POLYCONDENSATION PRODUCT BASED ON AROMATIC COMPOUNDS, METHOD FOR THE PREPARATION AND USE THEREOF

Abstract

Proposed is a polycondensation product comprising as monomer components at least one aryl polyoxyalkylene ether, at least one vicinally disubstituted aromatic compound, at least one aldehyde and also optionally further aromatic compounds; processes for preparing same, and also use thereof as dispersant for aqueous suspensions of inorganic binders and as grinding assistant for inorganic binders.

Claims

1. A process comprising utilizing a polycondensation product as a dispersant for aqueous suspensions of inorganic binders selected from the group encompassing latent hydraulic binders, pozzolanic binders, alkali-activated and/or alkali-activatable aluminosilicate binders, and also mixtures thereof, wherein said polycondensation product comprises as monomer components: A) at least one aryl polyoxyalkylene ether of the formula (I) ##STR00004## where Ar is an aryl group, R.sub.1 and R.sub.2 each independently of one another are selected from H, methyl and ethyl, with optionally at least one of the groups R.sub.1 and R.sub.2 being H, m is an integer from 1 to 300 and R.sub.3 is selected from the group consisting of H, alkyl, aryl, aralkyl, alkaryl, phosphate, and also mixtures thereof; B) at least one aromatic compound of the formula (II), ##STR00005## where R.sub.4 and R.sub.5 each independently of one another are selected from H, R.sub.8, OH, OR.sub.8, C(O)R.sub.8, COOH, COOR.sub.8, SO.sub.3H, SO.sub.3R.sub.8 and NO.sub.2 and also alkali metal salts, alkaline earth metal salts and ammonium salts thereof, or together are a further fused-on ring, where R.sub.8 each independently is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl, and R.sub.6 and R.sub.7 each independently of one another are selected from OH, OR.sub.9, C(O)R.sub.9, COOH and COOR.sub.9 and also alkali metal salts and alkaline earth metal salts and ammonium salts thereof, where R.sub.9 each independently is selected from the group consisting of alkyl, aryl, aralkyl, alkaryl; C) at least one aldehyde; and also optionally D) at least one further aromatic compound, selected from the group consisting of phenol, 2-phenoxyethanol, 2-phenoxyethyl phosphate, 2-phenoxyethyl phosphonate, 2-phenoxyacetic acid, 2-(2-phenoxyethoxy)ethanol, 2-(2-phenoxyethoxy)ethyl phosphate, 2-(2-phenoxyethoxy)ethyl phosphonate, 2-[4-(2-hydroxyethoxy)phenoxy]ethyl phosphate, 2-[4-(2-hydroxyethoxy)phenoxy]ethyl phosphonate, 2-[4-(2-phosphonatooxyethoxy)phenoxy]ethyl phosphate, 2-[4-(2-phosphonatooxyethoxy)phenoxy]ethyl phosphonate, methoxyphenol, phenolsulphonic acid, furfuryl alcohol, and also mixtures thereof.

2. The process of claim 1, wherein the latent hydraulic binders are selected from industrial and/or synthetic slags, blast furnace slag, slag sand, ground slag sand, electrothermic phosphorus slag, stainless-steel slag, and also mixtures thereof, and the pozzolanic binders are selected from amorphous silica, precipitated silica, pyrogenic silica, microsilica, finely ground glass, fly ash, brown-coal fly ash, mineral-coal fly ash, metakaolin, natural pozzolans, tuff, trass, volcanic ash, natural zeolites, and synthetic zeolites, and also mixtures thereof.

3. The process of claim 1, wherein the alkali-activated aluminosilicate binders comprise the latent hydraulic and/or the pozzolanic binders and also alkaline activators, optionally aqueous solutions of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides, alkali metal aluminates, alkali metal silicates, soluble waterglass, and also mixtures thereof.

4. The process of claim 1, wherein the polycondensation product is utilized as a constituent of construction material formulations and/or construction material products, on-site concrete, pre-cast concrete parts, concrete ware, cast concrete stones, in-situ concrete, air-placed concrete, ready-mixed concrete, construction adhesives, adhesives for thermal insulation composite systems, concrete repair systems, one-component sealing slurries, two-component sealing slurries, screeds, filling and levelling compounds, tile adhesives, renders, adhesives, sealants, coating systems optionally for tunnels, wastewater channels, splash protection and condensate lines, dry mortars, joint grouts, drainage mortars and/or repair mortars.

5. The process of claim 1, wherein the group Ar is an aryl group having 6 to 10 carbon atoms in the ring system, optionally a phenyl group or a naphthyl group.

6. The process of claim 1, wherein m is an integer from 3 to 280.

7. The process of claim 1, wherein R.sub.3 is selected from the group consisting of H, C.sub.1-10 alkyl, C.sub.6-10 aryl, C.sub.7-11 aralkyl, C.sub.7-11 alkaryl and phosphate.

8. The process of claim 6, wherein the oxyalkylene groups of the aryl polyoxyalkylene ether of the formula (I) are selected from ethylene oxide groups and/or propylene oxide groups, which are arranged randomly, alternatingly, graduatedly and/or blockwise along the chain.

9. The process of claim 6, wherein the aryl polyoxyalkylene ether of the formula (I) is a polyethylene glycol monophenyl ether of the formula (III) ##STR00006## where m is an integer from 3 to 280.

10. The process of claim 9, wherein the polyethylene glycol monophenyl ether of the formula (III) is a mixture having different values for m.

11. The process of claim 1, wherein R.sub.8 and R.sub.9 each independently are selected from H, C.sub.1-10 alkyl, C.sub.6-10 aryl, C.sub.7-11 aralkyl and C.sub.7-11 alkaryl.

12. The process of claim 1, wherein the aromatic compound of the formula (II) is selected from the group consisting of benzene-1,2-diol, benzene-1,2,3-triol, 2-hydroxybenzoic acid, 2,3- and 3,4-dihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, phthalic acid, 3-hydroxy-phthalic acid, 2,3- and 3,4-dihydroxybenzenesulphonic acid, 1,2- and 2,3-dihydroxynaphthalene, 1,2- and 2,3-dihydroxynaphthalene-5- or -6-sulphonic acid, and also mixtures thereof.

13. The process of claim 1, wherein the aldehyde component C) is selected from the group consisting of formaldehyde, paraformaldehyde, glyoxylic acid, benzaldehyde, benzaldehydesulphonic acid, benzaldehydedisulphonic acid, vanillin and isovanillin, and also mixtures thereof.

14. The process of claim 1, wherein the molar ratio of components C:(A+B) is from 1:3 to 3:1.

15. The process of claim 1, wherein the molar ratio of components A:B is from 1:10 to 10:1.

16. The process of claim 1, wherein the polycondensation product is in the form of a comb polymer with novolak structure.

17. The process of claim 1, wherein the polycondensation product has a molecular weight in the range from 1000 to 100,000 g/mol.

18. The process of claim 1, wherein the polycondensation product is utilized together with further compounds selected from the group consisting of: glycols, polyalcohols, amine alcohols, organic acids, amino acids, sugars, molasses, organic salts, inorganic salts, polycarboxylate ethers, naphthalenesulphonate, melamine/formaldehyde polycondensation products, lignosulphonate and mixtures thereof.

Description

[0074] The present invention is now elucidated with greater precision by means of the examples below and the appended drawings. In the drawing:

[0075] FIG. 1 shows a graphic representation of the particle size distributions of ground slag sand as a function of the grinding assistant used during cold grinding;

[0076] FIG. 2 shows a graphic representation of the particle size distributions of ground slag sand as a function of the grinding assistant used during hot grinding.

EXAMPLES

Example 1

[0077] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 320 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 49 parts of 3,4-dihydroxybenzoic acid and 16 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 C. until all of the solids have dissolved, and then 44 parts of methanesulphonic acid (70% strengthhere and in all subsequent syntheses, in the form of an aqueous solution) are added over the course of 20 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 3 hours. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 2

[0078] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 300 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 46 parts of vanillin (>99%, 4-hydroxy-3-methoxybenzaldehyde) and 14.9 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 C., and then 51.4 parts of methanesulphonic acid (70%) are added over the course of 20 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 2.5 hours. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 3

[0079] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 400 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 5000 g/mol), 24.6 parts of 3,4-dihydroxybenzoic acid and 8 parts of paraformaldehyde. The reaction mixture is heated with stirring to 115 C., and then 38.4 parts of methanesulphonic acid (70%) are added over the course of 10 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 3 hours. It is then left to cool, admixed with 400 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 4

[0080] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 80 C. with 260 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 43 parts of pyrocatechol (1,2-dihydroxybenzene), 80 parts of water and 15.6 parts of paraformaldehyde. The reaction mixture is subsequently admixed with 12.5 parts of methanesulphonic acid (50%) over the course of 20 minutes at a rate such that the reaction temperature does not exceed 80 C. After the end of metering, the reaction mixture is stirred at 80 C. for a further 2 hours. It is then left to cool, admixed with 350 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 5

[0081] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 300 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 46.2 parts of 3,4-dihydroxybenzoic acid, 33 parts of 2-phenoxyethyl phosphate and 19.9 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 C., and then 41 parts of methanesulphonic acid (70%) are added over the course of 25 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 2.5 hours. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

[0082] The said 2-phenoxyethyl phosphate is synthesized generally by charging a heatable reactor, equipped with stirrer and metering pump, under nitrogen at 20 C. with 621.8 parts of 2-phenoxyethanol. Subsequently, with cooling, 449.7 parts of polyphosphoric acid are added over 100 minutes at a rate such that the temperature does not rise above 35 C. After the end of metering, the reaction mixture is stirred at about 70 C. for a further 15 minutes and is discharged prior to solidification.

Example 6

[0083] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 300 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 45.7 parts of vanillin (>99%, 4-hydroxy-3-methoxybenzaldehyde), 32.7 parts of 2-phenoxyethyl phosphate and 19.9 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 C., and then 41.1 parts of methanesulphonic acid (70%) are added over the course of 20 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 2.5 hours. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 7

[0084] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 300 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 45.6 parts of isovanillin (3-hydroxy-4-methoxybenzaldehyde), 33 parts of 2-phenoxyethyl phosphate and 19.9 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 C., and then 41 parts of methanesulphonic acid (70%) are added over the course of 20 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 1100 C. for a further 2 hours. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 8

[0085] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 80 C. with 300 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 72.1 parts of 2,3-dihydroxynaphthalene and 18.0 parts of paraformaldehyde. The reaction mixture is subsequently admixed with 12.5 parts of methanesulphonic acid (50%) over the course of 30 minutes at a rate such that the reaction temperature does not exceed 80 C. After the end of metering, the reaction mixture is stirred at 80 C. for a further 75 minutes. It is then left to cool, admixed with 350 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 9

[0086] A heatable reactor equipped with stirrer and metering pump is charged with 225 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol) and 41.5 parts of 2-phenoxyethanol. Subsequently, with cooling, 66.0 parts of polyphosphoric acid are added over 30 minutes and the mixture is stirred at 90-95 C. for 60 minutes. Added to this reaction mixture at 90 C. under a stream of nitrogen are 92.5 parts of 3,4-dihydroxybenzoic acid and 39.8 parts of paraformaldehyde. The reaction mixture is heated to about 100 C. with stirring, and then 57.6 parts of methanesulphonic acid (70%) are added over the course of 25 minutes at a rate such that the reaction temperature does not exceed 105 C. After the end of metering, the reaction mixture is stirred at 100 C. for a further 15 minutes. It is then left to cool, admixed with 350 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 10

[0087] A heatable reactor equipped with stirrer and metering pump is charged with 225 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol) and 82.9 parts of 2-phenoxyethanol. Subsequently, with cooling, 99.0 parts of polyphosphoric acid are added over 20 minutes and the mixture is stirred at 90-95 C. for 40 minutes. Added to this reaction mixture at 90 C. under a stream of nitrogen are 46.2 parts of 3,4-dihydroxybenzoic acid and 39.8 parts of paraformaldehyde. The reaction mixture is heated to about 100 C. with stirring and then 57.6 parts of methanesulphonic acid (70%) are added over the course of 25 minutes at a rate such that the reaction temperature does not exceed 105 C. After the end of metering, the reaction mixture is stirred at 100 C. for a further 15 minutes. It is then left to cool, admixed with 350 parts of water and neutralized to a pH of about 7.0 using polyethyleneimine (Lupasol G100, BASF SE).

Example 11

[0088] Aluminosilicate mortars were produced in accordance with the following formula:

TABLE-US-00001 Microsilica 150 g Fly ash, type F 150 g Silica sand 700 g KOH (0.2%) 250 g

[0089] The starting materials were mixed in the laboratory with a mortar mixer in accordance with DIN EN 196-1. The mixing operation was carried out as described in DIN EN 196-1, with the difference that the silica sand was added right at the beginning, and not only subsequently, to the mixing trough. The alkaline activator used was a 0.2% strength by weight aqueous KOH solution. All of the polymeric dispersants were defoamed using Defoamer DF93 from BASF SE or triisobutyl phosphate.

[0090] The dispersant was used as an aqueous solution as obtained in the examples above. The level of addition in each case was 3 g (calculated as solid). For comparison, determinations were made of the slump without additive and with in each case 3 g of the polycarboxylate ethers Melflux 2453 (Comparative Example 1), Glenium 51 (Comparative Example 2) and Melflux PCE 26L (Comparative Example 3), all available from BASF SE.

[0091] The compositions of the ground slag sand and type F fly ash were as follows [% by weight]:

TABLE-US-00002 SiO.sub.2 Fe.sub.2O.sub.3 TiO.sub.2 Al.sub.2O.sub.3 CaO MgO K.sub.2O remainder Slag sand 34.0 0.4 1.1 11.6 43.0 7.3 0.5 2.1 Fly ash 53.4 5.7 1.1 26.8 3.1 2.0 4.5 3.4

[0092] The slump was determined in each case by tapping 15 times on a slump table with a Hgermann cone (DIN EN 1015-3). The results are shown in Table 1.

TABLE-US-00003 TABLE 1 Example Slump [cm] Density [g/cm.sup.3] Without additive 19.9 1.94 Comparative Example 1 18.4 1.83 Comparative Example 2 18.9 1.95 Example 5 24.3 1.83 Example 6 >30.0 1.85 Example 7 >30.0 1.79

Example 12

[0093] Example 11 was repeated with the modification that 5.0% strength by weight aqueous KOH solution was used as activator. The results are shown in Table 2.

[0094] Formula:

TABLE-US-00004 Microsilica 150 g Fly ash, type F 150 g Silica sand 700 g KOH (5.0%) 262.63 g

TABLE-US-00005 TABLE 2 Example Slump [cm] Density [g/cm3] Without additive 17.5 1.96 Comparative Example 1 19.1 1.83 Comparative Example 2 19.0 1.98 Example 1 28.4 1.96 Example 3 23.0 1.91 Example 5 >30.0 1.93

Example 13

[0095] Example 11 was repeated with the modification that ground slag sand was used in the formulation. The results are shown in Table 3.

[0096] Formula:

TABLE-US-00006 Ground slag sand 300 g Silica sand 700 g KOH (0.2%) 250 g

TABLE-US-00007 TABLE 3 Example Slump [cm] Density [g/cm3] Without additive 17.1 2.11 Comparative Example 1 22.7 2.00 Example 3 25.4 2.02 Example 5 25.8 2.03 Example 6 >30.0 2.05 Example 7 >30.0 2.13 Example 8 28.2 2.06

Example 14

[0097] Example 13 was repeated with the modification that 5.0% strength by weight aqueous KOH solution was used as activator. The results are shown in Table 4.

[0098] Formula:

TABLE-US-00008 Ground slag sand 300 g Silica sand 700 g KOH (5.0%) 189.09 g

TABLE-US-00009 TABLE 4 Example Slump [cm] Density [g/cm3] Without additive 17.4 2.12 Comparative Example 1 17.9 1.86 Comparative Example 2 21.5 2.11 Example 1 28.4 2.09 Example 3 28.1 2.05 Example 5 >30.0 2.10 Example 6 >30.0 2.07 Example 7 >30.0 2.08

Example 15

[0099] Example 14 was repeated with the modification that a 3.3% strength by weight aqueous Na.sub.2CO.sub.3 solution was used as activator. The slump [in cm] was determined after 6 minutes and 30 minutes. The results are shown in Table 5.

[0100] Formula:

TABLE-US-00010 Ground slag sand 300 g Silica sand 700 g Na.sub.2CO.sub.3 (3.3%) 181 g

TABLE-US-00011 TABLE 5 Slump Example Slump (6 min) (30 min) Density [g/cm3] Without additive 17.5 16.6 2.00 Comparative Example 3 17.8 17.0 2.03 Example 9 20.4 19.9 2.01 Example 10 19.7 18.8 1.99

Example 16

[0101] Example 15 was repeated with the modification that a 3.3% strength by weight aqueous Na.sub.2SiO.sub.3 solution was used as activator. The slump [in cm] was determined after 6 minutes and 30 minutes. The results are shown in Table 6.

[0102] Formula:

TABLE-US-00012 Ground slag sand 300 g Silica sand 700 g Na.sub.2SiO.sub.3 (3.3%) 181 g

TABLE-US-00013 TABLE 6 Slump Example Slump (6 min) (30 min) Density [g/cm3] Without additive 17.6 16.1 1.99 Comparative Example 3 18.3 16.2 2.00 Example 9 20.0 19.0 1.97 Example 10 19.6 18.7 1.96

[0103] As becomes clear from these performance tests, the polymers of the invention enable a distinct improvement in the consistency of the aluminosilicate mortars in comparison to the sample without dispersants. In some cases the flow of the mortar mixtures, as a result of the addition of the polymers of the invention, exceeds the dimensions of the 30 cm tapping board. A plasticizing performance can be achieved here in different binding compositions and with different activators such as KOH, Na.sub.2CO.sub.3 or waterglass. Moreover, it can be seen that in contrast to the polycarboxylate ethers, the plasticizing of alkali-activated aluminosilicate binders is possible with the polymers of the invention.

Example 17

[0104] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 320 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 44.2 parts of salicylic acid and 15.9 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 C. until all of the solids have dissolved, and then 66 parts of methanesulphonic acid (70%) are added over the course of 15 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 4 hours. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 18

[0105] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 320 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 44.2 parts of salicylic acid, 35 parts of 2-phenoxyethyl phosphate and 21.2 parts of paraformaldehyde. The reaction mixture is heated with stirring to 110 C. and then 44 parts of methanesulphonic acid (70%) are added over the course of 15 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 2.75 hours. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 19

[0106] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 225 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), 82.9 parts of salicylic acid, 65.4 parts of 2-phenoxyethyl phosphate, 25 parts of water and 39.8 parts of paraformaldehyde. The reaction mixture is heated with stirring to 100 C. and then 115.2 parts of methanesulphonic acid (50%) are added over the course of 40 minutes at a rate such that the reaction temperature does not exceed 105 C. After the end of metering, the reaction mixture is stirred at 105 C. for a further 4 hours. It is then left to cool, admixed with 400 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 20

[0107] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 225 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), 165.7 parts of salicylic acid and 48.4 parts of paraformaldehyde. The reaction mixture is heated with stirring to 95 C. and then 57.6 parts of methanesulphonic acid (50%) are added over the course of 25 minutes at a rate such that the reaction temperature does not exceed 115 C. After the end of metering, the reaction mixture is stirred at 105 C. for a further 90 minutes. It is then left to cool, admixed with 300 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 21

[0108] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 225 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), 82.9 parts of salicylic acid, 65.4 parts of 2-phenoxyethyl phosphate and 127.6 parts of formalin (30% strength in H.sub.2O). The reaction mixture is heated with stirring to 100 C. and then 85.2 parts of sulphuric acid (70%) are added over the course of 20 minutes at a rate such that the reaction temperature does not exceed 105 C. After the end of metering, the reaction mixture is stirred at 105 C. for a further 3 hours. It is then left to cool, admixed with 300 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 22

[0109] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 90 C. with 320 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 44.2 parts of salicylic acid, 22.1 parts of 2-phenoxyethanol and 21.2 parts of paraformaldehyde. Added to the reaction mixture then are 43.9 parts of methanesulphonic acid (70%) over the course of 15 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 110 C. for a further 1 hour. It is then left to cool, admixed with 350 parts of water, heated to 100 C. for 30 minutes and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 23

[0110] A heatable reactor equipped with stirrer and metering pump is charged under nitrogen at 95 C. with 225 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), 82.9 parts of salicylic acid, 65.4 parts of 2-phenoxyethyl phosphate and 82.3 parts of methanesulphonic acid (70%). The reaction mixture is heated with stirring to about 105 C. and then 128.2 parts of formalin (30% strength) are added over the course of 70 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 100 C. for a further 4.75 hours. It is then left to cool, admixed with 300 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 24

[0111] A heatable reactor equipped with stirrer and metering pump is charged with 263 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol) and conditioned to 30 C. Then, over the course of 20 minutes, 42 parts of polyphosphoric acid are added, followed by subsequent reaction for 15 minutes. This reaction mixture is admixed with 96.7 parts of salicylic acid, 76.4 parts of 2-phenoxyethyl phosphate, 50 parts of water and 46.5 parts of paraformaldehyde under nitrogen at 95 C. The reaction mixture is heated to about 105 C. with stirring, and in this stage 66.2 parts of methanesulphonic acid (70%) are added over the course of 30 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 105 C. for a further 3.25 hours. It is then left to cool, admixed with 300 parts of water and neutralized to a pH of about 7.0 using 50% strength aqueous sodium hydroxide solution.

Example 25

[0112] Example 12 was repeated with the salicylic acid-containing polymers of Examples 19 to 24. The results are shown in Table 7.

[0113] Formulation:

TABLE-US-00014 Microsilica 150 g Fly ash, type F 150 g Silica sand 700 g KOH (5.0%) 262.63 g

TABLE-US-00015 TABLE 7 Example Slump [cm] Density [g/cm3] Without additive 17.5 1.95 Comparative Example 1 19.1 1.83 Comparative Example 2 19.0 1.98 Example 19 23.5 1.95 Example 21 30.0 1.92 Example 23 30.0 1.91 Example 24 27.3 1.94

Example 26

[0114] Example 25 was repeated with the modification that 0.2% strength by weight aqueous KOH solution was used as activator. The results are shown in Table 8.

[0115] Formulation:

TABLE-US-00016 Microsilica 150 g Fly ash, type F 150 g Silica sand 700 g KOH (0.2%) 250 g

TABLE-US-00017 TABLE 8 Example Slump [cm] Density [g/cm3] Without additive 19.9 1.94 Comparative Example 1 18.4 1.83 Comparative Example 2 18.9 1.95 Example 18 23.6 1.83 Example 19 25.4 1.85 Example 23 25.8 1.85 Example 24 30.0 1.97

Example 27

[0116] Example 13 was repeated with the salicylic acid-containing polymers of Examples 17 to 24. The results are shown in Table 9.

[0117] Formulation:

TABLE-US-00018 Ground slag sand 300 g Silica sand 700 g KOH (0.2%) 180 g

TABLE-US-00019 TABLE 9 Example Slump [cm] Density [g/cm3] Without additive 17.1 2.11 Comparative Example 1 22.7 2.00 Example 17 25.4 2.05 Example 18 30.0 2.11 Example 19 29.3 2.05 Example 22 22.9 1.88 Example 23 28.5 2.01 Example 24 24.7 2.12

Example 28

[0118] Example 27 was repeated with the modification that 5.0% strength by weight aqueous KOH solution was used as activator. The results are shown in Table 10.

[0119] Formulation:

TABLE-US-00020 Ground slag sand 300 g Silica sand 700 g KOH (5.0%) 189.09 g

TABLE-US-00021 TABLE 10 Example Slump [cm] Density [g/cm3] Without additive 17.4 2.12 Comparative Example 1 17.9 1.86 Comparative Example 2 21.5 2.11 Example 17 28.4 2.09 Example 18 30.0 2.13 Example 19 30.0 2.09 Example 21 30.0 2.06 Example 22 30.0 2.00 Example 23 30.0 2.08 Example 24 29.3 2.07

Example 29

[0120] Example 28 was repeated with the modification that 15.0% strength by weight aqueous KOH solution was used as activator. The results are shown in Table 11.

[0121] Formulation:

TABLE-US-00022 Ground slag sand 300 g Silica sand 700 g KOH (15%) 211.34 g

TABLE-US-00023 TABLE 11 Example Slump [cm] Density [g/cm3] Without additive 18.6 2.07 Comparative Example 1 19.7 1.85 Comparative Example 2 19.4 2.05 Example 19 23.7 2.11 Example 21 27.4 2.09 Example 24 30.0 2.11

[0122] As these examples show, the polymers of the invention enable a significant improvement in the consistency of the aluminosilicate mortars. Here, the polymers of the invention permit an improvement in the consistency of geopolymer systems with different binder compositions, such as fly ashes, microsilica or ground slag sands, and with different activator solutions. Moreover, it can be seen from the tests that standard plasticizers such as polycarboxylic ethers exhibit virtually no effect, whereas the polymers of the invention enable outstanding plasticization and hence water reduction.

Example 30

[0123] A heatable reactor equipped with stirrer and metering pump is charged with 262.5 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol) and 48.4 parts of 2-phenoxyethanol. Subsequently, with cooling, 77.0 parts of polyphosphoric acid are added over 15 minutes and the mixture is stirred at about 95 C. for 45 minutes. Added to this reaction mixture at about 90 C. under a stream of nitrogen are 96.7 parts of salicylic acid, 50 parts of water and 46.5 parts of paraformaldehyde. The reaction mixture is heated to about 90 C. with stirring and then 67.3 parts of methanesulphonic acid (70%) are added over the course of 30 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at about 100 C. for a further 120 minutes. It is then left to cool, admixed with 350 parts of water and neutralized to a pH of about 7.0 using aqueous sodium hydroxide solution (50%). The neutralized dispersant is in the form of an about 35.0% strength by weight aqueous solution.

Example 31

[0124] A heatable reactor equipped with stirrer and metering pump is charged with 225 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol) and 82.9 parts of 2-phenoxyethanol. Subsequently, with cooling, 99.0 parts of polyphosphoric acid are added over 35 minutes and the mixture is stirred at about 90-95 C. for 60 minutes. Added to this reaction mixture under a stream of nitrogen are 41.4 parts of salicylic acid, 40 parts of water and 39.8 parts of paraformaldehyde. The reaction mixture is heated to about 85 C. with stirring and then 57.7 parts of methanesulphonic acid (70%) are added over the course of 35 minutes at a rate such that the reaction temperature does not exceed 105 C. After the end of metering, the reaction mixture is stirred at 100 C. for a further 140 minutes. It is then left to cool, admixed with 350 parts of water and neutralized to a pH of about 7.0 using polyethyleneimine (Lupasol G100 from BASF SE). The neutralized dispersant is in the form of an about 30.4% strength by weight aqueous solution.

Example 32

[0125] Aluminosilicate mortars were produced in accordance with the following formula:

TABLE-US-00024 Microsilica 150 g Fly ash, type F 150 g Silica sand 700 g Na.sub.2Al.sub.2O.sub.4 15 g Defoamer 0.12 g Water, total 250 g

[0126] The starting materials were mixed in the laboratory with a mortar mixer in accordance with DIN EN 196-1. The mixing operation was carried out as described in DIN EN 196-1, with the difference that the silica sand was added right at the beginning, and not only subsequently, to the mixing trough. The alkaline activator used was the sodium aluminate dissolved in the make-up water. As the defoamer, the product Defoamer DF40 from BASF SE was used. The dispersant was used as an aqueous solution as obtained in Examples 1 and 2 (indicated as polymer solids content).

[0127] The compositions of the type F fly ash and the microsilica were as follows [% by weight]:

TABLE-US-00025 SiO.sub.2 Fe.sub.2O.sub.3 TiO.sub.2 Al.sub.2O.sub.3 CaO MgO K.sub.2O Remainder Fly ash 53.4 5.7 1.1 26.8 3.1 2.0 4.5 3.4 Microsilica 98.1 0.0 0.0 0.0 0.23 0.2 0.77 0.7

[0128] The slump was determined after 6 minutes in each case by tapping 15 times on a slump table with a Hgermann cone (DIN EN 1015-3). The results are shown in Table 12.

TABLE-US-00026 TABLE 12 Reference Example 30 Example 31 Dispersant 0.0 g 3.0 g 3.0 g Slump 18.6 cm 27.5 cm 27.3 cm

[0129] This table shows that the dispersants of the invention also enable a significant improvement in the slumps of the aluminosilicate mortar mixtures when in combination with sodium aluminate as alkaline activator. Here, an improvement in consistency is obtained both by Na salts and by polyethyleneimine salts of the polymers of the invention.

Example 33

[0130] Example 3 was repeated. A fully water-soluble, brown polymer was obtained which had a molecular weight (max. peak) Mp=24.3 kDa (column combinations: OH-Pak SB-G, OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Shodex, Japan; eluent: 80% by volume aqueous ammonium formate solution (0.05 mol/I) and 20% by volume acetonitrile; injection volume 100 l; flow rate 0.5 ml/min).

Example 34

[0131] A heatable reactor equipped with stirrer, reflux condenser and metering pump is charged with 150 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), 101 parts of hydroquinone bis(2-hydroxyethyl) ether and 28 parts of salicylic acid and heated to 90 C. under nitrogen. Then 132 parts of polyphosphoric acid are added over the course of 33 minutes, followed by subsequent reaction for 10 minutes. This reaction mixture is admixed with 48 parts of methanesulphonic acid (70%) and 2 parts of water at 98 C. The reaction mixture is cooled to about 90 C., with stirring, and 95 parts of formalin solution (30%) are added over the course of 50 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 100 C. for a further 20 minutes. It is then left to cool, admixed with 760 parts of water and neutralized to a pH of about 7.3 using 50% strength aqueous sodium hydroxide solution.

Example 35

[0132] A heatable reactor equipped with stirrer, reflux condenser and metering pump is charged with 188 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol) and parts of phenoxyethanol and heated to 25 C. under nitrogen. Then 55 parts of polyphosphoric acid are added over the course of 8 minutes, after which the reaction mixture is heated to 92 C. and subsequently reacted at this temperature for 100 minutes. The reaction mixture is admixed with 104 parts of salicylic acid and 69 parts of methanesulphonic acid (70%) and, after 10 minutes, 131 parts of formalin solution (30%) are added over the course of 60 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 100 C. for a further 3.5 hours. It is then left to cool, admixed with 500 parts of water and neutralized to a pH of about 7.3 using 50% strength aqueous sodium hydroxide solution.

Example 36

[0133] A heatable reactor equipped with stirrer, reflux condenser and metering pump is charged with 188 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), and additionally 28 parts of polyphosphoric acid are added under nitrogen over the course of 8 minutes. After 10 minutes from the end of metering, the reaction mixture is heated to 90 C. with stirring and subsequently reacted at around 95 C. for 4 hours. Then 35 parts of phenoxyethanol and, 30 minutes later, 104 parts of salicylic acid and 69 parts of methanesulphonic acid (70%) are added. The reaction mixture is heated to around 100 C. with stirring, and when that temperature has been attained, 132 parts of formalin solution (30%) are added over the course of 50 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 95 C. for a further 3.7 hours. It is then left to cool, admixed with 450 parts of water and neutralized to a pH of about 7.3 using 50% strength aqueous sodium hydroxide solution.

Example 37

[0134] A heatable reactor equipped with stirrer, reflux condenser and metering pump is charged with 135 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), and additionally 20 parts of polyphosphoric acid are added under nitrogen over the course of 6 minutes. After 10 minutes from the end of metering, the reaction mixture is heated to 90 C. with stirring and subsequently reacted at around 95 C. for 4 hours. Then 50 parts of phenoxyethanol and, 15 minutes later, 149 parts of salicylic acid and 99 parts of methanesulphonic acid (70%) are added. The reaction mixture is heated to around 90 C. with stirring, and when that temperature has been attained, 170 parts of formalin solution (30%) are added over the course of 60 minutes at a rate such that the reaction temperature does not exceed 110 C. After the end of metering, the reaction mixture is stirred at 95 C. for a further 2.75 hours. It is then left to cool, admixed with 500 parts of water and neutralized to a pH of about 7.3 using 50% strength aqueous sodium hydroxide solution.

Example 38

[0135] Aluminosilicate mortars were produced in accordance with the following formula:

TABLE-US-00027 Ground slag sand 300 g Silica sand 700 g KOH 12 g Na.sub.2CO.sub.3 12 g Defoamer 0.12 g Water, total 175 g

[0136] The starting materials were mixed in the laboratory with a mortar mixer in accordance with DIN EN 196-1. The mixing operation was carried out as described in DIN EN 196-1, with the difference that the silica sand was added right at the beginning, and not only subsequently, to the mixing trough. The alkaline activator used was the potassium hydroxide and sodium carbonate dissolved in the make-up water. As the defoamer, the product Defoamer DF93 from BASF SE was used. The dispersant was used as an aqueous solution as obtained in Examples 1 and 2 (polymer solids content in the mortar mixture: 3 g).

[0137] The composition of the ground slag sand was as follows [% by weight]:

TABLE-US-00028 SiO.sub.2 Fe.sub.2O.sub.3 TiO.sub.2 Al.sub.2O.sub.3 CaO MgO K.sub.2O Remainder Slag sand 33.1 0.6 0.6 15.0 41.3 6.1 0.3 3.0

[0138] The slump was determined after 6 minutes and after 30 minutes in each case by tapping times on a slump table with a Hgermann cone (DIN EN 1015-3). The results are shown in Table 13.

TABLE-US-00029 TABLE 13 Slump after Slump after Density Example 6 min [cm] 30 min [cm] [g/cm.sup.3] Without additives 15.7 15.2 1.98 Comparative example (Melflux 16.6 15.5 1.96 2424) Example 34 16.6 16.3 2.05 Example 35 20.8 20.6 2.02 Example 36 23.7 23.3 2.08 Example 37 24.6 24.0 2.08

Example 39

[0139] Weighed out in a metal vessel were 100.0 g of a composite slag sand cement of type CEM III/A 32.5 N. The amount of dispersant indicated below, calculated as solids content, was mixed, taking account in the calculation of the water present in the dispersant, with the amount of water corresponding to a water/cement ratio of 0.3. In this context, the expression bwoc is intended to denote % by weight, based on the amount of cement. Following addition of the water/dispersant mixture to the cement, the mixture was stirred intensely with a paddle stirrer for 1 minute. The cement paste obtained in this way was introduced into a metal cone (internal diameter top/bottom 2.0/4.0 cm, height 6.0 cm) which stood on a horizontally disposed glass plate. The metal cone was lifted, and the cement paste underwent slump flow. The slump flow (SF or spread, diameter of the cement paste cake) was subsequently determined at 3 points, and the average was taken. The averaged values are shown in Table 14. (Glenium SKY 115 is a commercial high-performance dispersant from BASF Construction Polymers GmbH, based on polycarboxylate ether.)

TABLE-US-00030 TABLE 14 Amount Amount added added Dispersant [g] [bwoc] SF [cm] Comparative 1 Glenium SKY 115 0.67 0.67% 10.8 Comparative 2 Glenium SKY 115 0.34 0.34% <8 Example 39 Glenium SKY 115 0.34 0.87% 10.6 Polycondensation product 0.53

[0140] It was found that when the amount of high-performance dispersant added was halved (Comparative 2), it was, as expected, not possible to achieve the reference slump flow of the cement paste from Comparative 1. Only by adding the polycondensation product of the invention (Example 33) was it possible to bring back the slump flow almost to the reference level.

[0141] A defined amount of the cement paste thus obtained was transferred to a calorimeter, and the development of the heat of hydration was recorded calorimetrically. For this purpose, the calorimeter was equilibrated beforehand to 20.0 C. (isothermal reference calorimeter from TA Instruments, Model TAM-AIR). After 48 hours, measurement was halted and the data was evaluated. For this purpose, the differential heat generation dH/dt (mW/g, standardized for 1 g of cement paste) and also the integral heat generation H (J/g; after 6, 12, 24 and 48 hours) were employed. The results are shown in Table 15.

TABLE-US-00031 TABLE 15 dH/dt max. H [J/g] [mW/g] at t [h, min] 6 h 12 h 24 h 48 h Comparative 1 1.58/23 h, 54 min 5.52 10.96 47.60 146.11 Example 39 1.66/18 h, 54 min 5.76 13.48 71.59 157.00

[0142] It was found that significantly quicker hydration was achievable by using the polycondensation product from Example 33. In spite of the addition of polymer at a higher level overall, a significantly more rapid release of heat was observed, which suggests a quicker hydration of the cement. The maximum in the heat generation of the cement paste formulated using the polycondensation product of the invention was achieved after just 18 hours and 54 minutes, whereas the cement paste formulated using the commercial high-performance concrete plasticizer did not achieve its maximum heat generation until 5 hours later. This is also reflected in the integral heat generation; after 6, 12, 24 and 48 hours, the levels of heat generation observable were always higher.

Example 40

[0143] Weighed out in a metal vessel were 100.0 g of a composite slag sand/fly ash cement of type CEM V/A 32.5 N. The amount of dispersant indicated below, calculated as solids content, was mixed, taking account in the calculation of the water present in the dispersant, with the amount of water corresponding to a water/cement ratio of 0.33. Following addition of the water/dispersant mixture to the cement, the mixture was stirred intensely with a paddle stirrer for 1 minute. The cement paste obtained in this way was introduced into a metal cone (internal diameter top/bottom 2.0/4.0 cm, height 6.0 cm) which stood on a horizontally disposed glass plate. The metal cone was lifted, and the cement paste underwent slump flow. The slump flow was subsequently determined at 3 points, and the average was taken. The averaged values are shown in Table 16.

TABLE-US-00032 TABLE 16 Amount Amount added added Dispersant [g] [bwoc] SF [cm] Comparative 3 Glenium SKY 115 0.67 0.67% 17.0 Example 40 Glenium SKY 115 0.34 0.67% 15.9 Polycondensation product 0.33

[0144] It was found that when the amount of high-performance dispersant was halved and the polycondensation product of the invention was added, the reference slump flow of the cement paste from Comparative 3 could be raised to close to the reference level.

Example 41

[0145] Example 3 was repeated with 450 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 5000 g/mol), 27.3 parts of 3,4-dihydroxybenzoic acid, 9.3 parts of paraformaldehyde and 49.4 parts of methanesulphonic acid (70%). The pH after neutralization with 50% strength aqueous sodium hydroxide solution was about 7.3. The polymer obtained was fully water-soluble and dark brown, in the form of an about 32.4% strength by weight aqueous solution. The molecular weight was about 12-23 kDa (Mp=11.6 and 22.5 kDa; GPC conditions as in Example 33).

Example 42

[0146] Example 20 was repeated with 262.5 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 750 g/mol), 145.0 parts of salicylic acid, 50 parts of water, 46.5 parts of paraformaldehyde and 67.2 parts of methanesulphonic acid (70%). The pH after neutralization with 50% strength aqueous sodium hydroxide solution was about 7.3. The polymer obtained was fully water-soluble and yellowish, in the form of an about 28.0% strength by weight aqueous solution. The average molecular weight was about 5.4 kDa (GPC conditions as in Example 33).

Example 43

[0147] Example 20 was repeated with 300 parts of poly(ethylene oxide) monophenyl ether (average molecular weight 2000 g/mol), 82.9 parts of salicylic acid, 26.1 parts of paraformaldehyde and 72.1 parts of methanesulphonic acid (50%). The reaction took place at 105-108 C. The molecular weight was about 16 kDa.

Example 44

[0148] 12.3 kg of ground slag sand (GBFS) from Salzgitter, admixed with a 32.4% strength aqueous solution of the polymer from Example 41 (identified as E41 in FIG. 1 and in Tables 17 and 18) or with a 28.0% strength aqueous solution of the polymer from Example 42 (identified as E42 in FIG. 1 and in Tables 17 and 18) (in each case 0.03% by weight polymer, based on the weight of the sand) were ground for 125 minutes with stainless steel balls in a laboratory ball mill (LABBAS LM0504-S7, CEMTEC GmbH) without additional external heating. The resulting powder was sieved through a 5 mm sieve. For comparison, a GBFS sample without addition of additives (identified as blank in FIG. 1) was ground and sieved. The particle size distributions of the resultant powders were determined using a Mastersizer 2000 from Malvern Instruments, and the Blaine values were determined using a Blaine analyser from SEGER Tonindustrie. The particle size distributions are shown in FIG. 1. From each of the resulting samples of ground slag sand, 700 g were separated into coarse and fine fractions, using a 100 MZR (Plain) cyclone from Hosokawa Alpine with a set limit particle size of 15 m, an air velocity of 49 m/s (constant) and a rotational speed of 6000 rpm. For each of the separated samples, the particle size distribution of the coarse and fine fractions was measured.

Example 45

[0149] Example 44 was repeated. 0.08% by weight of each of the following additives, based on the weight of the ground slag sand, was used: TEA (triethanolamine), RheoPlus 18 (44.2% strength aqueous solution, containing 5% of the defoamer Plurafac LF305), polymer from Example 41 (identified as E41, in the form of a 32.4% strength aqueous solution, containing 5% of the defoamer Plurafac LF305), polymer from Example 42 (identified as E42, in the form of a 28.0% strength aqueous solution, containing 5% of the defoamer Plurafac LF305) and polymer from Example 43 (identified as E43 in FIG. 2, in the form of a 31.7% strength aqueous solution, containing 5% of the defoamer Plurafac LF305). Grinding took place at 120 C. Here again, for comparison, a GBFS sample without addition of additives (identified as blank in FIG. 2) was ground and sieved. FIG. 2 shows the corresponding particle size distributions.

Discussion:

[0150] FIG. 1 shows that the main difference in the particle size distribution lies in the region of the coarse particles (15-300 m), in other words that the addition of the corresponding grinding assistant leads to a reduction in the amount of coarse particles, with a significant fall in the d (0.5) and d (0.9) values with the grinding assistants, and a significant increase in the Blaine values (cf. Table 17). The time for complete separation of the fractions is shortened when the grinding assistants of the invention are used, with beneficial consequences for the energy costs, and the average particle size of the coarse fraction is significantly reduced (cf. Table 18). From this it can be inferred that the polycondensation products of the invention enhance the grindability of the slag.

TABLE-US-00033 TABLE 17 Sample d (0.1) d (0.5) d (0.9) d (0.450) d (0.632) n Blaine Density GBFS E42 1.403 10.556 45.621 8.816 16.885 1.03 3937 2.891 GBFS E41 1.375 10.69 49.021 8.875 17.391 0.98 3902 2.897 GBFS blank 1.419 11.528 65.982 9.38 20.158 0.97 3758 2.905

TABLE-US-00034 TABLE 18 d (0.5) coarse/fine separation time d (0.5) of the fine of the coarse Sample (m/m) [min] fraction [m] fraction [m] E42 1.15 31 5.645 29.553 E41 0.76 31 5.584 28.249 blank 0.71 38 5.413 36.618

[0151] FIG. 2 and Table 19 show particle size distributions and Blaine values of slag sands ground hot with the various additives identified in Example 40. The average particle sizes d (0.5) of the slag sands ground with the polymers E42 and E43 are significantly smaller, and the corresponding Blaine values higher, than those of the sample without additives (blank) and of the sample ground with TEA or RheoPlus 18 (high-performance cement plasticizer from BASF SE).

TABLE-US-00035 TABLE 19 Sample d (0.5) d (0.9) Blaine value GBFS + E42 10.54 43.36 3818 GBFS + E43 10.72 44.01 3877 GBFS + TEA 11.12 41.25 3735 GBFS + RheoPlus 18 11.72 45.17 3560 GBFS + E41 11.86 48.08 3612 GBFS blank 12.23 72.43 3482