DISPERSANT COMPOSITION FOR INORGANIC SOLID SUSPENSIONS

Abstract

The invention relates to a composition in the form of a solid and suitable as a dispersant for inorganic solids suspensions, comprising A) at least one water-soluble polymer comprising polyether groups, and B) at least one water-soluble condensation product comprising acid groups and/or salts thereof and based on monomers, the monomers comprising at least ) a monomer having a ketone radical and ) formaldehyde. Further disclosed are a method for producing the composition of the invention, and the use thereof in an inorganic binder composition.

Claims

1. A composition, in the form of a solid and suitable as a dispersant for inorganic solids suspensions, the composition comprising A) at least one water-soluble polymer comprising a polyether group and B) at least one water-soluble condensation product which comprises an acid group and/or a salt thereof and is based on monomers, the monomers comprising ) a monomer having a ketone radical and ) formaldehyde.

2. The composition of claim 1, wherein the polyether group of the at least one water-soluble polymer A) is comprised by a structural unit (I) which is represented by the following formula,
*U(C(O)).sub.kX-(AlkO).sub.nW(I) wherein * indicates the bonding site to the at least one water-soluble polymer A), U is a chemical bond or an alkylene group having 1 to 8 carbon atoms, X is oxygen, sulfur, or NR.sup.1, wherein R.sup.1 is hydrogen, a C.sub.1-C.sub.4 alkyl group, or a benzyl group, k is 0 or 1, n is an integer whose average value based on the at least one water-soluble polymer A) is in a range of from 3 to 300, and each Alk is independently a C.sub.2-C.sub.4 alkylene group, W is hydrogen, a C.sub.1-C.sub.6 alkyl group, or an aryl radical or is a group represented by YF, wherein Y is a linear or branched alkylene group having 2 to 8 carbon atoms and may comprise a phenyl ring, and F is a 5- to 10-membered nitrogen heterocycle which is bonded via nitrogen and which may have 1, 2, or 3 heteroatoms as ring members in addition to the nitrogen, wherein the heteroatoms are selected from the group consisting of oxygen, nitrogen, and sulfur, it being possible for 1 or 2 carbon ring members to be present in the form of a carbonyl group, and for the nitrogen ring members to have a group R.sup.2, wherein R.sup.2 is hydrogen, a C.sub.1-C.sub.4 alkyl group or a benzyl group.

3. The composition of claim 1, wherein the at least one water-soluble polymer A) further comprises at least one selected from the group consisting of a carboxyester group, a carboxyl group, a phosphono group, a sulfino group, a sulfo group, a sulfamido group, a sulfoxy group, a sulfoalkyloxy group, a sulfinoalkyloxy group, and a phosphonooxy group.

4. The composition of claim 1, wherein the at least one water-soluble polymer A) is a polycondensation product comprising (II) a structural unit comprising an aromatic or heteroaromatic group and the polyether group, and (III) a phosphated structural unit comprising an aromatic or heteroaromatic group.

5. The composition of claim 4, wherein the structural units (II) and (III) are represented by the following general formulae
A-U(C(O)).sub.kX-(AlkO).sub.nW(II) wherein each A is independently a substituted or unsubstituted, aromatic or heteroaromatic compound having 5 to 10 carbon atoms in the aromatic or heteroaromatic system, and the other radicals are defined as in structural unit (I); and ##STR00006## wherein each D is independently a substituted or unsubstituted, aromatic or heteroaromatic compound having 5 to 10 carbon atoms in the aromatic or heteroaromatic system, each E is independently N, NH or O, m=2 if E=N and m=1 if E=NH or O, each R.sup.3 and each R.sup.4 is independently a branched or unbranched C.sub.1 to C.sub.10 alkyl radical, C.sub.5 to C.sub.8 cycloalkyl radical, aryl radical, or heteroaryl radical or H, and each b is independently an integer from 0 to 300.

6. The composition of claim 4, wherein the polycondensation product further comprises a structural unit (IV) which is represented by the following formula ##STR00007## wherein each Y is independently the structural unit (II), the structural unit (III) or a further constituent of the polycondensation product, and each R.sup.5 and each R.sup.6 is independently H, CH.sub.3, COOH, or a substituted or unsubstituted, aromatic or heteroaromatic compound having 5 to 10 carbon atoms.

7. The composition of claim 1, wherein the at least one water-soluble polymer A) comprises at least one copolymer which is obtainable by polymerizing a monomer mixture comprising (V) at least one ethylenically unsaturated monomer comprising at least one radical selected from the group consisting of a carboxylic acid, a carboxylic salt, a carboxylic ester, a carboxylic amide, a carboxylic anhydride, and a carboxylic imide, and (VI) at least one ethylenically unsaturated monomer comprising the polyether group.

8. The composition of claim 7, wherein the ethylenically unsaturated monomer (V) is represented by at least one of the following general formulae (Va), (Vb), and (Vc) ##STR00008## wherein each R.sup.7 and each R.sup.8 is independently hydrogen or an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, B is H, COOM.sub.a, COO(C.sub.qH.sub.2qO).sub.rR.sup.9, or CONH(C.sub.qH.sub.2qO).sub.rR.sup.9, M is hydrogen, a mono-, di- or trivalent metal cation, an ammonium ion, or an organic amine radical, a is , , or 1, R.sup.9 is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, or an optionally substituted aryl radical having 6 to 14 carbon atoms, each q is independently 2, 3, or 4, r is 0 to 200 Z is O, or NR.sup.16, and each R.sup.16 is independently hydrogen or a branched or unbranched C.sub.1 to C.sub.10 alkyl radical, C.sub.5 to C.sub.8 cycloalkyl radical, aryl radical, or heteroaryl radical, ##STR00009## wherein each R.sup.10 and each R.sup.11 is independently hydrogen, an aliphatic hydrocarbon radical having 1 to 20 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, or an optionally substituted aryl radical having 6 to 14 carbon atoms, each R.sup.12 is independently (C.sub.nH.sub.2n)SO.sub.3H where n=0, 1, 2, 3 or 4, (C.sub.nH.sub.2n)OH where n=0, 1, 2, 3 or 4 (C.sub.nH.sub.2n)PO.sub.3H.sub.2 where n=0, 1, 2, 3 or 4, (C.sub.nH.sub.2OOPO.sub.3H.sub.2 where n=0, 1, 2, 3 or 4, (C.sub.6H.sub.4)SO.sub.3H, (C.sub.6H.sub.4)PO.sub.3H.sub.2, (C.sub.6H.sub.4)OPO.sub.3H.sub.2, or (C.sub.nH.sub.2n)NR.sup.14.sub.b where n=0, 1, 2, 3 or 4 and b=2 or 3, R.sup.13 is H, COOM.sub.a, COO(C.sub.qH.sub.2qO).sub.rR.sup.9, or CONH(C.sub.qH.sub.2qO).sub.rR.sup.9, wherein M.sub.a, R.sup.9, q, and r are defined as in formulae (Va) and (Vb), R.sup.14 is hydrogen, an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, or an optionally substituted aryl radical having 6 to 14 carbon atoms, and each Q is independently NH, NR.sup.15, or O; where R.sup.15 is an aliphatic hydrocarbon radical having 1 to 10 carbon atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, or an optionally substituted aryl radical having 6 to 14 carbon atoms.

9. The composition of claim 1, wherein the acid group of the at least one water-soluble condensation product B) comprises at least one selected from the group consisting of a carboxyl group, a phosphono group, a sulfino group, a sulfo group, a sulfamido group, a sulfoxy group, a sulfoalkyloxy group, a sulfinoalkyloxy group, and a phosphonooxy group and/or a salt thereof.

10. The composition of claim 1, wherein the at least one water-soluble condensation product B) has a monomer ratio of the monomers ) to ) of 1:2 to 3.

11. The composition of claim 1, wherein the monomer having the ketone radical ) in the at least one water-soluble condensation product B) comprises at least one ketone selected from the group consisting of methyl ethyl ketone, acetone, diacetone alcohol, ethyl acetoacetate, levulinic acid, methyl vinyl ketone, mesityl oxide, 2,6-dimethyl-2,5-heptadien-4-one, acetophenone, 4-methoxyacetophenone, 4-acetylbenzenesulfonic acid, diacetyl, acetylacetone, benzoylacetone, and cyclohexanone.

12. The composition of claim 1, which is in the form of powder or granules.

13. The composition of claim 1, which comprises 5 to 95 wt % of the at least one water-soluble polymer A), and 5 to 95 wt % of the at least one water-soluble condensation product B).

14. A method for producing the composition of claim 1, the method comprising: a) providing at least one water-soluble polymer A), b) providing at least one water-soluble condensation product B), c) preparing an aqueous mixture comprising the at least one water-soluble polymer A) and the at least one water-soluble condensation product B), and d) spray-drying the aqueous mixture to obtain a solid.

15. An inorganic binder composition, comprising the composition of claim 1.

Description

EXAMPLES

[0121] Preparation of the Polymers

[0122] The acetone resin was prepared in accordance with polymer 6 of WO15039890 (see table 1 on page 13 in conjunction with page 15, protocol C)) The cyclohexanone resin was prepared in accordance with polymer 14 of WO15039890 (see table 1 on page 13 in conjunction with page 15, protocol B))

[0123] Polymer A is a copolymer of ethoxylated vinyloxybutanol having a chain length of 23 ethylene oxide units and acrylic acid. The copolymer was prepared as follows: a glass reactor fitted with a number of feed facilities, stirrer, and dropping funnel was charged with 500 ml of water and 359 g of macromonomer 1 (prepared by ethoxylation of vinyloxybutanol with 23 mol of EO), and this initial charge was conditioned to 13 C. Added to this were 0.01 g of iron(II) sulfate heptahydrate and 5.5 g of Brggolit FF6. After that, 57.9 g of acrylic acid and 5 g of 30% hydrogen peroxide solution were added. The reaction mixture was stirred at 25 to 35 C. for 0.5 h. Thereafter it was neutralized to a pH of 5 using sodium hydroxide solution. The molecular weight determined by GPC is 22 000 g/mol.

[0124] Polymer B is a copolymer of hydroxyethyl acrylate and ethoxylated isoprenol having 23 ethylene oxide units (EO). The copolymer was prepared as follows: a glass reactor was fitted with a stirrer mechanism, pH meter, and metering units and was charged with 267 g of water. 330 g of the melted ethoxylated isoprenol were mixed with the water. The temperature was set at 13 C. and the pH at around 7 by addition of 25% sulfuric acid. This mixture was admixed with 4 mg of iron(II) sulfate heptahydrate, 8.25 g of mercaptoethanol, and 3.2 g of hydrogen peroxide. After that a solution of 200 g of water and 136 g of hydroxyethyl acrylate and also 5 g of Brggolit E01 and 32 g of water were added over a period of 20 minutes. During the reaction the pH was maintained at 7 by addition of 50% NaOH. The reaction mixture was stirred at 20 C. for 40 minutes. The molecular weight determined by GPC is 18 000 g/mol.

[0125] Polymer C is a copolymer of methacrylic acid and methyl-polyethylene glycol methacrylate with 23 ethylene oxide units (EO). The polymer was prepared as follows: 330 g of the methacrylate were melted in a 500 ml three-necked flask equipped with a paddle stirrer at 70 C. The amount of methacrylic acid (70.0 g) and 0.1 g of sodium persulfate were added. The reaction mixture was stirred at 80 C. for 5 hours. The resulting polymer was mixed with 500 ml of water and then neutralized to a pH of 7 using 50% aqueous sodium hydroxide solution. The molecular weight of the resulting polymer was 28 000 g/mol.

[0126] The auxiliary polymer was prepared in analogy to page 18, synthesis example 1 of WO 03/097721.

[0127] The lignosulfonate used was a commercially available Bretax lignosulfonate from Burgos.

[0128] The sulfonated melamine-formaldehyde condensation product used was Melment F10 from BASF Construction Solutions GmbH.

[0129] The molecular weight was determined by gel permeation chromatography (GPC) with the following method: column combination: Shodex OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Showa Denko, Japan; eluent: 80 vol % aqueous solution of HCO.sub.2NH.sub.4 (0.05 mol/l) and 20 vol % MeOH; injection volume 100 l; flow rate 0.5 ml/min. The molecular weight was calibrated using standards from PSS Polymer Standard Service, Germany. For the UV detector, poly(styrene-sulfonate) standards were used, and poly(ethylene oxide) standards for the RI detector. The molecular weight was determined using the results of the RI detector.

[0130] Spray Drying

[0131] An aqueous mixture was prepared from the respective carrier material in accordance with the conditions of table 3. With vigorous stirring, the polymer was added in the form of an aqueous solution.

[0132] The mixtures were dried using a GEA Niro Mobile Minor MM-I spray dryer. Drying took place by means of a two-fluid nozzle at the top of the tower. Drying was dried with nitrogen, which was blown in cocurrent with the material for drying, from top to bottom. 80 kg/h of drying gas were used for the drying. The temperature of the drying gas at the tower entry was 220 C. The feed rate of the material for drying was set such that the outgoing temperature of the drying gas at the tower exit was 100 C. The powder discharged from the drying tower with the drying gas was separated from the drying gas by means of a cyclone.

[0133] Spray-dryability was assessed as follows:

TABLE-US-00001 TABLE 1 Grading Description 1 Fine, dustlike powder in the sample glass beneath the cyclone; pipelines and cyclone exhibit only dustlike wetting; possibly, fine powder-like deposits in the cone of the drying tower 2 Fine powder (d(90) particle size <500 m) in the sample glass beneath the cyclone; only slight deposits in cyclone and pipelines; possibly, fine powder-like deposits in the cone of the drying tower 3 Coarser powder (d(90) particle size >500 m) in the sample glass beneath the cyclone, deposits in cyclone and pipelines; after 10 seconds of mixing of the powder in a RETSCH Grindomix GM 200 at 8000 revolutions/min, a sample is obtained with particle sizes d(99) <500 m. 4 Possibly a few larger lumps in the sample glass beneath the cyclone, sample very largely in the dryer tower, severe encrustation in pipelines; 10 seconds of mixing in the RETSCH Grindomix GM 200 at 8000 revolutions/min sample produce a sample with particle sizes d(80) <500 m 5 Empty, possibly waxily wetted sample glass beneath the cyclone, sample very largely in the form of waxlike coating in dryer tower and pipelines The particle size was determined using a Mastersizer 2000 from Malvern Instruments. It represents the volumetric particle diameter.

[0134] The thermomechanical properties of the powder were tested as follows: All of the metal parts required were heated in a drying cabinet at 80 C. before use. A brass tube with a length of 70 mm and an internal diameter of 50 mm for a wall thickness of 2.5 mm were placed onto a brass baseplate with a tube attachment 7 mm high and 55 mm internal diameter. 2 g of powder were introduced into the pipe, followed by a brass cylinder having a weight of 1558 g. This cylinder was rotated by 360 10 times without pressure. The cylinder and the pipe were then removed, and the sample was classed on the basis of the following factors:

TABLE-US-00002 TABLE 2 Powders produced were as follows: Grading Description 1 Sample is still in powder form 2 Sample is a compacted powder, and can be broken apart by the finger or the spatula without application of force 3 Sample undergoes compaction, force required in order to disintegrate the sample, possibly slightly tacky 4 Sample is of waxlike form; initially there are soft lumps, after cooling there are hard lumps

TABLE-US-00003 TABLE 3 Mass Carrier [% of Mass Assessment Assessment Powder Polymer Solids (grams) total weight] Solids (grams) A B 1 A 40.5 123.5 Cyclohexanone 41.1 365.0 2 2 resin [75%] 2 A 40.5 246.9 Cyclohexanone 41.1 243.3 2 2 resin [50%] 3 A 40.5 370.4 Cyclohexanone 41.1 121.7 2 2 resin [25%] 4 B 52 153.8 Cyclohexanone 41.1 292.0 2 2 resin [60%] 5 B 52 153.8 Acetone resin 41.6 288.5 2 2 [60%] 6 C 39.2 306.1 Cyclohexanone 41.1 194.6 2 2 resin [40%] 7 A 40.5 216.6 Acetone resin 41.6 136 2 2 [40%] C1 A 2 4 C2 A 40.5 246.9 Auxiliary 36.3 275.5 1-2 1-2 polymer [50%] C3 A 40.5 246.9 Lignosulfonate 45.5 219.8 2 2 [50%] C4 Cyclohexanone 2 2 resin C5 Acetone resin 2 C6 B Not dryable C7 C 2 3-4 C8 C 39.2 306.1 Sulfonated 39.1 204.6 2 2 melamine- formaldehyde condensation product [40%] Solids = Solids content of the aqueous mixture Assessment A: Spray-dryability Assessment B: After thermal/mechanical loading

[0135] The dispersant properties were determined with a mortar test.

[0136] The cement mortar was composed of 40.0 wt % of Portland cement (CEM I 52.5 N, Milke) and 60.0 wt % of standard sand (DIN EN 196-1). The water/cement ratio (the weight ratio of water to cement) was 0.35. To plasticize the cement mortar, a polymer powder according to table 3 was added. The amount of the polymer powder is shown in table 4 and is based on the amount of cement.

[0137] The cement mortar was produced in a method based on DIN EN 196-1:2005 in a mortar mixer having a capacity of approximately 5 liters. For the mixing procedure, water, polymer powder, 0.45 g of the pulverulent defoamer Vinapor DF 9010 F (available from BASF Construction Solutions GmbH) and cement were placed into the mixing vessel. Immediately thereafter the mixing operation was commenced, with the fluidizer at low speed (140 revolutions per minute (rpm)). After 30 seconds, the standard sand was added at a uniform rate within 30 seconds to the mixture.

[0138] The mixture was then switched to a higher speed (285 rpm) and mixing was continued for 30 seconds more. The mixer was subsequently halted for 90 seconds. During the first 30 seconds, the cement mortar, which stuck to the wall and to the lower part of the bowl, was removed using a rubber scraper and was put into the middle of the bowl. After the break, the cement mortar was mixed at the higher mixing speed for a further 60 seconds. The total mixing time was 4 minutes.

[0139] Immediately after the end of the mixing operation, the slump flow was determined on all samples, using a Hgermann cone, with no compaction energy being supplied, in a method based on the SVB guidelines of the Deutscher Ausschuss fr Stahlbeton (German Reinforced Concrete Committee; see: Deutscher Ausschuss fr Stahlbetonbau (ed.): DAfStbGuidelines for self-compacting concrete (SVB Guidelines), Berlin, 2003). The Hgermann cone (d top=70 mm, d bottom=100 mm, h=60 mm) was placed centrally on a dry glass plate having a diameter of 400 mm and was filled with cement mortar to the level intended. Immediately after leveling had taken place, or 5 minutes after the first contact between cement and water, the Hgermann cone was taken off, held over the slumping cement mortar for 30 seconds to allow for dripping, and then removed. As soon as the slump flow came to a standstill, the diameter was determined, using a caliper gauge, at two axes lying at right angles to one another, and the average was calculated. The slump flow profile over time was characterized by repeating the slump flow test after 10, 20, 30, 45, 60, 90, and 120 minutes. Prior to each test, the cement mortar was mixed up in a mortar mixer at a rate of 140 revolutions per minute (rpm) for 10 seconds.

[0140] The solidification times were determined to DIN EN 196, part 3.

[0141] The results of these tests are set out in table 4.

TABLE-US-00004 TABLE 4 Slump flow/cm Vicat Metering 5 10 30 60 120 solidification ES/ Powder % bwoc min min min min min BS/min min 1 0.45 28.4 26.6 23.8 21.3 345 436 2 0.32 30.4 27.4 23.2 22.2 19.5 419 474 3 0.24 29.7 28.0 26.5 25.3 23.1 432 505 4 0.5 10.0 10.0 20.8 28.3 372 418 5 0.6 10 10 20.2 24.8 385 456 6 0.3 26.2 23.8 21.9 21.8 403 496 7 0.3 29.8 28.7 27.0 24.8 445 506 C1 0.18 30.4 29.5 27.5 26.8 394 466 C2 0.3 28.6 27.8 26.4 24.9 654 699 C3 0.38 28 23.4 20.8 19.3 507 544 C4 0.7 Not flowable C5 0.6 Not flowable C7 0.17 26.8 24.6 23.3 23.1 366 458 C8 0.45 27.6 27.7 27.5 27.3 398 543 BS: Beginning of solidification ES: End of solidification

[0142] As can be seen from the experiments, only the powders 1 to 7 of the invention have not only good powder properties but also at the same time good dispersing properties in mortars and permit a low mortar solidification time.

[0143] Powder C8 was produced in analogy to the disclosure in WO 2013/020862 and is directly comparable with powder 6 of the invention. In this case it is found that in comparison to powder C8, powder 6 of the invention causes much less retardation of the setting of the inorganic binder and, furthermore, exhibits much better metering efficiency.