Rapidly suspendable pulverulent composition

Abstract

The invention relates to a pulverulent composition preparable by contacting a powder with 0.01 to 50 wt %, based on the overall mass of the composition, of a liquid component comprising at least one copolymer obtainable by polymerizing a mixture of monomers comprising (I) at least one ethylenically unsaturated monomer which comprises at least one radical from the series carboxylic acid, carboxylic salt, carboxylic ester, carboxylic amide, carboxylic anhydride, and carboxylic imide and (II) at least one ethylenically unsaturated monomer having a polyalkylene oxide radical, the liquid component comprising at least 1 wt % of the at least one copolymer and at least 30 wt % of an organic solvent, and the powder which is contacted with the liquid component comprising no inorganic binder. Further disclosed is a binder composition which comprises a pulverulent composition of the invention and an inorganic binder.

Claims

1. A pulverulent composition, obtained by contacting a powder with 0.01 to 50 wt %, based on the overall mass of the composition, of a liquid component comprising at least one copolymer produced by a process comprising polymerizing a mixture of monomers comprising (I) at least one ethylenically unsaturated monomer which comprises at least one radical selected from the group consisting of carboxylic acid, carboxylic salt, carboxylic ester, carboxylic amide, carboxylic anhydride, and carboxylic imide and (II) at least one ethylenically unsaturated monomer having a polyalkylene oxide radical, the liquid component comprising at least 1 wt % of the at least one copolymer and at least 30 wt % of an organic solvent, and the powder which is contacted with the liquid component comprising no inorganic binder, wherein the powder is coated with the liquid component, the copolymer is present in solution in the liquid component, and wherein no drying of the composition is performed after the contacting of the powder with the liquid component.

2. The pulverulent composition according to claim 1, wherein the powder comprises at least one compound selected from the group consisting of silica sand, finely ground quartz, limestone, heavy spar, calcite, aragonite, vaterite, dolomite, talc, kaolin, mica, chalk, titanium dioxide, rutile, anatase, aluminum hydroxide, aluminum oxide, magnesium hydroxide and brucite.

3. The pulverulent composition according to claim 1, wherein the powder comprises at least one pigment selected from the group consisting of an organic pigment and an inorganic pigment.

4. The pulverulent composition according to claim 1, wherein the ethylenically unsaturated monomer (I) is represented by at least one of the following formulae (Ia), (Ib), and (Ic) ##STR00009## wherein R.sup.1 and R.sup.2 independently of one another are hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, Y is H, COOM.sub.a, COO(C.sub.qH.sub.2qO).sub.rR.sup.3 or CONH(C.sub.qH.sub.2qO).sub.rR.sup.3, M is hydrogen, a mono- or divalent metal cation, ammonium ion, or an organic amine radical, a is or 1, R.sup.3 is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, or an optionally substituted aryl radical having 6 to 14 C atoms, q independently at each occurrence for each (C.sub.qH.sub.2qO) unit is identical or different and is 2, 3, or 4, r is 0 to 200, Z is O or NR.sup.3, ##STR00010## wherein R.sup.4 and R.sup.5 independently of one another are hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, or an optionally substituted aryl radical having 6 to 14 C atoms, Q is identical or different and is also represented by NH, NR.sup.3, or O; where R.sup.3 possesses the definition stated above, R.sup.6 is identical or different and is also represented by (C.sub.nH.sub.2n)SO.sub.3H, (C.sub.nH.sub.2n)OH, (C.sub.nH.sub.2n)PO.sub.3H.sub.2, (C.sub.nH.sub.2n)OPO.sub.3H.sub.2, (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, and (C.sub.nH.sub.2n)NR.sup.8.sub.b, and b is 2 or 3, wherein n is 0, 1, 2, 3 or 4, R.sup.7 is H, COOM.sub.a, COO(C.sub.qH.sub.2qO).sub.rR.sup.3, CONH(C.sub.qH.sub.2qO).sub.rR.sup.3, wherein M.sub.a, R.sup.3, q, and r are defined above, R.sup.8 is hydrogen, an aliphatic hydrocarbon radical having 1 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, or an optionally substituted aryl radical having 6 to 14 C atoms.

5. The pulverulent composition according to claim 1, wherein the ethylenically unsaturated monomer (II) is represented by the following formula ##STR00011## wherein p is an integer between 0 and 6, y is 0 or 1, v is an integer between 3 and 500, w independently at each occurrence for each (C.sub.wH.sub.2wO) unit is identical or different and is an integer between 2 and 18, T is oxygen or a chemical bond, R.sup.1 and R.sup.2 independently of one another are hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, R.sup.3 is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, or an optionally substituted aryl radical having 6 to 14 C atoms.

6. The pulverulent composition according to claim 1, wherein the fraction of the monomer (I) in the copolymer is 5 to 95 mol %.

7. The pulverulent composition according to claim 1, wherein the fraction of the monomer (II) in the copolymer is 1 to 89 mol %.

8. The pulverulent composition according to claim 1, wherein the organic solvent is selected from the group consisting of ethyl acetate, n-butyl acetate, 1-methoxy-2-propyl acetate, ethanol, isopropanol, n-butanol, 2-ethylhexanol, 1-methoxy-2-propanol, ethylene glycol, propylene glycol, acetone, butanone, pentanone, hexanone, methyl ethyl ketone, ethyl acetate, butyl acetate, amyl acetate, tetrahydrofuran, diethyl ether, toluene, xylene, higher-boiling alkylbenzenes, a polyethylene glycol ether, a polypropylene glycol ether, a random ethylene oxide/propylene oxide copolymers having an average molar mass of 200 to 2000 g/mol, monoethylene glycol, diethylene glycol, triethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, methyl, ethyl, propyl, butyl, or higher alkyl polyalkylene glycol ethers having 1, 2, 3, or more ethylene glycol and/or propylene glycol units, a glycerol ethoxylate having a molecular weight of 200 to 20,000 g/mol, pentaerythritol alkoxylates, ethylene carbonate, propylene carbonate, glycerol carbonate, glycerol formal and 2,3-O-isopropylideneglycerol.

9. The pulverulent composition according to claim 1, wherein the monomer (I) or (II) comprises a random ethylene oxide/propylene oxide copolymer having a molecular weight of 160 to 10,000 g/mol.

10. The pulverulent composition according to claim 1, wherein the powder comprises silica sand.

11. The pulverulent composition according to claim 1, wherein the powder comprises finely ground quartz.

12. The pulverulent composition according to claim 1, wherein the powder comprises limestone.

13. The pulverulent composition according to claim 12, wherein the organic solvent is methyl polyethylene glycol.

14. The pulverulent composition according to claim 1, wherein the liquid component comprises water.

15. A binder composition comprising a pulverulent composition according to claim 1 and an inorganic binder.

16. The binder composition according to claim 15, wherein the inorganic binder is at least one member selected from the group consisting of cement based on Portland cement, white cement, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate n-hydrate, and latent hydraulic and pozzolanic binder.

17. A method for producing a binder composition comprising mixing a pulverulent composition according to claim 1 with an inorganic binder.

Description

EXAMPLES

Gel Permeation Chromatography

(1) Sample preparation for determination of the molar weight was carried out by dissolving copolymer solution in the GPC eluent, giving a polymer concentration in the GPC eluent of 0.5 wt %. Thereafter this solution was filtered through a syringe filter with polyethersulfone membrane and a pore size of 0.45 m. The injection volume of this filtrate was 50-100 l.

(2) The average molecular weights were determined on a GPC instrument from Waters with the model name Alliance 2690 with a UV detector (Waters 2487) and RI detector (Waters 2410). Columns: Shodex SB-G Guard Column for SB-800 HQ series Shodex OHpak SB 804HQ and 802.5HQ (PHM gel, 8300 mm, pH 4.0 to 7.5) Eluent: 0.05 M aqueous ammonium formate/methanol mixture=80:20 (parts by volume) Flow rate: 0.5 ml/min Temperature: 50 C. Injection: 50 to 100 l Detection: RI and UV

(3) The molecular weights of the copolymers were determined relative to polyethylene glycol standards from the company PSS Polymer Standards Service GmbH. The molecular weight distribution curves of the polyethylene glycol standards were determined by means of light scattering. The masses of the polyethylene glycol standards were 682 000, 164 000, 114 000, 57 100, 40 000, 26 100, 22 100, 12 300, 6240, 3120, 2010, 970, 430, 194, and 106 g/mol.

(4) Composition of the Copolymers

(5) The synthesis of the copolymers used is described for example in WO2006133933 page 12, line 5 to page 13, line 26. The composition of the copolymers used is as follows:

(6) TABLE-US-00001 TABLE 1 Mol of acrylic Mol of Mw Solids Polymer acid macromonomer Macromonomer (g/mol) % A 5 1 VOBPEG-3000 32 000 51 B 10 1 VOBPEG-3000 25 000 51 C 5 1 VOBPEPG-3000 27 000 51 D 10 1 VOBPEPG-3000 21 000 51

(7) The abbreviation VOBPEG-3000 stands for vinyoxybutyl-polyethylene glycol with a molar mass of 3000 g/mol, i.e. of formula (III) k=0, l=0, and n68.

(8) The abbreviation VOBPEPG-3000 stands for vinyloxybutyl-polyethylene/propylene glycol of blockwise construction. Block A contains only polyethylene glycol; block B is a random mixture of ethylene glycol and propylene glycol. The molar mass is 3000 g/mol. The structure corresponds to formula (III) with n23, k13, l28.

PREPARATION EXAMPLES

General Preparation Example (Copolymer in Methyl Polyethylene Glycol 500)

(9) A 2000 ml round-bottom flask is charged with a 51% strength aqueous solution of the copolymer. Methyl polyethylene glycol 500 (Pluriol A 500 E from BASF SE) is added. The water is then stripped off at 70 C. and 40 mbar on a rotary evaporator. At a water content of below 1 wt %, stripping is discontinued and the batch is cooled. The resulting solution is slightly opalescent and has an active ingredient content of 50 wt %.

(10) TABLE-US-00002 TABLE 2 Copolymer Methyl Active (aqueous polyethylene ingredient Example Copolymer solutions) glycol 500 content [%] 1 A 980 g, 500 g 50 51% strength solution 2 C 980 g, 500 g 50 51% strength solution 3 D 980 g, 500 g 50 51% strength solution

General Preparation Example (Liquid Component on Finely Ground Limestone

(11) A Grindomix GM 200 (Retsch GmbH) is charged with finely ground limestone (Omyacarb 20 BG from Omya GmbH). The liquid component is then added by pipette. Homogenization takes place at 5000 revolutions/minute for 5 minutes. The product is a readily free-flowing, finely ground limestone coated with the liquid component.

(12) TABLE-US-00003 TABLE 3 Finely ground Example Liquid component limestone 4 (inventive) 20 g (50% strength solution) from example 2 180 g 5 (inventive) 20 g (50% strength solution) from example 3 180 g 6 (comparative) 25 g (40% strength aqueous solution) 190 g copolymer A

APPLICATION EXAMPLES

(13) 285 g of self-leveling filling compound (see tables 4 and 5) and 285 g of cement mortar (see tables 4 and 6) are each admixed with 0.25 wt % of copolymer, based on the overall mass. For the comparative examples C1 and C2, the copolymer is weighed in as spray-dried polymer powder. For the comparative example C3, a finely ground, copolymer-coated limestone from example 6 is added to the self-leveling filling compound (copolymer is applied to the limestone in the form of an aqueous solution). For comparative example C4, the self-leveling filling compound is treated beforehand with a 40% strength solution of the copolymer and is then homogenized together with the finely ground limestone. After storage for a day, this mixture is subjected to the application testthat is, the development of the dispersing effect of the copolymer following addition of mixing water is tested. For application examples A1 and A2, finely ground limestones (15 g each from examples 2 and 3 respectively) coated with copolymer and with methyl polyethylene glycol 500 were mixed with the pulverulent composition. To assess the development of the dispersing effect of the copolymers following addition of mixing water, 300 g of the pulverulent composition thus treated are placed in a beaker and stirred with an axial stirrer at 500 revolutions per minute. Then mixing water is added and a measurement is made of the time after which the fresh mortar acquires, visually, a homogeneous consistency.

(14) Binder Composition (Self-Leveling Filling Compound and Cement Mortar)

(15) TABLE-US-00004 TABLE 4 Self-leveling filling Cement compound mortar [parts by [parts by Manufacturer weight] weight] Portland cement Heidelberg 30.00 46.00 (Milke CEM I 52.5N) Cement AG Calcium aluminate Kerneos Inc 10.00 cement (Fondu Ciment) Calcium sulfate binder Lanxess AG 6.00 CAB 30 Calcium carbonate Omya GmbH 10.00 10.00 (Omyacarb 6AL) Calcium carbonate Omya GmbH 15.00 15.00 (Omyacarb 15AL) Calcium carbonate Omya GmbH 26.38 26.6 (Omyacarb 130AL) Lithium carbonate Chemmetall GmbH 0.10 0.10 Defoamer BASF Construction 0.15 0.15 (Vinapor DF 9010 F) Polymers GmbH Dispersible powder Wacker AG 2.00 2.00 (Vinnapas 5023L) Tartaric acid DU Chemie GmbH 0.12

(16) The data in tables 5 and 6 show that the pulverulent compositions comprising finely ground, copolymer-coated limestone (A1-A4) ensure a much quicker development of the dispersing effect of the copolymers following addition of mixing water than when the pulverulent copolymers are added together with the mixing water (C1, C2, C5, C6) or when a finely ground limestone coated with an aqueous solution of a copolymer is added (C3), or when the aqueous polymer solution is premixed with the self-leveling filling compound before the mixing water is added (C4).

(17) TABLE-US-00005 TABLE 5 C1 C2 C3 C4 A1 A2 [g] [g] [g] [g] [g] [g] Self-leveling filling 285 285 285 285 285 285 compound (see table 4) Copolymer A 0.75 (spray-dried polymer powder) Copolymer B 0.75 (spray-dried polymer powder) Example 4 15 Example 5 15 Example 6 15 Copolymer A (40% 1.88 strength aqueous solution) Methyl polyethylene 0.75 0.75 glycol 500 in mixing water Omyacarb 20 BG 13.5 13.5 13.5 Mixing water 57 57 57 55.87 57 57 Time until mixture 10 10 10 12 6 5 homogeneous, in seconds

(18) TABLE-US-00006 TABLE 6 C5 C6 A3 A4 [g] [g] [g] [g] Cement mortar (see table 4) 285 285 285 285 Copolymer A (spray-dried polymer 0.75 powder) Copolymer B (spray-dried polymer 0.75 powder) Example 4 15 Example 5 15 Methyl polyethylene glycol 500 in 0.75 0.75 mixing water Omyacarb 20 BG 13.5 13.5 Mixing water 57 57 57 57 Time until mixture homogeneous, in 13 11 5 4 seconds