chains,
[0005] WO 2013/083627 describes a method for producing a setting and hardening accelerator for mineral binders, comprising the steps of reacting a calcium compound with a silicon compound and adding an acid compound having a molecular weight of no more than 200 g/mol. It involves adding an excess of the acidic compound and always adding an additional hardening accelerator, namely methdiethanolamine, to a solution of the calcium compound. The mixture is then mixed with a solution of the silicon compound, without using a dispersant.
[0006] Mainly because of the anions that remain in the product, known hardening accelerators have a number of disadvantages. Hardening accelerators based on calcium silicate hydrate prepared using the indicated calcium compounds as their calcium source lose a considerable part of their activity on drying. This is especially the case when using calcium formate. The use of calcium chloride produces mixtures having a corrosive effect. The use of calcium nitrate with organic substances, such as other additives for hydraulically settling compositions, for example, is questionable on the basis of oxidizing nitrate ions. Calcium acetate based products are hygroscopic. Calcium sulfate, in turn, can give rise to solubility problems. The hardening accelerator effect obtained by the method described in WO 2013/083627 is inadequate in the range of up to about six hours. In particular, it will hardly be possible for concrete molds to be taken out of the molds at the beginning and therefore for production cycles to be accelerated.
[0007] Because of the stated disadvantages, the various hardening accelerators each can only be used under defined conditions. Since water, even in small amounts, is harmful to dry binders, especially cement, hardening accelerators based on calcium silicate hydrate in suspension form cannot be used as additives for dry binders. Also, for many applications, chloride-containing concrete admixtures are prohibited.
[0008] It is therefore an object of the present invention to provide an additive for hydraulically settling compositions that acts as a hardening accelerator, more particularly to increase early strengths, with initial strength, preferably referring to the compressive strength after 24 hours, especially preferably to compressive force after ten hours and very especially preferably to compressive force after six hours.
[0009] The present invention is further based on the object of providing an additive in the form of a dry product, more particularly a powder, for compositions that set hydraulically, which acts as a hardening accelerator and can be added to dry hydraulic binders . More particularly, the present invention is based on the object of providing a universally useful additive for hydraulically settling compositions in the form of a dry product, more particularly a powder, the effect of which even in the dry state is substantially comparable to the suspending effect. .
[0010] These objects are achieved by an additive for hydraulically settling compositions, comprising a dispersant, at least one non-polymeric sulfonic acid compound and calcium silicate hydrate particles.
[0011] The invention provides an additive for hydraulically settling compositions. Modalities of the invention are as follows: 1. Additive for hydraulically settling compositions comprising at least one polymeric dispersant comprising structural units having anionic or anionogenic groups and structural units having polyether side chains, b) at least one sulfonic acid compound of formula (I)
where A1 is NH2, NHMe, NMe2, N(CH2-CH2-OH)2, CH3, C2H5, CH2-CH2-OH, phenyl, or p-CH3-phenyl, and Kn+ is an alkali metal cation, or a bivalent or trivalent cation preferably selected from Ca2+, Mg2+, Sr2+, Ba2+, Zn2+, Fe2+, Fe3+, Al3+, Mn2+, or Cu2+, preferably an alkali metal cation or Ca2+, and n is the value of the cation; and c) calcium silicate hydrate particles. 2. The additive according to modality 1, wherein A1 is NH2 or CH3. 3. The additive according to modality 1 or 2, where Kn+ is Na+, K+, or Ca2+. 4. The additive according to modality 3, where Kn+ is Ca2+. 5. The additive, according to any of the above embodiments, wherein the dispersant comprises at least one polymer obtained by polymerizing at least one monomer having at least one anionic or anionogenic group and at least one monomer comprising at least one side chain of polyether. 6. The additive, according to modality 5, characterized in that the polymer as an anionic or anionogenic group has at least one structural unit of the general formulas (Ia), (Ib), (Ic) and/or (Id): ( a)
wherein R1 is H or an unbranched or branched C1-C4 alkyl group, CH2COOH, or CH2CO-X-R3; X is NH-(CnH2n) or O-(CnH2n) with n =1, 2, 3, or 4, or is a chemical bond, the nitrogen atom or the oxygen atom, respectively, being attached to the CO group; 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; (Ib)
wherein R3 is H or an unbranched or branched C1-C4 alkyl group; n is 0, 1, 2, 3, 4; R4 is PO3M2, or O-PO3M2; (Ic)
Wherein R5 is H or an unbranched or branched C1-C4 alkyl group; Z is O or NR7; and R7 is H, (CnH2n)-OH, (CnH2n)-PO3M2, (CnH2n)-OPO3M2, (C6H4)-PO3M2, or (C6H4)-OPO3M2; n is 1, 2, 3 or 4; (Id)
wherein R6 is H or an unbranched or branched C1-C4 alkyl group; Q is NR7, N or O; R7 is H, (CnH2n)-OH, (CnH2n)-PO3M2, (CnH2n)-OPO3M2, (C6H4)-PO3M2, or (C6H4)-OPO3M2; n is 1, 2, 3, or 4; and each M independently of any other is H or an equivalent cation. 7. The additive according to modality 17, wherein the polymer as anionic or anionogenic group has at least one structural unit of formula (Ia), wherein R1 is H or CH3; and/or at least one structural unit of formula (Ib), wherein 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. 8. The additive according to Modality 6 or 7, wherein the polymeric dispersant as anionic or anionogenic group has 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. 9. The additive according to any one of embodiments 5 or 8, wherein the polymer as the polyether side chain has at least one structural unit of the general formulas (IIa), (IIb), (IIc) and/or (IId ):: (IIa)
wherein R10, R11, and R12, independently of one another, are H or a branched or unbranched C1-C4 alkyl group; Z is O or S; E is C1-C6-branched or unbranched alkylene group, a cyclohexylene group, CH2-C6H10, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene; G is O, NH, or CO-NH; or E and G together are a chemical bond; A is CxH2x with x = 2, 3, 4, or 5, or CH2CH(C6H5); n is 0, 1, 2, 3, 4, and/or 5; a is an integer from 2 to 350; R13 is H, an unbranched or branched C1-C4 alkyl group, CO-NH2 or COCH3; (IIb)
wherein R16, R17 and R18 are independently of one another H or a branched or unbranched C1 -C4 alkyl group; E is a C1-C6-branched or unbranched alkylene group, a cyclohexylene group, CH2-C6H10, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, or a chemical bond; A is CxH2x with x = 2, 3, 4, or 5, or CH2CH(C6H5); L is CxH2x with x = 2, 3, 4, or 5, or CH2-CH(C6H5); a is an integer from 2 to 350; d is an integer from 1 to 350; branched; R20 is H or an unbranched or branched C1-C4 alkyl group; and n is 0, 1, 2, 3, 4 or 5; (IIc)
wherein R21, R22 and R23 are independently of one another H or a branched or unbranched C1-C4 alkyl group; 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, or CH2CH(C6H5); a is an integer from 2 to 350; R24 is H or an unbranched or branched C1-C4 alkyl group; R25 is H or an unbranched or branched C1-C4 alkyl group; (IId)
wherein R6 is H or an unbranched or branched C1-C4 alkyl group; Q is NR10, N or O; Y is 1 if Q = O or NR10, and is 2 if Q = N; R10 is H or an unbranched or branched C1-C4 alkyl group; A is CxH2x with x = 2, 3, 4, or 5, or CH2CH(C6H5); R24 is H or an unbranched or branched C1-C4 alkyl group; M is H or an equivalent cation; and a is an integer from 2 to 350; 10. The additive according to embodiment 9, wherein the polymeric dispersant as polyether side chain has: at least one structural unit of formula (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 and/or 3, a is 3 to 150, and R13 is H or a branched or unbranched C1-C4 alkyl group; and/or (b) at least one structural unit of formula (IIb), wherein R16 and R18 are H, R17 is H or CH3, E is a C1-C6-branched or unbranched alkylene group, A is CxH2x with x = 2 and/or 3 , L is CxH2x with x = 2 and/or 3, a is an integer from 2 to 150, d is an integer from 1 to 150, R19 is H or a branched or unbranched C1-C4 alkyl group branched; and R20 is H or a branched or unbranched C1-C4 alkyl group; and/or (c) at least one structural unit of formula (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 from 2 to 150, and R24 is H or a branched or unbranched C1-C4 alkyl group; and/or (d) at least one structural unit of the formula (IId), wherein R6 is H, Q is O, R7 is (CnH2n)-O-(AO)α-R9, n is 2 and/or 3, A is CxH2x with x = 2 and/or 3, α is an integer from 1 to 150, and R9 is H or a branched or unbranched C1-C4 alkyl group. 11. The additive according to Modality 9 or 10, wherein the polymeric dispersant comprises at least one structural unit of formula (IIa) and/or (IIc). 12. The additive according to any one of embodiments 1 to 4, wherein the polymeric dispersant is a polycondensate comprising at least one aromatic or heteroaromatic structural unit having a polyether side chain and at least one aromatic or heteroaromatic structural unit having at least one phosphoric ester group or a salt thereof. 13. The additive according to modality 5, wherein the dispersant comprises at least one polymer which is a polycondensation product comprising structural units (III) and (IV): (III)
wherein T is a substituted or unsubstituted phenyl radical, a substituted or unsubstituted naphthyl radical, or substituted or unsubstituted heteroaromatic radical, having from 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N , O and S; n is 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, or CH2CH(C6H5); a is an integer from 1 to 300; R25 is H, a branched or unbranched C1 to C10 alkyl radical, C5 to C8 cycloalkyl radical, aryl radical or heteroaryl radical having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N, O and S the structural unit (IV) is selected from units
wherein D is a substituted or unsubstituted phenyl radical, a substituted or unsubstituted naphthyl radical, or substituted or unsubstituted heteroaromatic radical, having from 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N , O and S; E is N, NH or O, with the proviso that m is 2 if E is N and with the proviso that m is 1 if E is NH or O; A is CxH2x with x = 2, 3, 4, or 5, or CH2CH(C6H5); b is an integer from 1 to 300; M independently at each occurrence is H or an equivalent cation; (IVb) wherein V is a substituted or unsubstituted phenyl radical or a substituted or unsubstituted naphthyl radical; R7 is COOM, OCH2COOM, SO3M, or OPO3M2; M is H or an equivalent cation; and the phenyl, naphthyl or heteroaromatic radicals mentioned, optionally being substituted by 1 or two radicals, selected from R8, OH, OR8, (CO)R8, COOM, COOR8, SO3R8, and NO2; and R8 is C1-C4 alkyl, phenyl, naphthyl, phenyl-C1-C4 alkyl, or C1-C4 alkylphenyl. 14. Additive according to modality 13, wherein T is a substituted or unsubstituted phenyl radical or naphthyl radical, E is NH or OH, A is CxH2x with x = 2 and/or 3, a is an integer from 1 to 150, and R25 is H or a branched or unbranched C1 to C10 alkyl radical. 15. Additive according to embodiment 13, wherein D is a substituted or unsubstituted phenyl radical or naphthyl radical, E is NH or O, A is CxH2x with x = 2 and/or 3, and b is an integer of 1 to 150. 16. Additive according to any one of embodiments 13 to 15, 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 groups . 17. Additive according to embodiment 13, 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. 18. Additive according to any one of embodiments 13 to 17, wherein the polycondensation product comprises an additional structural unit of formula (V)
wherein R 5 and R 6 may be identical or different and are H, CH 3 , COOH or substituted or unsubstituted phenyl or naphthyl group, or are a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S. 19. Additive, according to modality 18, wherein R5 and R6 can be the same or different and are H, CH3, or COOH, more particularly H or one of the radicals R5 and R6 is H and the other is CH3. 20. Additive according to any one of embodiments 1 to 11, wherein the polymeric dispersants have units of formulas (I) and (II), more particularly of formulas (Ia) and (IIa). 21. The additive according to embodiment 20, wherein the polymeric dispersant has structural units of formulas (Ia) and (IIc). 22. The additive according to embodiment 20, wherein the polymeric dispersant has structural units of formulas (Ic) and (IIa). 23. The additive according to embodiment 20, wherein the polymeric dispersant has structural units of formulas (Ia), (Ic) and (IIa). 24. The additive, according to any one of the modalities 1 to 11 or 20 to 23, in which the polymeric dispersant is composed of anionic or anionogenic structural units (i) derived from acrylic acid, methacrylic acid, maleic acid, phosphoric esters hydroxyethyl acrylate and/or hydroxyethyl methacrylate phosphoric esters, hydroxyethyl acrylate phosphoric diesters and/or hydroxyethyl methacrylate phosphoric diesters, and (ii) polyether side chain structural units derived from C1-C4 alkyl polyethylene glycol acrylic esters, acrylic esters of polyethylene glycol, C1-C4 alkyl-polyethylene glycol methacrylic esters, polyethylene glycol methacrylic esters, polyethylene glycol acrylic esters, vinyloxy C2-C4 alkylene-polyethylene glycol, vinyloxy C2-C4 alkylene-polyethylene glycol C1-C4 alkyl ethers, ethers glycol C1-C4 alkyl allyloxy-polyethylene glycol, polyethylene-allyloxy C1-C4, metallyloxy-polyethylene glycol, meta glycol C1-C4 alkyl ethers liloxy-polyethylene, polyethylene-isoprenyloxy glycol and/or C1-C4 alkyl ethers isoprenyloxy-polyethylene glycol. 25. The additive according to embodiment 24, wherein the polymeric dispersant is composed of structural units (i) and (ii) derived from (i) hydroxyethyl acrylate phosphoric esters and/or hydroxyethyl methacrylate phosphoric esters and (ii) C1-C4 alkyl polyethylene glycol acrylic esters and/or C1-C4 alkyl polyethylene glycol methacrylic esters; or (i) Acrylic acid and/or methacrylic acid and (ii) C1-C4 alkyl polyethylene glycol acrylic ester and/or C1-C4 alkyl polyethylene glycol methacrylic 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. 26. The additive according to embodiment 25, wherein the polymeric dispersant is composed of structural units (i) and (ii) derived from (i) hydroxyethyl methacrylate phosphoric esters and (ii) C1-C4 alkyl glycol methacrylic esters -polyethylene or polyethylene glycol methacrylic esters; or (i) methacrylic acid and (ii) polyethylene glycol C1-C4 alkyl methacrylic ester or polyethylene glycol methacrylic 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 (i) maleic acid and (ii) methyloxy-polyethylene glycol or 27. The additive according to any one of embodiments 5 to 11, wherein the molar ratio of structural units (I) ):(II) is from 1:4 to 15:1, more particularly from 1:1 to 10:1. 28. Process according to any one of the modalities 13 to 19, wherein the molar ratio of structural units (III):(IV) 'r is from 4:1 to 1:15, in particular from 2:1 to 1 :10. 29. The additive, according to any one of the modalities from 13 to 20, wherein the molar ratio of structural units (III + IV):(V) is from 2:1 to 1:3, more in particular from 1: 0.8 to 1:2. 30. The additive according to any one of embodiments 13 to 20, 28 or 29, wherein the polymeric dispersant is composed of structural units of the formulas (III) and (IV) wherein T and D are phenyl or naphthyl, the phenyl or naphthyl optionally being substituted by 1 or 2 C1-C4 alkyl, hydroxy or 2 C1-C4 alkoxy groups, B and E are O, A is CxH2x with x = 2, a is from 3 to 150, in particular from 10 to 150, and b is 1, 2 or 3. 31. The additive, according to any one of the above embodiments, wherein it is in the form of an aqueous suspension or in solid form, more particularly as a powder. 32. The additive according to embodiment 31, having, in solid form, a water content of less than 10% by weight. 33. The additive, according to any of the above embodiments, 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 from 1.0 to 1.5. 34. The additive according to any of the above embodiments, 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 of 0.8 to 2. 35. The additive according to any of the above embodiments, further comprising the formulation of auxiliaries selected more particularly from defoamers, air builders, solidification retarders, shrinkage reducers, redispersible powders, other hardening accelerators, frost inhibitors, anti-efflorescence agents and mixtures of two or more of these. 36. The additive according to any of the above embodiments, wherein the calcium silicate hydrate particles have been prepared in the presence of the polymeric dispersant. 37. The additive, according to any of the above embodiments, which is obtainable by reacting a calcium salt of at least one sulfonic acid compound of formula (1) with at least one water-soluble inorganic silicate compound in the presence of an aqueous solution of the dispersant. 38. The additive according to modality 37, wherein the calcium salt of the sulfonic acid compound is obtained by reacting a water-soluble calcium salt with a compound of formula I, wherein K is H and n is 1, this compound being used in no more than the stoichiometric amount based on the calcium salt. 39. The additive according to either of embodiments 5 and 6, wherein the dispersant does not consist exclusively of units of formula (Ia) where X is a chemical bond and R2 is M and of formula (IIc), or not comprises units of formula (IIc), when it comprises units of formula (Ia) where X is a chemical bond and R2 is M. 40. The process for preparing an additive according to any one of embodiments 1 to 39, by reaction of at least one sulfonic acid compound of formula (I) wherein Kn+ is Ca2+ with at least one water-soluble inorganic silicate compound in the presence of an aqueous solution of a dispersant. 41. The process according to modality 40, wherein the calcium salt of the sulfonic acid compound of formula (I) is obtained by reacting a water-soluble calcium salt with a compound of formula, wherein Kn+ is H+ , this compound being used in no more than the stoichiometric amount based on the calcium salt. 42. The process for preparing an additive according to any one of embodiments 1 to 39, by reacting a water-soluble calcium compound with at least one water-soluble inorganic silicate compound in the presence of a dispersant, and adding of at least one sulfonic acid compound of the formula (I). 43. The process according to embodiment 42, wherein the water-soluble calcium salt compound is selected from calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, calcium bromide calcium, calcium carbonate, calcium citrate, calcium chlorate, calcium fluoride, calcium gluconate, calcium hydroxide, calcium oxide, calcium hypochlorite, calcium iodate, calcium iodide, calcium calcium lactate, calcium nitrite calcium, calcium oxalate, calcium phosphate, calcium propionate, calcium silicate, calcium stearate, calcium sulfate, calcium sulfate hemihydrate, calcium sulfate dihydrate, calcium sulfide, calcium tartrate, calcium aluminate calcium, and mixtures of two or more of these components. 44. The process according to embodiment 43, wherein the water-soluble calcium compound is selected from calcium citrate, calcium acetate, calcium formate, calcium sulfate and mixtures of two or more of these components. 45. The process according to embodiment 43, wherein the water-soluble calcium compound is selected from calcium chloride and calcium nitrate or mixtures thereof. 46. The process according to any one of Modalities 40 to 45, wherein the water-soluble silicate compound is selected from sodium silicate, potassium silicate, water glass, aluminum silicate, calcium silicate, acid silicic acid, potassium metasilicate, sodium metasilicate, and mixtures of two or more of these components. 47. The process according to embodiment 45, wherein the water-soluble silicate compound is selected from an alkali metal silicate having the formula m SiO2^n M2O, where M is Li, Na, K and NH4, 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, preferably from about 0.9 to about 3.8, and more particularly from about 0.9 to about 3.6. The process according to any one of claims 40 to 47, which comprises an additional step of the drying process of the setting accelerator composition, the drying preferably taking place by spray drying or roller drying. 49. Use of an additive, according to any one of the modalities 1 to 39, which takes place in mixtures of building materials comprising a hydraulic binder. 50. Use of an additive, according to any one of modalities 1 to 39, which is given as an admixture for hydraulic binders. 51. Use of an additive, according to any one of modalities 1 to 39, which acts as a settlement accelerator for hydraulic binders. 52. The use according to any of the modalities, 49-51, in which the hydraulic binder is selected from cement (portland), gypsum, anhydrite, slag, preferably granulated blast furnace slag, slag sand, fly ash , finely ground silica, metakaolin, natural and artificial pozzolans, calcined bituminous shales, calcium sulfoaluminate cement, calcium aluminate cement and mixtures of two or more of these components. 53. The use of a water-soluble calcium sulfonic acid salt of formula (I) according to modality 4 for the production of calcium silicate hydrate particles. 54. The use of a water-soluble calcium sulfonic acid salt of formula (I) according to modality 4 to produce the additive according to any one of embodiments 1 to 39. 55. The use of a salt of water-soluble calcium sulfonic acid of formula (I) according to modality 4 as drying assistant. 56. The use of an additive, according to any of the modalities 1 to 39, in which it is used as a grinding assistant in the production of cement (portland), slag, fly ash, lime, pozzolans or a mixture thereof, preferably for the cement (portland). 57. The use of an additive according to any one of modalities 1 to 39 in mineral oil and natural gas wells, more particularly in the development, exploration and completion of underground deposits of mineral oil and natural gas and also in deep drilling. 58. The use of an additive in accordance with modality 57 to accelerate the settlement of cement slurries in the cementation of well drilling wells and mineral oil and natural gas. 59. A building material mixture comprising an additive according to any one of embodiments 1 to 39 and a hydraulic binder. 60. The building material mixture, according to modality 59, wherein the hydraulic binder is selected from cement (portland), blast furnace slag, slag sand, fly ash, silica powder, metakaolin, pozzolans natural, calcined bituminous shales, calcium aluminate cement and mixtures thereof. 61. The building material mixture according to modality 59 or 60 comprising cement (portland) as a hydraulic binder. The building material mixture according to any one of embodiments 59 to 61, in the form of an aqueous suspension.
[0012] In accordance with an embodiment of the invention, the particle diameter - as determined by dynamic light scattering (Malvern Zetasizer NanoZS) in the suspension according to the invention - of 90% of the calcium silicate hydrate particles is smaller than than 1000 nm, preferably less than 500 nm, more preferably less than 300 nm and most preferably less than 200 nm.
[0013] The term "sulfonic acid compound" is applied to all compounds that have a structural unit -SO3 - in which all three oxygen atoms are directly attached to the sulfur atom.
[0014] In particular, the term "sulfonic acid compound" is not limited to sulfonic acids and also encompasses their salts that contain sulfonic acid anions.
[0015] The sulfonic acid compound is mainly a compound of the formula (I)
wherein A1 is NH2, NHMe, NMe2, N(CH2-CH2-OH)2CH3, C2H5, CH2-CH2-OH, phenyl or p-CH3-phenyl, and Kn+ is an alkali metal cation, more particularly Na+, K+, or an equivalent cation selected from Ca2+, Mg2+, Sr2+, Ba2+, Zn2+, Fe2+, Fe3+, Al3+, Mn2+, and/or Cu2+.
[0016] In a particularly preferred embodiment, the anion of formula (I) is selected from amidosulfonate (H2N-SO3-) and methylsulfonate (H3C-SO3-). More particularly preferably, the anion of formula (I) is amidosulfonate (H2N-SO3-).
[0017] In at least one embodiment, the polymeric dispersant comprising at least one polymer comprising structural units having anionic and/or anionogenic groups and structural units having polyether side chains. less regular in a linear main chain, they have relatively long side chains (having a molecular weight of in each case at least 200 g/mol, more preferably at least 400 g/mol). The lengths of these side chains are often approximately equal, but they can also differ considerably from each other (eg when Polyether Macromonomers with side chains of different length are polymerized). Polymers of these types are obtained, for example, by the radical polymerization of acid monomers and polyether macromonomers. An alternative route to comb polymers of this type is the esterification and/or amidation of poly(meth)acrylic acid and similar (co)polymers, such as for example acrylic/maleic acid copolymers, for example with appropriate functional monohydroxy or glycols of monoamino functional polyalkylene, respectively, preferably alkyl polyethylene glycols. Comb polymers can be obtained by esterification and/or amidation of poly(meth)acrylic acid and are described for example in EP 1138697B1, the disclosure of which is incorporated by reference.
[0018] The average molecular weight Mw of the polymer as determined by gel permeation chromatography (GPC) is preferably from 5,000 to 200,000 g/mol, preferably from 10,000 to 80,000 g/mol, and most preferably, from 20,000 to 70,000 g/mol. Average molecular weight of polymers and conversion were analyzed by GPC (column combinations: OH-Pak SB-G, OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Shodex, Japan; eluent: 80% in 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 copolymer peak is standardized to a relative height of 1 and the peak height of the unreacted macromonomer/PEG-containing oligomer is used as a measure of the residual monomer content.
[0019] The polymeric dispersant preferably meets the requirements of industry standard EN 934-2 (February 2002).
[0020] The polymer preferably comprises, as an anionic or anionogenic group, at least one structural unit of the general formulas (Ia), (Ib), (Ic) and/or (Id): (Ia)
wherein R1 is H or branched or unbranched C1-C4 alkyl group, 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 an X= or O(CnH2n) chemical bond; 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; (Ib)
wherein R3 is H or branched or unbranched C1-C4 alkyl group, preferably H or CH3; n is 0, 1, 2, 3, or 4, preferably 0 or 1; R4 is PO3M2 or O-PO3M2; (Ic)
wherein R5 is H or branched or unbranched C1-C4 alkyl group, preferably H; Z is O or NR7, preferably O; and 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 group, preferably H; Q is NR7 or 0, preferably 0; R7 is H, (CnH2n)-0H, (CnH2n)-P03M2, (CnH2n)-0P03M2, (C6H4)-P03M2, or (C6H4)-0P03M2, n is 1, 2, 3, or 4, preferably 1.2 , or 3; and Each M independently of any other is H or an equivalent cation.
[0021] The polymer preferably additionally comprises, as anionic or anionogenic group, 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 0; and/or at least one structural unit of formula (Id), wherein R6 is H and Q is 0.
[0022] The polymer more preferably includes, as an anionic or anionogenic group at least one structural unit of formula (Ia), wherein R1 is H or CH3 and XR2 is 0M or X is 0 (CnH2n) with n = 1.2 , 3 or 4, in particular 2 and R2 is 0-P03M2.
[0023] The polymer preferably comprises as polyether side chains at least one structural unit, having the general formulas (IIa), (IIb), (IIc) and/or (IId) (IIa)
wherein R10, R11 and R12 are independently of one another H or a branched or unbranched C1-C4 alkyl group; Z is O or S; E is C1-C6-branched or unbranched alkylene group, a cyclohexylene group, CH2-C6H10, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene; G is O, NH, or CO-NH; or E and G together are a chemical bond; A is CxH2x with x = 2, 3, 4, or 5, or CH2CH(C6H5), preferably 2 or 3; n is 0, 1, 2, 3, 4, and/or 5, preferably 0, 1, or 2; a is an integer from 2 to 350 preferably 5 to 150; R13 is H, an unbranched or branched C1-C4 alkyl group; CO-NH2 and/or COCH3; (IIb)
wherein R16, R17 and R18 are independently of one another H or a branched or unbranched C1-C4 alkyl group; E is a C1-C6-branched or unbranched alkylene group, a cyclohexylene group, CH2-C6H10, 1,2-phenylene, 1,3-phenylene, or 1,4-phenylene, or a chemical bond; A is CxH2x with x = 2, 3, 4, or 5, or CH2CH(C6H5), preferably 2 or 3; L is CxH2x with x = 2, 3, 4, or 5, or CH2-CH(C6H5), preferably 2 or 3; 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 an unbranched or branched C1-C4 alkyl group; R20 is H or an unbranched or branched C1-C4 alkyl group; and n is 0, 1, 2, 3, 4 or 5, preferably 0, 1 or 2; (IIc)
wherein R21, R22 and R23 are independently of one another H or a branched or unbranched C1-C4 alkyl group; 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, or CH2CH(C6H5), preferably 2 or 3; a is an integer from 2 to 350 preferably 5 to 150; R24 is H or an unbranched or branched C1-C4 alkyl group; R25 is H or an unbranched or branched C1-C4 alkyl group; (IId)
R6 is H or an unbranched or branched C1-C4 alkyl group; Q is NR10, N or O; Y is 1 if W = O or NR10, and is 2 if W = N; R10 is H or an unbranched or branched C1-C4 alkyl group; R24 is H or an unbranched or branched C1-C4 alkyl group; M is H or an equivalent cation; A is CxH2x with x = 2, 3, 4, or 5, or CH2C(C6H5)H, preferably 2 or 3; and a is an integer from 2 to 350 preferably 5 to 150;
[0024] More preferably, the polymer comprises as polyether side chain: (a) at least one structural unit of formula (IIa), wherein R10 and R12 are H, R11 is H or CH3, E and G together form a chemical bonding, A is CxH2x with x = 2 and/or 3, a is 3 to 150, and R13 is H or a branched or unbranched C1-C4 alkyl group; and/or (b) at least one structural unit of formula (IIb), wherein R16 and R18 are H, R17 is H or CH3, E is a C1-C6-branched or unbranched alkylene group, A is CxH2x with x = 2 and/or 3 , L is CxH2x with x = 2 and/or 3, a is an integer from 2 to 150, d is an integer from 1 to 150, R19 is H or a branched or unbranched C1-C4 alkyl group branched; and R20 is H or a branched or unbranched C1-C4 alkyl group; and/or (c) at least one structural unit of formula (IIc), wherein R21 and R23 are H, R22 is H or CH3, A is CxH2x with x = 2 and/or 3, a is an integer from 2 to 150, and R24 is H or a branched or unbranched C1-C4 alkyl group; and/or (d) at least one structural unit of the formula (IId), wherein R6 is H, Q is O, R7 is (CnH2n)-O-(AO)α-R9, n is 2 and/or 3, A is CxH2x with x = 2 and/or 3, α is an integer from 1 to 150, and R9 is H or a branched or unbranched C1-C4 alkyl group.
[0025] Especially preferably, the polymer comprises at least one structural unit of formula (IIa) and/or (IIc).
[0026] According to a further modality, the polymeric dispersant is a polycondensed product, comprising at least one aromatic or heteroaromatic structural unit with a side chain of at least one polyether side chain and an aromatic or heteroaromatic structural unit with at least one group of phosphoric acid or a salt thereof.
[0027] The polycondensation product preferably comprises structural units (III) and (IV):
wherein T is a substituted or unsubstituted phenyl radical, a substituted or unsubstituted naphthyl radical, or substituted or unsubstituted heteroaromatic radical, having from 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms selected from N , O and S; n is 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, or CH2CH(C6H5), preferably 2 or 3; a is an integer from 1 to 300 preferably 5 to 150; R25 is H or branched or unbranched C1 to C10 alkyl radical, C5 to C8 cycloalkyl radical, aryl radical or heteroaryl radical having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S preferably is H; the structural unit (IV) is selected from the structural units (IVa) and (IVb):
wherein D is substituted or unsubstituted phenyl radical, a substituted or unsubstituted naphthyl radical, or a substituted or unsubstituted heteroaromatic radical having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from of N, O and S; E is N, NH, or O, with the proviso that m 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, or CH2CH(C6H5), preferably 2 or 3; b is an integer from 1 to 300 preferably 5 to 150; M independently at each occurrence is H or an equivalent cation; (IVb) wherein V is a substituted or unsubstituted phenyl radical or a substituted or unsubstituted naphthyl radical; and is optionally substituted by one or two radicals selected from R8, OH, OR8, (CO)R8, COOM, COOR8, SO3R8 and NO2, preferably, alkyl OH, OC1-C4 and alkyl C1-C4; R7 is COOM, OCH2COOM, SO3M, or OPO3M2; M is H or an equivalent cation; the phenyl, naphthyl or heteroaromatic radicals mentioned, optionally being substituted by 1 or two radicals, selected from R8, OH, OR8, (CO)R8, COOM, COOR8, SO3R8, and NO2; and R8 is C1-C4 alkyl, phenyl, naphthyl, phenyl-C1-C4 alkyl, or C1-C4 alkylphenyl.
[0028] Preferably, the polymer comprises a polycondensation product comprising structural units (III) and (IV), wherein T is substituted or unsubstituted phenyl radical or naphthyl radical, E is NH or O, A is CxH2x with x = 2 and/or 3, a is an integer from 1 to 150, and R25 is H or a branched or unbranched C1 to C10 alkyl radical.
[0029] Preferably, the polymer comprises a polycondensation product comprising structural units (III) and (IV), wherein D is a substituted or unsubstituted phenyl or naphthyl radical, E is NH or O, A is CxH2 x with x = 2 or 3, and b is an integer from 1 to 150.
[0030] Especially preferably, the polymer comprises a polycondensation product comprising structural units (III) and (IV), wherein T and/or D is phenyl or naphthyl which is substituted by 1 or 2 C1-C4 alkyl, hydroxy or 2 C1-C4 alkoxy groups.
[0031] 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.
[0032] The polycondensation product may include an additional structural unit (V), derived from the corresponding carbonyl compound and the formula (V)
on what
[0033] R5 and R6 may be identical or different and are H, CH3, COOH or substituted or unsubstituted phenyl or naphthyl group, or are a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, of which 1 or 2 atoms are heteroatoms, which are selected from N, O and S.
[0034] Preferably, R5 and R6 in structural unit (V) may be the same or different and are H, CH3, or COOH, in particular H or one of the radicals R5 and R6 is H and the other is CH3.
The structural units (III) are preferably derived from alkoxylated, phenoxyethanol, phenoxypropanol, 2-alkoxyphenoxyethanols, 4-alkoxyphenoxyethanols, 2-and 4-alkylphenoxyethanols alkylphenoxyethanols, N, N-(dihydroxyethyl) aniline, N-(hydroxyethyl) aromatic or heteroaromatic aniline or hydroxyl, examples being amino-functionalized alkoxylated, N,N-(dihydroxypropyl)aniline, and N-(hydroxypropyl)aniline. Particularly preferred are alkoxylated phenol derivatives (for example phenoxyethanol or phenoxypropanol), most preferably alkoxylated phenol derivatives, more particularly ethoxylated, having a weight average molecular weight of between 300 g/mol and 10,000 g/mol (for example polyethylene glycol monophenyl ether).
The structural units (IV) are preferably derived from phosphated, alkoxylated, hydroxyl or aromatic or heteroaromatic, examples being phenoxyethanol phosphate, phosphates of polyethylene glycol monophenyl ethers, functionalized-amino N, N-(dihydroxyethyl) aniline diphosphate, N,N-(dihydroxyethyl) aniline phosphate, N-(hydroxypropyl) aniline phosphate, which has at least one phosphoric ester group and/or a salt of the phosphoric ester group (eg by esterification with acid phosphoric, and optional addition of bases). Especially preferred are alkoxylated phenols with at least one phosphoric ester group and/or a salt of the phosphoric ester group (for example polyethylene glycol monophenyl ether phosphates with less than 25 ethylene glycol units) and preferably in particular it is given to the respective alkoxylated phenols having weight average molecular weights from 200 g/mol to 600 g/mol (for example phenoxyethanol phosphate, polyethylene glycol monophenyl ether phosphates with 2 to 10 µm ethylene glycol), alkoxylated phenols having 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).
[0037] Structural units (IV) preferably are derived from formaldehyde, acetaldehyde, acetone, glyoxylic acid, and/or benzaldehyde. Formaldehyde is preferred.
[0038] In one embodiment the polymer comprises structural units of formulas (I) and (II), in particular of formulas (Ia) and (IIa).
[0039] In another embodiment, the polymer comprises structural units of formulas (Ia) and (IIc).
[0040] In one embodiment the polymer comprises structural units of formulas (Ic) and (IIa).
[0041] In one embodiment the polymer comprises structural units of formulas (Ia), (Ic), and (IIa).
[0042] The polymer can be composed of anionic or anionogenic structural units (i) derived from acrylic acid, methacrylic acid, maleic acid, hydroxyethyl acrylate phosphoric esters and/or hydroxyethyl methacrylate phosphoric esters, hydroxyethyl acrylate phosphoric diesters and/or phosphoric methacrylate diesters hydroxyethyl, and (ii) polyether side chain structural units derived from C1-C4 alkyl polyethylene glycol acrylic esters, polyethylene glycol acrylic esters, C1C4 alkyl polyethylene glycol methacrylic esters, polyethylene glycol methacrylic esters, polyethylene glycol acrylic esters polyethylene glycol, vinyloxy C2-C4 alkylene-polyethylene glycol, vinyloxy glycol C1-C4 alkyl ethers C2-C4 alkylene-polyethylene glycol, allyloxy-polyethylene glycol C1-C4 alkyl ethers, polyethylene-C1-C4 allyloxy, methalyloxy-polyethylene glycol , methylyloxy-polyethylene glycol C1-C4 alkyl ethers, polyethylene glycol-isoprenyloxy and/or C1-C4 alkyl isoprenyl ethers loxy-polyethylene glycol. Preferably, the polymer is composed of structural units (i) and (ii) which are derived from hydroxyethyl acrylate phosphoric esters and/or hydroxyethyl methacrylate phosphoric esters and (ii) C1-C4 alkyl-polyethylene glycol acrylic esters and/ or C1-C4 alkyl polyethylene glycol methacrylic esters; or (i) Acrylic acid and/or methacrylic acid and (ii) C1-C4 alkyl polyethylene glycol acrylic ester and/or C1-C4 alkyl polyethylene glycol methacrylic 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 and/or isoprenyloxy-polyethylene glycol. Preferably, the polymer is composed of structural units (i) and (ii) which are derived from (i) hydroxyethyl methacrylate phosphoric esters and (ii) C1-C4 alkyl polyethylene glycol methacrylic esters or polyethylene glycol methacrylic esters; or (i) methacrylic acid and (ii) polyethylene glycol C1-C4 alkyl methacrylic ester or polyethylene glycol methacrylic 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 (i) maleic acid and (ii) methyloxy-polyethylene glycol.
[0043] In one embodiment, the molar ratio of structural units (I):(II) is from 1:4 to 15:1, more particularly from 1:1 to 10:1.
[0044] In another embodiment, the molar ratio of structural units (III):(IV) 4:1 to 1:15, in particular 2:1 to 1:10.
[0045] In another embodiment, the molar ratio of structural units (III+IV):(V) is from 2:1 to 1:3, in particular from 1:0.8 to 1:2.
[0046] 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 is optionally 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, in particular from 10 to 150, and b is 1, 2 or 3.
[0047] The polymeric dispersants comprising the structural units (I) and (II) are prepared in a customary way, such as by radical polymerization. This is described, for example, in EP0894811, EP1851256, EP2463314, EP0753488, incorporated in its entirety herein by reference.
[0048] Polymeric dispersants comprising the structural units (III), (IV), and (V) are generally prepared by a process in which the compounds forming the bases for the structural units (III), (IV) and (V) ) are reacted with each other in a polycondensation. The preparation of polycondensates is described for example in US 2008/0108732, WO 2006/042709, and WO 2010/026155, fully incorporated herein by reference.
[0049] The additive may take the form of an aqueous suspension, or, after drying, the form of a dry product, such as a piece of material, a powder material, a bulk material and/or a powder, preferably a dust. If the additive is present in suspension form, the compound of formula (I) can be present in dissolved or suspended form. As a dry product, the additive has a water content of less than 15% by weight, preferably less than 10% by weight, more preferably less than 7% by weight.
[0050] The water content is checked by determining the mass loss of the powder at 100°C by storing 1 g of powder in a forced air drying cabinet at 100°C for 3 hours.
[0051] The term "calcium silicate hydrate" also encompasses calcium silicate hydrate containing extraneous ions, such as magnesium and aluminum cations, for example.
[0052] The composition of CSH particles can be described in general through the following empirical formula: a CaO, SiO2, b Al2O3, c H2O, d X, and WX is an alkali metal is an alkaline earth metal 0.1 < a < 2 preferably 0.66 < a < 1.8 0 < b < 1 preferably 0 < b < 0.1 1 < c < 6 preferably 1 < c < 6.0 0 < d < 1 preferably 0 < d < 0.4 0 < e < 2 preferably 0 < e < 0.1
[0053] 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. Aluminum salts used can preferably be aluminum halide, aluminum nitrate, aluminum hydroxide or aluminum sulphate. Within the group of aluminum halides, aluminum chloride is particularly preferred. Magnesium salts can preferably be magnesium nitrate, magnesium chloride and/or magnesium sulphate. Aluminum salts and magnesium salts have the advantage that defects in the calcium silicate hydrate can be created by introducing ions other than calcium and silicon. This leads to a better hardening acceleration effect. Preferably the molar ratio of aluminum and/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).
[0054] Calcium silicate hydrate particles are normally present, at least in part, in one or more of the following crystal structures: phoshagite, hillebrandite, xonotlite, nekoite, clinotobermorite, 9A-tobermorite (riversiderite), 1lA-tobermorite , 14A-tobermorite (plombierite), jennite, metajennite, calcium chondrodite, afwillite,α - C 2 SH, dellaita, jaffeita, rosenhahnite, killalaita or suolunite.
With particular preference to calcium silicate hydrate, the particles are in the form of xonotlite, 9A-tobermorite (riversiderite), 11A-tobermorite, 14A-tobermorite (plombierite), jennite, metajennite, afwillitae/or jaffeta.
[0056] The molar ratio of calcium to silicon in the calcium silicate hydrate particles of the additive for hydraulically settling compositions is 0.6 to 2, preferably 0.8 to 1.8, more preferably 0.9 to 1.6 and in particular from 1.0 to 1.5.
[0057] The molar ratio of calcium to water in the additive calcium silicate hydrate particles for hydraulically settling compositions is 0.6 to 6, preferably 0.6 to 4, more preferably 0.8 to 2. These molar ratios are similar to those found, for example, in the calcium silicate hydrate phases, which are formed during cement hydration.
The additive in suspension form for hydraulically settling compositions preferably comprises i) 0.1 to 20% by weight, preferably 1 to 15% by weight, and most preferably 3 to 10% by weight of the calcium silicate hydrate particles , ii) 0.1 to 30% by weight, preferably 1 to 20% by weight, and most preferably 1 to 10% by weight of the dispersant, iii) 1 to 30% by weight, preferably 5 to 25% by weight, and most preferably 10 to 20% by weight of the sulfonic acid compound, and iv) 24 to 99% by weight, more preferably 50 to 99% by weight, and most preferably 60 to 90% by weight of water. v)
[0059] Particularly preferably, the additive is in powder form and then comprises: vi) 10 to 70% by weight, preferably 20 to 50% by weight, and most preferably 20 to 30% by weight of the silicate hydrate particles of calcium, vii) 5 to 50% by weight, preferably 10 to 30% by weight, and most preferably 15 to 25% by weight of the dispersant, viii) 30 to 80% by weight, preferably 45 to 65% by weight, of the compound of sulfonic acid, and ix) 1 to 15% by weight and preferably 2 to 10% by weight of water.
[0060] It is particularly advantageous to use the additive of the invention in combination with cements with a relatively high content of soluble sulfates (0.1 to 5% by weight, based on cement). Cements of this type are commercially available, or can be admixed with the water-soluble sulfate salt. Said cement is preferably rich in anhydrous aluminate phases. Preferably the water-soluble sulphate is selected from sodium sulphate and/or potassium sulphate. The combination of the invention's soluble sulfates and setting accelerator results in a synergistic effect to accelerate cement setting.
[0061] The additive of the invention can be mixed with hardening accelerators from the group of alkanolamines, preferably triisopropanolamine and/or tetrahydroxyethylethylenediamine (THEED). Alkanolamines are preferably used in an addition of 0.01 to 2.5% by weight, based on the weight of the hydraulic binder, preferably cement.
[0062] When amines are used, more particularly, triisopropanolamine and tetrahydroxyethyl ethylene diamine synergistic effects can be found, especially with regard to the early strength development of hydraulic binder systems, especially cementitious systems.
[0063] The additive of the invention may preferably contain solidification retarders selected from the group consisting 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 of acids, and pyrophosphates, pentaborates, metaborates and/or sugars (eg glucose, molasses). The advantage of adding solidification retarders is that the opening moment can be controlled and in particular, optionally, it can be extended. Solidification retarders are preferably used in an addition of 0.01 to 0.5% by weight, based on the weight of the hydraulic binder, preferably cement.
[0064] The additive of the invention may also include formulation components that are generally used in the field of construction chemicals, preferably defoamers, air builders, retarders, shrinkage reducers, redispersible powders, other hardening accelerators, inhibitors of frost and/or anti-efflorescence agents.
[0065] An additive of the invention is first obtainable by A) the reaction of at least one water-soluble calcium salt of a non-polymeric sulfonic acid with at least one water-soluble inorganic silicate compound in the presence of a solution aqueous of a dispersant. The calcium sulfonic acid salt of the non-polymeric sulfonic acid in reaction A) serves as (a) reactant in the reaction (calcium source) in which calcium silicate hydrate particles are formed.
[0066] According to the invention, after reaction A), sulfonic salts or sulfonic acid anions are present in the additive.
[0067] An additive of the invention is secondly obtainable by B) reacting a water-soluble calcium compound (which preferably is not the calcium salt of a non-polymeric sulfonic acid) with at least one inorganic silicate compound. water in the presence of an aqueous solution of a dispersant, with the addition of a water-soluble non-polymeric sulfonic salt. The sulfonic salt can be added before, during and - preferably - after the reaction. It improves the drying properties of the C-S-H suspension and allows the setting acceleration property of the additive of the invention to be kept the same through a subsequent drying step. Thus, it acts as a drying assistant.
[0068] In a preferred modality of the additive for hydraulically settling compositions, the molar ratio of the present sulfonic acid composition to silicon is in the range from 0.5 to 8, preferably from 0.5 to 5, more particularly 1 to 5 . If the additive is obtained by reaction A), the ratio is preferably in the range 1 to 4, more particularly 2 to 4. If the additive is obtained by reaction A), the ratio is preferably in the range 1 to 4, more particularly from 2.5 to 5.5.
[0069] The additive of the invention is preferably free of hydraulic binders, more particularly in cement free form. "Free" or "cement-free" means that the additive generally contains less than 10% by weight, preferably less than 5% by weight, more particularly less than 1% by weight, and more preferably 0% by weight of hydraulic binder, more particularly of cement.
[0070] The invention also relates to processes for the preparation of the additive described above.
[0071] Process A) to prepare an additive of the invention is possible by A) the reaction of at least one water-soluble calcium salt of a non-polymeric sulfonic acid of formula (1) (Kn+ is H+) with at least one compound of water-soluble inorganic silicate in the presence of an aqueous solution of a dispersant polymer. In this case, it is preferable to use the sulfonic acid in the largest stoichiometric amount, ie no excess sulfonic acid is used. According to the invention, sulfonic salts and/or sulfonic acid anions of the formula (I) are present in the additive in the product of process A).
[0072] Process B) for preparing an additive of the invention is carried out by reacting a water-soluble calcium compound (which is preferably not the calcium salt of a non-polymeric sulfonic acid) with at least one soluble inorganic silicate compound in water in the presence of an aqueous solution of a dispersant, and the addition of a water-soluble non-polymeric sulfonic salt. The water-soluble sulfonic salt can be added before, during and - preferably - after the reaction. In an optional drying step, which can take place after the addition of the water-soluble sulfonic salt, the water-soluble sulfonic salt serves as a drying assistant.
[0073] As a water-soluble calcium sulfonic acid salt, as a water-soluble inorganic silicate compound, as a water-soluble calcium compound, and as a water-soluble sulfonic salt, compounds that are suitable include compounds that have only a solubility in relatively poor water. However, it is necessary to ensure that the reactivity is sufficient for the reaction in the aqueous environment with the corresponding reagent (water-soluble silicate compound or water-soluble calcium compound). The solubility of the water-soluble calcium sulfonic acid salt, the water-soluble inorganic silicate compound, the water-soluble calcium compound and the water-soluble sulfonic salt is generally in each case greater than 0.01 g/l, preferably greater than 0.1 g/l, more preferably greater than 1 g/l, most preferably greater than 10 g/l, especially preferably greater than 50 g/l. Solubility is based on water as a solvent at 20°C and 1 bar (absolute).
[0074] In a preferred embodiment of process A), the water-soluble calcium sulfonic acid salt and the water-soluble inorganic silicate compound are each at least partially dissolved in the water in separate vessels and then reacted by adding both the solutions to the aqueous solution of the dispersant, the temperature being kept constant at 20 °C. As an alternative the solutions of the water-soluble sulfonic salt of calcium and/or the water-soluble silicate compound may firstly also be mixed with at least a part of the aqueous solution of the dispersant. The dispersant, therefore, can be divided over at least two or three solutions. Advantageously, 1% to 50% and preferably 10% to 25% of the total amount of the dispersant is present in the solution of the water-soluble sulfonic salt of calcium and/or in the solution of the water-soluble inorganic silicate compound.
[0075] In a preferred embodiment of process B), the water-soluble calcium compound and the water-soluble inorganic silicate compound are each at least partially dissolved in the water in separate vessels and then reacted by adding both solutions to the aqueous solution of the dispersant, the temperature being kept constant at 20°C. Alternatively, solutions of the water-soluble calcium compound and/or the water-soluble silicate compound may firstly also be mixed with at least a part of the aqueous solution of the dispersant. The dispersant, therefore, can be divided over at least two or three solutions. Advantageously, 1% to 50% and preferably 10% to 25% of the total amount of the dispersant is present in the solution of the water-soluble calcium compound and/or in the solution of the water-soluble inorganic silicate compound.
[0076] In addition to water, the aqueous solution of the dispersant may also comprise one or more other solvents (examples being alcohols such as ethanol and/or isopropanol). The weight fraction of the non-water solvent, relative to the sum of all solvents, preferably 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. The temperature range over which the process is carried out is not subject to any particular restrictions. However, certain limits are imposed by the physical state of the system. It is preferred to operate in the range from 0 to 100°C, more preferably from 5 to 80°C and very preferably from 15 to 35°C.
[0077] The process can also be carried out under various pressures, preferably in the range of 1 to 5 bar.
[0078] The pH is dependent on the amount and nature of the reactants and the amount and nature of the dispersant. It is preferred that the pH value is greater than 8 at the end of the synthesis, more preferably in a range of 8 and 13.5. Alternatively, the pH can be adjusted by adding acid or base.
[0079] In a preferred embodiment of process A), the addition of the water-soluble calcium sulfonic salt and the water-soluble inorganic silicate compound in the aqueous dispersant solution occurs in a cyclic semi-batch process with first and second reactors arranged in series. In this case, the aqueous dispersant solution is charged to the second reactor. The first reactor is charged with the water-soluble inorganic silicate compound solution, the water-soluble sulfonic salt calcium solution and the contents of the second reactor, and the outflow from the first reactor is passed to the second reactor .
[0080] In another preferred embodiment of the processes, the addition is made as part of a continuous process, in which the water-soluble calcium sulfonic acid salt, the water-soluble inorganic silicate compound and the aqueous dispersant solution are mixed in the first reactor and the outflow from the first reactor is introduced into a second reactor (mixed-flow reactor or plug-flow reactor).
[0081] Preferably the ratio of the volumes of the first and second reactors is from 1/10 to 1/2000. Preferably the mass flow rate of the water soluble sulfonic salt of calcium and the water soluble inorganic silicate compound is small compared to the mass flow, leaving the second reactor and entering the first reactor, preferably the ratio is 1 /5 to 1/1000. The first reactor can generally be a static or dynamic mixing unit; the mixture should preferably be effective in the first reactor.
[0082] The combination and mixing of the components in accordance with processes A) and B) will take place, preferably with the use of a dispersion medium that is capable of introducing mechanical energy into the mixture, more particularly by milling, in order to activate and /or accelerating the conversion of the reaction components and in order to, if desired, reduce the size of CSH particles. Suitable dispersion media are those which exert high shear forces in the reaction mixture. Examples of suitable dispersion media are planetary ball mills, ultra-dispersion apparatus, rotor-stator dispersion apparatus and agitator apparatus with grinding media. Such media are commercially available - for example, Dispermat from VMA Getzmann GmbH, Disperser DAS H 200 from Lau GmbH, or Magic Lab from Ika-Werke GmbH.
[0083] The additive of the invention is added to the hydraulically settling compositions preferably in an amount of 0.01 to 10% by weight and most preferably from 0.1 to 2% by weight of the solids content, based on the hydraulic binder, preferably cement. The solids content is determined in an oven at 60 °C until reaching a constant sample weight.
[0084] The water-soluble calcium compound of process B) is generally selected from calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium bicarbonate, calcium bromide, calcium carbonate, calcium citrate calcium, calcium chlorate, calcium fluoride, calcium gluconate, calcium hydroxide, calcium oxide, calcium hypochlorite, calcium iodate, calcium iodide, calcium lactate, calcium nitrite, calcium oxalate, calcium phosphate , calcium propionate, calcium silicate, calcium stearate, calcium sulfate, calcium sulfate hemihydrate, calcium sulfate dihydrate, calcium sulfate, calcium tartrate, calcium aluminate, tricalcium silicate, dicalcium silicate and mixtures of two or more of them. Preferably, the water-soluble calcium compound is not a calcium silicate. Silicates - calcium silicate, dicalcium silicate and/or tricalcium silicate - are less preferred because of their low solubility (particularly in the case of calcium silicate) and for economic reasons (price) (more particularly in the case of dicalcium silicate and tricalcium silicate ).
[0085] The water-soluble calcium complex of process B) is preferably selected from calcium citrate, calcium tartrate, calcium formate and/or calcium sulfate. The advantage of these calcium compounds lies in their non-corrosive characteristic. Calcium citrate and/or calcium tartrate, due to the possible retarding effect of these anions when used in high concentrations, are preferably used in combination with other sources of calcium.
[0086] In a further embodiment, the water-soluble calcium compound of process B) is selected from calcium chloride and/or calcium nitrate. The advantage of these calcium compounds lies in their ready solubility in water, their low price and ready availability.
The water-soluble inorganic silicate compound is generally in the form of sodium silicate, potassium silicate, water glass, aluminum silicate, silicic acid, sodium metasilicate or potassium metasilicate.
[0088] The water-soluble inorganic silicate compound is preferably in the form of sodium metasilicate, potassium metasilicate and/or water glass. The advantage of these silicate compounds lies in their extremely good water solubility.
[0089] Particularly preferably, the water-soluble inorganic silicate compound is selected from an alkali metal silicate with the formula m SiO2^n M2O, and mixtures thereof, wherein M is Li, Na, K and NH4, preferably Na or K, m and m are molar numbers and the m:n ratio is from about 0.9 to about 4, preferably from about 0.9 to about 3.8, and more particularly from about 0.9 to about of 3.6.
[0090] The invention also relates to a process for preparing the additive for hydraulically settling compositions by reacting a calcium compound, preferably a calcium salt, most preferably a water-soluble calcium salt, with a dioxide-containing component of silicon under alkaline conditions, the reaction being carried out in the presence of an aqueous solution of the dispersant and a water-soluble sulfonic salt being added.
[0091] The calcium compound preferably comprises calcium salts (eg calcium salts of carboxylic acids). The calcium salt can be, for example, calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium hydrogencarbonate, calcium bromide, calcium carbonate, calcium citrate, calcium chlorate, calcium fluoride, calcium gluconate, calcium hydroxide, calcium oxide, calcium hypochlorite, calcium iodate, calcium iodide, calcium lactate, calcium nitrite, calcium oxalate, calcium phosphate, calcium propionate, calcium silicate, calcium stearate calcium, calcium sulfate, calcium sulfate hemihydrate, calcium sulfate dihydrate, calcium sulfide, calcium tartrate, calcium aluminate, tricalcium silicate and/or dicalcium silicate. Calcium hydroxide and/or calcium oxide are preferred because of their strong alkaline properties. Preferably, the water-soluble calcium compound is not a calcium silicate. Silicates - calcium silicate, dicalcium silicate and/or tricalcium silicate are 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). Also less preferred are calcium salts which are not as readily soluble, such as calcium carbonate, for example, and also calcium salts with anions which have a retarding effect (for example citrate, gluconate and tartrate can retard hardening of hydraulic binders). In the case of neutral or acidic calcium salts (eg calcium chloride or calcium nitrate), preference is given to using a suitable base to adjust the pH to alkaline conditions (eg lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia, magnesium hydroxide or other alkaline earth metal hydroxide). Preference is given to a pH of more than 8, more preferably more than 9 and most preferably more than 11. The pH is preferably measured at 25°C, with a suspension solids content of 1% by weight.
[0092] It is possible for any desired material comprising silicon dioxide to be used as a silicon component containing dioxide, - examples are microsilica, fumed silica, precipitated silica, blast furnace slag and/or silica sand. Small particle sizes of the dioxide-containing silicon material are preferred, more particularly particle sizes below 1 µm. Furthermore, it is possible to use compounds which are capable of reacting to give silicon dioxide in an aqueous alkaline environment, such as, for example, tetraalkoxysilicate compounds of the general formula Si(OR)4. R can be the same or different and can be selected, for example, from a branched or unbranched C1 to C10 alkyl group. Preferably R is methyl, more preferably ethyl.
[0093] In a preferred embodiment, the silicon compound containing dioxide is selected from the group consisting of microsilica, fumed silica, precipitated silica, blast furnace slag and/or silica sand. Preference is given to microsilica, fumed silica and/or precipitated silica, more particularly precipitated and/or fumed silica. The silica types listed above are defined in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Release 2009, 7th edition, DOI10.1002/14356007.a23_583.pub3.
[0094] It is preferable to apply mechanical energy to the reaction mixture, preferably by milling, in order to activate and/or accelerate the reaction of the calcium salt with the normally less water-soluble component containing silicon dioxide. Mechanical energy is also advantageous to achieve the desired small particle sizes of calcium silicate hydrates. The word "milling" in the present patent specification denotes any method in which high shear forces are exerted on the reaction mixture in order to accelerate the reaction and obtain a suitable particle size. Milling can be carried out, for example, in an agitated ball mill in continuous or batch mode of operation. As an alternative to this an ultradisperser can be used, preferably with a rotary speed of more than 5000 rpm. Another possibility is to use an agitator device in which small grinding media, preferably with a diameter of less than 1 mm, are combined with the reaction mixture in a vessel and stirred. The agitator device is obtained, for example, from the company Fast& Fluid.
[0095] Alkaline conditions mean a process pH typically greater than 9.
[0096] The molar ratio of calcium of the calcium compound to silicon of the dioxide-containing silicon component is preferably 0.6 to 2, preferably 1.0 to 1.5.
[0097] The weight ratio of water to the sum of calcium compound and silicon component containing dioxide, is typically 0.2 to 50, preferably 2 to 10 and very, preferably 4 to 6. Water in this context means a water in the reaction mixture, in which the process is carried out. The process is preferably carried out in relatively low water content in order to increase the production rate of the process. This also facilitates drying. A ratio of 2 to 10 or 4 to 6 is particularly preferred as a pasty consistency product can be obtained, which is preferred for the milling process.
[0098] In a further embodiment of the invention, the reaction is carried out at least partially in the presence of an aqueous solution containing a viscosity-enhancing polymer, selected from the group of polysaccharide derivatives and/or (co)polymers, having 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. The additives of the invention thus optionally include such viscosity enhancing polymers. It is possible for the viscosity enhancer polymer to be 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 enhancing agent has a stabilizing function as segregation (aggregation and sedimentation) of for example calcium silicate hydrate can be prevented. Viscosity enhancing agents are preferably employed at an addition of from 0.001 to 10% by weight and more preferably from 0.001 to 1% by weight, based on the weight of the hardening accelerator suspension. The viscosity enhancer polymer should preferably be measured so as to produce hardening accelerator suspensions having a plastic viscosity of more than 80 mPas.
Preferred polysaccharide derivatives are 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), MHPC) and propylhydroxypropylcellulose. Cellulose ether derivatives are methylcellulose (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 in the form of non-ionic structures, however, it would be possible to use, for example, also carboxymethylcellulose ( CMC). Furthermore, preference is given for the use of non-ionic starch ether derivatives such as hydroxypropyl starch, hydroxyethyl starch and methylhydroxypropyl starch. Hydroxypropyl starch is preferred. Also preferred are microbacterially prepared polysaccharides 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.
[00100] (co) Viscosity enhancing polymers with a molecular weight MW greater than 500,000 g/mol, more preferably greater than 1,000,000 g/mol can be produced (preferably by 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 consisting of acrylamide, preferably acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-cyclohexylacrylamide, N, N-benzylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminoethylacrylamide and/or N-tert-butylacrylamide and/or sulfonic acid monomer derivatives selected from the group consisting of styrene sulfonic acid, 2-acrylamido-2- acid methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, and/or 2-acrylamidebutanesulfonic acid, 2-acrylamide-2, 4,4-trimethylpentanesulfonic acid or the salts of the mentioned acids. The viscosity enhancing agent preferably comprises more than 50 mol% and more preferably more than 70 mol% of structural units derived from nonionic acrylamide monomer derivatives (methamphetamine) and/or sulphonic acid monomer derivatives. Other structural units preferably present in the copolymers can be derived, for example, from the (meth)acrylic acid of monomers, (meth)acrylic acid esters with C1 to C10 branched or unbranched alcohols, vinyl acetate, vinyl propionate and/ or styrene.
[00101] In an additional embodiment of the invention, 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 radical polymerization) from monomer derivatives of nonionic (meth)acrylamide selected from the group of acrylamide, preferably acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylmethacrylamide, NN dimethylacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-cyclohexylacrylamide, N- benzylacrylamide, N,N-dimethylaminopropylacrylamide, N,N-dimethylaminoethylacrylamide and/or N-tert-butylacrylamide, and/or selected sulfonic acid monomer derivatives a 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 of nonionic (meth)acrylamide monomer derivatives, preference is given to methylacrylamide, N,N-dimethylacrylamide and/or methacrylamide, and particular preference is given to acrylamide. Within the group of sulfonic acid 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.
[00103] The process of the invention is preferably carried out at the concrete production site (for example, a ready-mix concrete plant or precast concrete plant or another plant in which mortar, concrete or other cement products are produced), the resulting additive, being suitable for use as batch water or as part of batch water.
[00104] Batch water in this context is water, which is used in the production of concrete or production of similar cementitious materials. Typically batch water is mixed with cement and for examples aggregated in a ready-mixed concrete plant or precast concrete plant or any other construction site or any other place where concrete or other cement materials are produced. Batch water can generally include a wide range of additives, such as, for example, plasticizers, hardening accelerators, retarders, shrinkage reducers, air builders and/or defoamers.
[00105] A high level of suspension dilution is advantageous for the effectiveness of the additive of the invention.
[00106] A preferred variant of process A) of the invention, therefore preferably performed at a concrete production site (for example a ready-mix concrete or precast concrete plant) is that the weight ratio of the sum of water-soluble sulfonic salt of calcium, of water-soluble inorganic silicate compound and of the dispersant, to water, preferably batch water, is between 1/1000 and 1/10, more preferably between 1/500 and 1/100.
[00107] A preferred variant of process A) of the invention, therefore preferably carried out at a concrete production site (for example a ready-mix concrete or precast concrete plant) is that the weight ratio of the sum of the calcium compound water-soluble, water-soluble inorganic silicate compound, the dispersant, and the water-soluble sulfonic salt, for water, preferably beating water, is between 1/1000 and 1/10, more preferably between 1/500 and 1 /100.
[00108] In a further embodiment of the process, the additive is prepared at least in part, in the presence of an aqueous solution comprising hardening accelerators from the group of alkanolamines, preferably, triisopropanolamine and/or tetrahydroxyethylethylenediamine (THEED). Alkanolamines are preferably used in an addition of 0.01 to 2.5% by weight, based on the weight of the hydraulic binder, preferably cement. If amines are used, more particularly triisopropanolamine and tetrahydroxyethylethylenediamine, they can produce synergistic effects with respect to early strength development in hydraulic binder systems, especially cementitious systems. Preferably, the amine is added at the end of the reaction.
[00109] In a variant of the preferred process, the additive for hydraulically settling compositions is dried, preferably by spray drying. The drying method is not subject to any particular restrictions. Drying can also take place in a fluid bed dryer. It is common knowledge that water, even in small amounts, is harmful to numerous binders, especially 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 semihydrate gypsum (bassanite), anhydrous calcium sulphate, slag, preferably comminuted granulated soil blast furnace slag, fly ash, finely ground silica, metakaolin, natural pozzolan, calcined shale, calcium sulfoaluminate cement and/or calcium aluminate cement.
[00110] The invention also relates to additives obtained by the processes of the invention.
[00111] The invention comprises the use of an additive of the invention in building material mixtures containing cement, gypsum, anhydrite, slag, preferably comminuted granulated blast furnace slag, fly ash, finely ground silica, metakaolin, natural pozzolans, bituminous shale calcined, calcium sulfoaluminate cement and/or calcium aluminate cement, preferably in building material mixtures which substantially contain cement as a hydraulic binder. Plaster comprises in this context all possible sources of calcium sulphate with different amounts of water crystallization molecules, including - for example - calcium sulphate hemidrate.
[00112] The additives of the invention surprisingly bring greater initial strength, more particularly after six hours. As a result of the greater development of early strength, early demolding of concrete bodies is enabled in the ready-mix concrete sector and in the precast concrete sector, thus allowing for shorter production cycles.
[00113] The present invention is also related to the use of additives of the invention as grinding assistants in the production of cement (portland), slag, fly ash, lime, pozzolans or a mixture thereof, preferably for cement (portland).
[00114] The present invention is additionally related to the use of additives of the invention in mineral oil and natural gas wells, more particularly in the development, exploration and completion of underground deposits of mineral oil and natural gas and also in deep drilling. The additives here serve as settling accelerators for inorganic binders, more particularly for accelerating the settling of cement slurries in mineral oil and natural gas well borehole cementation.
[00115] Suitable inorganic binders whose settlement is accelerated in accordance with the invention are preferably portland cements, calcium aluminate cements, gypsum, anhydrite, blast furnace slag, slag sands, fly ash, silica powder, metakaolin, pozzolans natural and synthetic and/or calcined shales, preferably portland cements.
[00116] The settlement accelerator composition is advantageously used according to the invention together with other usual additives in drilling hole cementation, more particularly plasticizers, water-retaining agents and/or rheology modifier additives.
[00117] The invention also relates to building material mixtures, which contain a composition, preferably an aqueous hardening accelerator suspension according to the present invention and cement, gypsum, anhydrite, slag, preferably granulated comminuted blast furnace slag , fly ash, finely ground silica, Metakaolin, natural pozzolans, calcined oil shale, calcium sulfoaluminate cement and/or calcium aluminate cement. Preferably, the building material mixtures predominantly contain cement as a hydraulic binder. The setting accelerator composition is present in the building material mixture preferably in an addition of 0.05% by weight to 5% by weight, based on the weight of the clinker.
[00118] For illustration, the term "building material mixtures" may 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 suspensions, pastes, fresh mortar or fresh concrete are produced by adding water to the binder(s) component(s) and the hardening accelerator composition, they then transform from the plastic to the hardened state.
[00119] The invention is illustrated in more detail by the attached figure and the examples that follow.
[00120] Figure 1 shows the heat flux of cement in settlement (A) when using the hardening accelerator suspension H1 (addition of 0.6% by weight of the suspension, solids in relation to the cement mass) and H2 (addition of 0.6% by weight of the suspension, solids in relation to the cement mass). t - time in h, HF - specific heat flux in mW/g cement
[00121] Polymers used to prepare the accelerator hardening suspensions are as follows: Polymer 1:
[00122] 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 and was determined by GPC. The solids content is 45% by weight. Synthesis is, for example, described in EP0894811. The charge density is 930 µeq/g. Polymer 2:
[00123] Comb polymer 2 is a condensate formed from the building blocks phenol PEG5000 and phenoxyethanol phosphate. The molecular weight is 23,000 g/mol. The synthesis is described in DE102004050395. The solids content is 31%. The charge density is 745 µeq/g. Polymer 3:
[00124] Polymer 3 is a comb polymer, based on acrylic acid and vinyloxybutyl polyethylene glycol-3000 monomers. MW = 23,000 g/mol and was determined by GPC. The solids content is 52% by weight. The charge density is 1410 µeq/g.
[00125] Examples for the use of sulfonic salts as drying assistants: EXAMPLE 1 PREPARATION OF H1 HARDENING ACCELERATOR SUSPENSION (NON-CREATIVE)
[00126] A source of calcium was prepared by weighing 600 g of Ca(OH)2 (92% purity) and 488 g of Ca(CH3COO-)2 (100% purity) in 4,328 kg of H2O. A silicate source was prepared by weighing 2.28 kg of sodium water glass (solids content = 36.1% by weight) with a SiO2/Na2O molar ratio of 3.4 in 1.15 kg of H2O. A dispersant solution was prepared by weighing 2.268 kg of polymer 3 (35% by weight polymer solution strength) and 0.523 kg of polymer 2 (35% by weight polymer solution strength) in 8.36 kg of H2O. The dispersant solution was initially introduced and was pumped into circulation through a high energy mixer equipped with a rotor/stator system. In the high energy mixer, the calcium source, which is agitated to prevent sedimentation, and the silicate source are monitored completely in the initially introduced solution over 80 minutes, with the rotor/stator system at a rotation speed of 8,000 rpm. During this procedure, the initial charge shown is maintained at 20°C.
[00127] H1 solids content is 14.7% by weight as determined by drying to constant weight in a forced air drying cabinet at 60°C. INFLUENCE OF ACCELERATING HARDENING SUSPENSIONS ON HARDENING (NON-INVENTIVE)
[00128] The effect of H1 hardening accelerator suspensions on hardening was tested on cement (CEM I Milke 52.5 R) by measuring heat release using heat flow calorimetry (Figure 1). The setting accelerating suspensions were mixed with the batch water and the resulting suspension obtained was mixed with 20 g of cement. The water-to-cement ratio (w/c) was set at 0.32. The level at which the accelerator under test was added was 0.6% by weight of the H1 solids content, based on the weight of cement. The heat flux curves are shown in Figure 1. The addition of the accelerating hardening suspension accelerates hardening (defined in H. F. W. Taylor (1997): Cement Chemistry, 2nd edition, p. 212ff).
[00129] The effect is summarized in table 1.
[00130] The reference represents the heat flux of CEM I Milke 52.5 R without the addition of an accelerator; curve 2 shows the heat flux for CEM I Milke 52.5 R are with addition of 0.6% by weight of hardening accelerator suspension H1. TABLE 1: HEAT FLOW IN THE MAIN HYDRATION PERIOD
EXAMPLE 2 PRODUCTION OF DRY HARDENING ACCELERATORS
[00131] H1 hardening accelerator suspension was mixed with drying assistants and dried. Drying took place by spray drying, with the drying assistant having been mixed with the hardening accelerating suspension H1 before the drying operation for about 5 minutes. The amounts of the H1 hardening accelerator suspension weighed for spray drying, and the amounts of the respective drying assistants used, are shown in table 2. For comparative examples TH1-e for TH1-h, calcium chloride is used as the drying assistant, which is disadvantageous due to the risk of corrosion. TABLE 2: PRODUCTION OF DRY HARDENING ACCELERATORS (TH1-A PARA)
EXAMPLE 3 EFFECT OF DRY HARDENING ACCELERATORS ON HARDENING
[00132] The effect of hardening accelerators obtained by drying on hardening was tested in cement (CEM I Milke 52.5 R) by measuring heat release using heat flow calorimetry. The heating accelerator was mixed with the batch water and the suspension obtained was then mixed with 20 g of cement. The water-to-cement ratio (w/c) was set at 0.32. The level at which the accelerators under test were monitored in table 3 was selected so as to use in each case the same amount of H1 solid, that is, 0.6% by weight, based on cement. Depending on the addition of the inventive drying assistant, the absolute amount of the inventive accelerator that is used may vary with the amount of H1 solids, based on cement, as described above, being kept constant. Addition of the additive of the invention accelerates hardening (defined in HFW Taylor (1997): Cement Chemistry, 2nd edition, p.212ff) Acceleration factors are summarized in table 3. TABLE 3: DRY HARDENING ACCELERATORS, NO HEAT FLOW MAIN HYDRATION PERIOD (TH1-A TO TH1-H ARE NON-INVENTIVE COMPARATIVE EXAMPLES)


[00133] Examples for the use of water-soluble sulfonic salts for the production of calcium silicate hydrate particles. EXAMPLE 4 (INVENTIVE) PREPARATION OF H2 HARDENING ACCELERATOR SUSPENSION
A calcium source was prepared by dissolving 122 g of amidosulfuric acid (100% purity) in 288.7 g of H2O, followed by the slow addition of 46.7 g of Ca(OH)2 (95% of purity). A silicate source was prepared by dissolving 104.9 g of sodium metasilicate pentahydrate (99% purity) in 109.7 g of H2O. A dispersant solution was prepared by weighing 82.8 g of a polymer solution 1 (45% by weight polymer solution strength) and 245.1 g of H 2 O. The dispersant solution was initially introduced and pumped into circulation through a high energy mixer with a 20 ml volume of mix and equipped with a rotor/stator system. In the high energy mixer, the calcium source and the silicate source are monitored completely in the initially introduced solution over 80 minutes, with the rotor/stator system operating at a rotational speed of 8,000 rpm. During this procedure, the initial solution presented is kept at 20°C. PREPARATION OF THE H3 HARDENING ACCELERATOR SUSPENSION (INVENTIVE)
[00135] A calcium source was prepared by dissolving 173.3 g of methanesulfonic acid (100% purity) in 236.7 g of H2O, followed by the slow addition of 46.7 g of Ca(OH)2 ( 95% purity). A silicate source was prepared by dissolving 104.9 g of sodium metasilicate pentahydrate (99% purity) in 109.7 g of H2O. A dispersant solution was prepared by weighing 101.9 g of a solution of polymer 1 (45% by weight of strength of polymer solution), 26.3 g of a solution of polymer 2 (35% by weight of strength of solution of polymer) and 200.3 g of water. The dispersant solution was initially introduced and pumped into circulation through a high energy mixer with a mixing volume of 20 ml and equipped with a rotor/stator system. In the high energy mixer, the calcium source and the silicate source are monitored completely in the initially introduced solution over 80 minutes, with the rotor/stator system operating at a rotational speed of 8,000 rpm. During this procedure, the initial solution presented is kept at a temperature of 20°C. Drying of the hardening accelerator suspensions H2 and H3 (inventive)
[00136] The curing accelerator suspensions H2 and H3 were dried by spray drying at an outlet temperature of 80°C, without addition of a drying assistant. This produced, from suspension H2, the dry hardening accelerator T2 and similarly, from H3, the dry hardening accelerator T3.
[00137] Influence of H2 and H3 hardening accelerator suspensions and dry hardening accelerators T2 and T3 on the hardening of cementitious systems
[00138] The hardening effect of accelerator suspensions T2 and T3, obtained by drying, was tested on cement (CEM I Milke 52.5 R) by measuring the heat release using heat flow calorimetry. The setting accelerating suspensions were mixed with the batch water and the resulting suspension obtained was mixed with 20 g of cement. The water-to-cement ratio (w/c) was set at 0.32. The measurement of the accelerators under test was selected such that in each case, the same amount of solids of H2 and H3 was used, ie 0.6% by weight based on cement. The addition of the additive of the invention accelerates hardening (defined in HFW Taylor (1997): Cement Chemistry, 2nd edition, p. 212ff). The effect is summarized in table 4. TABLE 4: H2 AND H3 HARDENING ACCELERATORS AND ALSO DRY HARDENING ACCELERATORS T2 AND T3; COMPARISON OF HYDRATION HEATS AFTER 6 H

权利要求:
Claims (13)
[0001]
1. ADDITIVE FOR COMPOSITIONS that settle hydraulically, characterized in that it comprises: a) at least one polymeric dispersant composed of structural units (i) and (ii) derived from: (i) acrylic acid, methacrylic acid and/or maleic acid and (ii) vinyloxy-C2-C4 alkylene-polyethylene glycol, allyloxy-polyethylene glycol, methyloxy-polyethylene glycol and/or isoprenyloxy-polyethylene glycol, or wherein the polymeric dispersant is a polycondensate comprising at least one aromatic or heteroaromatic structural unit having a side chain of polyether and at least one aromatic or heteroaromatic structural unit having at least one phosphoric ester group or a salt thereof, b) at least one sulfonic acid compound of formula (I)
[0002]
ADDITIVE according to claim 1, characterized in that A1 is NH2 or CH3.
[0003]
ADDITIVE according to any one of claims 1 to 2, characterized in that Kn+ is Ca2+.
[0004]
4. ADDITIVE according to any one of claims 1 to 3, characterized in that it is obtained by reacting a calcium salt of at least one sulfonic acid compound of the formula (I) with at least one water-soluble inorganic silicate compound in the presence of an aqueous solution of the dispersant.
[0005]
5. ADDITIVE according to claim 1, characterized in that the polymeric dispersant is composed of structural units (i) and (ii) derived from: (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 (i) maleic acid and (ii) methyloxy- polyethylene glycol.
[0006]
ADDITIVE according to any one of claims 1 to 5, characterized in that it is in the form of a suspension or in solid form, more particularly as a powder.
[0007]
ADDITIVE according to any one of claims 1 to 6, characterized in that 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 0.9 to 1.6 and particularly more preferably 1.0 to 1.5.
[0008]
8. A PROCESS FOR PREPARING AN ADDITIVE as defined in any one of claims 1 to 7, characterized by reacting at least one sulfonic acid compound of the formula (I) wherein Kn+ is Ca2+ with at least one water-soluble inorganic silicate compound in the presence of an aqueous solution of a dispersant.
[0009]
Process according to claim 8, characterized in that it comprises an additional step of the drying process of the setting accelerator composition, the drying preferably taking place by spray drying or roller drying.
[0010]
10. USE OF AN ADDITIVE as defined in any one of claims 1 to 7, characterized in that it is in mixtures of building materials comprising a hydraulic binder.
[0011]
11. USE OF AN ADDITIVE as defined in any one of claims 1 to 7, characterized in that it is a mixture for hydraulic binders.
[0012]
12. USE OF AN ADDITIVE as defined in any one of claims 1 to 7, characterized in that it is as a grinding assistant in the production of cement (portland), slag, fly ash, lime, pozzolans or a mixture thereof, preferably for the cement (portland).
[0013]
13. CONSTRUCTION MATERIAL MIXTURE, characterized in that it comprises an additive as defined in any one of claims 1 to 7 and a hydraulic binder.

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同族专利:

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公开号 | 公开日

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EP2948239B1|2017-10-18|

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US9802864B2|2017-10-31|

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WO2014114784A1|2014-07-31|

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ES2654628T3|2018-02-14|

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EP2759337A1|2014-07-30|

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CN105263614B|2017-10-17|

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RU2015135620A|2017-03-03|

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JP2016513144A|2016-05-12|

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AU2014209861A1|2015-08-13|

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JP6436914B2|2018-12-12|

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US20150344368A1|2015-12-03|

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CN105263614A|2016-01-20|

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RU2648382C2|2018-03-26|

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EP2948239A1|2015-12-02|

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PL2948239T3|2018-03-30|

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CA2898016C|2021-11-16|

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AU2014209861B2|2017-02-23|

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CA2898016A1|2014-07-31|

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法律状态:
2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-15| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-05-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 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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EP13152684.0|2013-01-25|

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EP13152684.0A|EP2759337A1|2013-01-25|2013-01-25|Additive for hydraulically setting masses|

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PCT/EP2014/051494|WO2014114784A1|2013-01-25|2014-01-27|Additive for masses that set hydraulically|

---