MIXTURES CONTAINING SUPERABSORBERS

Abstract

A mixture along with methods of preparing, uses and/or products made from the mixture and methods of preparing products made from the same. Where the mixture contains 0.5% to 10% by weight of one or more superabsorbent polymers and 90% to 99.5% by weight of one or more protective-colloid-stabilized polymers based on one or more ethylenically unsaturated monomers and optionally one or more additives. Where the percentages by weight are based on the dry weight of the mixture and wherein no mineral binder is present within the mixture.

Claims

1-13. (canceled)

14. A mixture, comprising: wherein the mixture contains 0.5% to 10% by weight of one or more superabsorbent polymers and 30% to 99.5% by weight of one or more protective-colloid-stabilized polymers based on one or more ethylenically unsaturated monomers selected from the group comprising vinyl esters of carboxylic acids having 1 to 15 carbon atoms, methacrylic esters or acrylic esters of carboxylic acids with unbranched or branched alcohols having 1 to 15 carbon atoms, olefins, dienes, vinylaromatics, and vinyl halides and optionally one or more additives; where the percentages by weight are based on the dry weight of the mixture; and wherein no mineral binder is present.

15. The mixture of claim 14, wherein the superabsorbers are based on one or more ethylenically unsaturated monomers bearing ionic groups, (ii) one or more crosslinking, ethylenically unsaturated monomers, (iii) optionally one or more monoethylenically unsaturated, nonionic monomers bearing (meth)acrylamido groups, and (iv) optionally one or more other monoethylenically unsaturated hydrophilic monomers.

16. The mixture of claim 14, wherein the superabsorbers are based on (i) 19.9 to 49.9 mol % of 2-acrylamido-2-methylpropanesulfonic acid, 50 to 80 mol % of acrylamide, and also a crosslinking monomer selected from the group comprising triallylamine, N,N′-methylenebisacrylamide, and pentaerythritol triallyl ether, (ii) 19.9 to 49.9 mol % of (meth)acrylic acid, 50 to 80 mol % of acrylamide, and also a crosslinking monomer selected from the group comprising triallylamine, N,N′-methylenebisacrylamide, and pentaerythritol triallyl ether, or (iii) 19.9 to 49.9 mol % of [3-(acryloylamino)propyl]trimethylammonium chloride, 50 to 80 mol % of acrylamide, and a crosslinking monomer selected from the group comprising triallylamine, N,N′-methylenebisacrylamide, and pentaerythritol triallyl ether.

17. The mixture of claim 14, wherein the polymers based on ethylenically unsaturated monomers are selected from the group comprising vinyl acetate homopolymers, copolymers of vinyl acetate with ethylene, copolymers of vinyl acetate with ethylene and one or more further vinyl esters, copolymers of vinyl acetate with ethylene and acrylic esters, copolymers of vinyl acetate with ethylene and vinyl chloride, styrene-acrylic ester copolymers, and styrene-1,3-butadiene copolymers.

18. The mixture of claim 14, wherein the polymers based on ethylenically unsaturated monomers are selected from the group comprising vinyl acetate homopolymers; copolymers of vinyl acetate with 1% to 40% by weight of ethylene; copolymers of vinyl acetate with 1% to 40% by weight of ethylene and 1% to 50% by weight of one or more further comonomers from the group of the vinyl esters having 1 to 12 carbon atoms in the carboxyl radical; copolymers of vinyl acetate, 1% to 40% by weight of ethylene, and 1% to 60% by weight of acrylic esters of unbranched or branched alcohols having 1 to 15 carbon atoms; copolymers with 30% to 75% by weight of vinyl acetate, 1% to 30% by weight of vinyl laurate or vinyl esters of an alpha-branched carboxylic acid having 5 to 13 carbon atoms, and also 1% to 30% by weight of acrylic esters of unbranched or branched alcohols having 1 to 15 carbon atoms, which may additionally contain 1% to 40% by weight of ethylene; copolymers with vinyl acetate, 1% to 40% by weight of ethylene, and 1% to 60% by weight of vinyl chloride; copolymers of n-butyl acrylate or 2-ethylhexyl acrylate; copolymers of methyl methacrylate with n-butyl acrylate and/or 2-ethylhexyl acrylate and optionally ethylene; styrene-acrylic ester copolymers with one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; vinyl acetate-acrylic ester copolymers with one or more monomers from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and optionally ethylene; styrene-1,3-butadiene copolymers; and wherein the figures in % by weight add up to 100% by weight in each case.

19. The mixture of claim 14, wherein the protective colloids are selected from the group comprising polyvinyl alcohols; polyvinyl acetals; polyvinylpyrrolidones; polysaccharides in water-soluble form, such as starches (amylose and amylopectin), celluloses and the carboxymethyl, methyl, hydroxyethyl, and hydroxypropyl derivatives thereof, dextrins and cyclodextrins; proteins; lignosulfonates; poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxy-functional comonomer units, poly(meth)acrylamide, polyvinylsulfonic acids, and the water-soluble copolymers thereof; melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, styrene-maleic acid copolymers and vinyl ether-maleic acid copolymers.

20. The mixture of claim 14, wherein the mixture is in the form of an aqueous dispersion.

21. The mixture of claim 14, wherein the mixture is used as leveling compounds, plasters, spackling compounds, jointing mortars, tile adhesives, full thermal insulation adhesives, sealing slurries or for producing thermal insulation composite systems.

22. A process for producing mixtures, comprising: mixing 0.5% to 10% by weight of one or more superabsorbers and 30% to 99.5% by weight of one or more protective-colloid-stabilized polymers based on one or more ethylenically unsaturated monomers selected from the group comprising vinyl esters of carboxylic acids having 1 to 15 carbon atoms, methacrylic esters or acrylic esters of carboxylic acids with unbranched or branched alcohols having 1 to 15 carbon atoms, olefins, dienes, vinylaromatics, and vinyl halides and optionally one or more additives, wherein the percentages by weight are based on the dry weight of the mixtures and wherein no mineral binder is used.

23. A process for producing a building material formulation, comprising: mixing one or more mineral binders, optionally one or more fillers, and optionally one or more additions; and admixing one or more mixtures comprising 0.5% to 10% by weight of one or more superabsorbent polymers and 30% to 99.5% by weight of one or more protective-colloid-stabilized polymers based on one or more ethylenically unsaturated monomers selected from the group comprising vinyl esters of carboxylic acids having 1 to 15 carbon atoms, methacrylic esters or acrylic esters of carboxylic acids with unbranched or branched alcohols having 1 to 15 carbon atoms, olefins, dienes, vinylaromatics, and vinyl halides and optionally one or more additives, where the percentages by weight are based on the dry weight of the mixture, and wherein no mineral binder is present

Description

EXAMPLE 1

[0120] Preparation of the Mixtures:

[0121] For the production of mixtures a) to h), the superabsorbers and additives specified hereinbelow were mixed in an Eirich mixer for a total of 10 min at room temperature.

[0122] a) 30 g of Starvis S 5514 F and 970 g of VINNAPAS 5010 N;

[0123] b) 30 g of superabsorber II and 970 g of VINNAPAS 5010 N;

[0124] c) 30 g of superabsorber II and 500 g of calcium formate;

[0125] d) 30 g of superabsorber II and 50 g of starch ether Casucol Fix 1;

[0126] e) 30 g of superabsorber II and 40 g of defoamer Agitan P804;

[0127] f) 30 g of superabsorber II and 50 g of Arbocel PWC 500;

[0128] g) 30 g of superabsorber II and 550 g of Tylose H 300 P2;

[0129] h) 30 g of superabsorber II and 50 g of tartaric acid.

EXAMPLE 2

[0130] Preparation of the Aqueous Mixtures:

[0131] The mixtures a) to h) were mixed for 5 min at room temperature in a Thinky ARE 250 planetary mixer with the amounts of water specified below. [0132] a) 2 g of the dispersible mixtures from example 1a was dispersed in 44 ml of water; [0133] b) 2 g of the dispersible mixtures from example 1b was dispersed in 40 ml of water; [0134] c) 1.06 g of the dispersible mixtures from example 1c was dispersed in 40 ml of water; [0135] d) 0.16 g of the dispersible mixtures from example 1d was dispersed in 44 ml of water; [0136] e) 0.14 g of the dispersible mixtures from example 1e was dispersed in 40 ml of water; [0137] f) 0.6 g of the dispersible mixtures from example 1f was dispersed in 44 ml of water; [0138] g) 1.16 g of the dispersible mixtures from example 1g was dissolved in 40 ml of water. The solution was allowed to stand at room temperature for 24 h to degas; [0139] h) 0.16 g of the dispersible mixtures from example 1h was dissolved in 40 ml of water.

EXAMPLE 3

[0140] Production of the Dry Mortars:

[0141] 320.0 g of Milke CEM I 42.5N cement, 331.3 g of F31 quartz sand, 331.0 g of F36 quartz sand, and the further components specified for the respective reference mortar or test mortar were mixed in a Toni mixer for 15 min.

[0142] a) Reference mortar:

[0143] 5.0 g of calcium formate, 2.7 g of Tylose MH 60.004 P6,

[0144] 0.3 g of Starvis S 5514 F, and 9.7 g of VINNAPAS 5010 N; [0145] Test mortar: [0146] 5.0 g of calcium formate and 2.7 g of Tylose MH 60.004 P6;

[0147] b) Reference mortar:

[0148] 5.0 g of calcium formate, 2.7 g of Tylose MH 60.004 P6,

[0149] 0.3 g of superabsorber II, and 9.7 g of VINNAPAS 5010 N; [0150] Test mortar: [0151] 5.0 g of calcium formate and 2.7 g of Tylose MH 60.004 P6;

[0152] c) Reference mortar:

[0153] 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6,

[0154] 5.0 g of calcium formate, and 0.3 g of superabsorber II; [0155] Test mortar: [0156] 9.7 g of VINNAPAS 5010 N and 2.7 g of Tylose MH 60.004 P6;

[0157] d) Reference mortar:

[0158] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6, [0159] 0.3 g of superabsorber II, and 0.5 g of Casucol Fix 1; [0160] Test mortar: [0161] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, and 2.7 g of Tylose MH 60.004 P6;

[0162] e) Reference mortar: [0163] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6, 0.3 g of superabsorber II, and 0.4 g of Agitan P 804; [0164] Test mortar: [0165] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, and 2.7 g of Tylose MH 60.004 P6;

[0166] f) Reference mortar:

[0167] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6, [0168] 0.5 g of Arbocel PWC 500, and 0.3 g of superabsorber II;

[0169] Test mortar: [0170] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, and 2.7 g of Tylose MH 60.004 P6;

[0171] g) Reference mortar:

[0172] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N,

[0173] 0.3 g of superabsorber II, and 5.5 g of Tylose H 300 P2; [0174] Test mortar: [0175] 5.0 g of calcium formate and 9.7 g of VINNAPAS 5010 N,

[0176] h) Reference mortar: [0177] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6, 0.5 g of tartaric acid, and 0.3 g of superabsorber II;

[0178] Test mortar: [0179] 5.0 g of calcium formate, 9.7 g of VINNAPAS 5010 N, and 2.7 g of Tylose MH 60.004 P6.

EXAMPLE 4

[0180] Production of the Fresh Mortars:

[0181] The respective dry mortar from example 3 was made by mixing with a hand mixer for 20 sec using the components specified below.

[0182] a) Reference mortar:

[0183] 200 g of the reference mortar from example 3a and 44 ml of water; [0184] Test mortar: [0185] 198 g of the test mortar from example 3a and also the aqueous mixture from example 2a;

[0186] b) Reference mortar:

[0187] 200 g of the reference mortar from example 3b and 40 ml of water; [0188] Test mortar: [0189] 198 g of the test mortar from example 3b and also the aqueous mixture from example 2b;

[0190] c) Reference mortar:

[0191] 200 g of the reference mortar from example 3c and 40 ml of water; [0192] Test mortar: [0193] 198.9 g of the test mortar from example 3c and also the aqueous mixture from example 2c;

[0194] d) Reference mortar:

[0195] 200.1 g of the reference mortar from example 3d and 44 ml of water; [0196] Test mortar: [0197] 199.9 g of the test mortar from example 3d and also the aqueous mixture from example 2d;

[0198] e) Reference mortar:

[0199] 200.1 g of the reference mortar from example 3e and 40 ml of water; [0200] Test mortar: [0201] 199.9 g of the test mortar from example 3e and also the aqueous mixture from example 2e;

[0202] f) Reference mortar:

[0203] 200.1 g of the reference mortar from example 3f and 44 ml of water; [0204] Test mortar: [0205] 199.9 g of the test mortar from example 3f and also the aqueous mixture from example 2f;

[0206] g) Reference mortar:

[0207] 200.6 g of the reference mortar from example 3g and 40 ml of water; [0208] Test mortar: [0209] 199.4 g of the test mortar from example 3g and also the aqueous mixture from example 2g;

[0210] h) Reference mortar:

[0211] 200.1 g of the reference mortar from example 3h and 40 ml of water; [0212] Test mortar: [0213] 199.9 g of the test mortar from example 3h and also the aqueous mixture from example 2h.

TABLE-US-00001 TABLE 1 Properties of the fresh mortars from example 4: Viscosity [mPa .Math. s] Wettability Reference Test Time Reference Test Example mortar mortar [min] mortar [%] mortar [%] 4a) 589.000 527.000 10 90 95 20 70 90 30 35 75 4b) 972.000 893.000 10 85 95 20 65 80 30 35 45 4c) 810.000 682.000 10 80 95 20 60 80 30 25 45 4d) 770.000 643.000 10 90 95 20 65 85 30 35 55 4e) 747.000 670.000 n.d. n.d. 4f) 548.000 511.000 10 90 95 20 70 80 30 35 45 4g) 417.000 382.000 10 90 95 20 75 80 30 50 75 4h) 649.000 541.000 n.d. n.d. n.d.: Measurement was not carried out.

EXAMPLE 5

[0214] Testing the Properties of the Fresh Mortars:

[0215] a) Determination of viscosity: [0216] The viscosity of the fresh mortars from example 4 was determined immediately after mixing using the Brookfield Helipath viscometer (5 rpm, spindle T96) at room temperature.

[0217] b) Determination of wettability: [0218] The fresh mortars produced in example 4 were allowed to stand for 10 min and then mixed up again with the hand mixer for 20 seconds. [0219] This was followed by determination of the wettability in accordance with DIN EN 1347. In the test, instead of glass plates, unglazed type Bla ceramic tiles (EN 12004) measuring 5 cm×5 cm were laid after 10, 20, and 30 min. [0220] After a total of 40 min, the tiles were turned over and the wetting of the back of the tiles determined as a percentage of the total tile area.

[0221] The results of the testing are summarized in Table 1 above.

EXAMPLE 6

[0222] Mortar having a lower proportion of methyl cellulose Tylose MH 60.004 P6.

[0223] Production of the Dry Mortars:

[0224] i) Test Mortar: [0225] In analogous manner to example 3c), but dosing with about 20% by weight less of methylcellulose (Tylose MH 60.004 P6): [0226] 320.2 g of Milke CEM I 42.5N cement, 331.5 g of F31 quartz sand, 331.2 g of F36 quartz sand, 9.7 g of VINNAPAS 5010 N, and 2.16 g of Tylose MH 60.004 P6 were mixed in a Toni mixer for 15 min.

[0227] ii) Test Mortar: [0228] In analogous manner to example 3d), but dosing with about 20% by weight less of methylcellulose (Tylose MH 60.004 P6): [0229] 320.2 g of Milke CEM I 42.5N cement, 331.5 g of F31 quartz sand, 331.2 g of F36 quartz sand, 5.0 g calcium formate, 9.7 g of VINNAPAS 5010 N, and 2.16 g of Tylose MH 60.004 P6 were mixed in a Toni mixer for 15 min Tylose MH 60.004 P6.

[0230] Mixing of the Fresh Mortars:

[0231] i) Test Mortar: [0232] In analogous manner to example 4c), 198.9 g of the dry mortar produced in example 6i) was sprinkled into the aqueous mixture produced in example 2c) while mixing. The mixture was mixed with the hand mixer. The total mixing time was 20 sec.

[0233] ii) Test Mortar: [0234] In analogous manner to example 4d), 199.9 g of the dry mortar produced in example 6ii) was sprinkled into the aqueous mixture produced in example 2d) while mixing. The mixture was mixed with the hand mixer. The total mixing time was 20 sec.

[0235] Testing the Properties of the Fresh Mortars:

[0236] The viscosity and wettability were tested as described for example 5.

[0237] The results are summarized in Table 2.

TABLE-US-00002 TABLE 2 Properties of the fresh mortars from example 6: Viscosity [mPa .Math. s] Wettability Reference Test Reference Test mortar mortar Time mortar mortar Example 4c) 6i) [min] 4c) [%] 6i) [%] 810.000 533.000 10 80 90 20 60 70 30 25 30 Reference Test Reference Test mortar mortar Time mortar mortar Example 4d) 6ii) [min] 4d) [%] 6ii) [%] 770.000 534.000 10 90 95 20 65 85 30 35 40

[0238] The examples with the inventive test mortars 6i) and 6ii) show that, by comparison with the corresponding reference mortars from examples 4c) and 4d), it is possible with the procedure according to the invention to reduce the amount of the thickener methylcellulose used and still improve the wettability of the mortars or even to reduce the amount of methylcellulose further and still be able to adjust the wettability to an acceptable value.

[0239] In addition, the inventive test mortars from example 6) advantageously also have a lower viscosity than the corresponding reference mortars from examples 4c) and 4d).

COMPARATIVE EXAMPLE 7

[0240] The aqueous premixes for comparative example 7 comprised superabsorber, but no further additives.

[0241] i) Production of the Aqueous Premix Containing Superabsorber: [0242] 0.3 g of superabsorber II was mixed with and suspended in 200 ml of water in a Thinky ARE 250 planetary mixer for 5 min at room temperature.

[0243] ii) Production of the Dry Mortars: [0244] c) The reference mortar differed from the test mortar from example 3c) in that calcium formate was added to the dry mortar: [0245] 320.0 g of Milke CEM I 42.5N cement, 331.3 g of F31 quartz sand, 331.0 g of F36 quartz sand, [0246] 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6, and [0247] 5.0 g of calcium formate were mixed in the Toni mixer for 15 min. [0248] d) The reference mortar differed from the test mortar from example 3d) in that Casucol Fix1 was added to the dry mortar: [0249] 320.0 g of Milke CEM I 42.5N cement, 331.3 g of F31 quartz sand, 331.0 g of F36 quartz sand, [0250] 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6, and [0251] 0.5 g of Casucol Fix1 were mixed in the Toni mixer for 15 min. [0252] e) The reference mortar differed from the test mortar from example 3e) in that Agitan P804 was added to the dry mortar: [0253] 320.0 g of Milke CEM I 42.5N cement, 331.3 g of F31 quartz sand, 331.0 g of F36 quartz sand, [0254] 9.7 g of VINNAPAS 5010 N, 2.7 g of Tylose MH 60.004 P6, and [0255] 0.4 g of Agitan P804 were mixed in the Toni mixer for 15 min.

[0256] iii) Mixing the fresh mortars: [0257] c) Reference mortar: [0258] 199.9 g of the dry mortar produced in comparative example 7-ii-c) was sprinkled into 40.06 g of the premix produced in comparative example 7-i) while mixing. The mixture was mixed with the hand mixer. The total mixing time was 20 sec. [0259] d) Reference mortar: [0260] 199.0 g of the dry mortar produced in comparative example 7-ii-d) was sprinkled into 44.06 g of the premix produced in comparative example 7-i) while mixing. The mixture was mixed with the hand mixer. The total mixing time was 20 sec. [0261] e) Reference mortar: [0262] 199.0 g of the dry mortar produced in comparative example 7-ii-e) was sprinkled into 40.06 g of the premix produced in comparative example 7-i) while mixing. The mixture was mixed with the hand mixer. The total mixing time was 20 sec.

[0263] Testing the properties of the fresh mortars:

[0264] The viscosity and wettability of the fresh mortars were tested as described for example 5.

[0265] The results are summarized in Table 3.

TABLE-US-00003 TABLE 3 Properties of the fresh mortars from comparative example 7 and examples 4c-e): Viscosity [mPa .Math. s] Wettability Test Reference Test Reference mortar mortar Time mortar mortar Example 4c) 7-iii-c) [min] 4c) [%] 7-iii-c) [%] 682.000 (4c) 741.000 10 95 90 20 80 70 30 45 30 Test Reference Test Reference mortar mortar Time mortar mortar Example 4d) 7-iii-d) [min] 4d) [%] 7-iii-d) [%] 643.000 (4d) 719.000 10 95 90 20 85 70 30 55 40 Test Reference Test Reference mortar mortar Time mortar mortar Example 4e) 7-iii-e) [min] 4e) [%] 7-iii-e) [%] 670.000 (4e) 750.000 n.d. n.d. n.d.: Measurement was not carried out.

[0266] The comparison of the inventive test mortars 4c-e) with the reference mortars from comparative examples 7-iii) shows that the viscosity and wettability of the fresh mortars were improved by introducing the superabsorbers and additives into the mortar in the form of a premix. By contrast, conventional separate introduction of the superabsorbers and additives into the mortar, as was done in comparative example 7-iii), did not achieve the desired effects.