COMPOSITION FOR INORGANIC BINDERS

Abstract

The invention relates to a composition for inorganic binders, comprising at least one ketone-formaldehyde condensation product on the basis of a cyclic ketone and at least one anionic or nonionic surfactant and/or a thickener, and also to building material mixtures which comprise this composition, and to the use of the composition. The compositions improve the applications properties of the binder formulations.

Claims

1: A composition, comprising a) at least one ketone-formaldehyde condensation product containing at least one acidic group selected from the group consisting of a phosphono, sulfite, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy, and phosphonooxy group, wherein the ketone is a ketone of formula R.sup.1COR.sup.2, where R.sup.1 and R.sup.2 taken together are a C.sub.3-C.sub.6 alkylene radical which optionally contains one or more substituents selected from the group consisting of an amino, hydroxyl, C.sub.1-C.sub.4 alkoxy or C.sub.1-C.sub.4 alkoxycarbonyl group, and b) at least one anionic or nonionic surfactant and/or at least one thickener, wherein a weight ratio of component (a) to component (b) is in the range from 3:1 to 1:10.

2: The composition according to claim 1, wherein the ketone is a cyclic ketone of formula ##STR00002## which where R.sup.3 to R.sup.7 each independently are H or C.sub.1-C.sub.4 alkyl, and n is 0, 1 or 2.

3: The composition according to claim 2, wherein the ketone is selected from the group consisting of cyclohexanone, 4-methylcyclo-hexanone, cyclopentanone, cycloheptanone, and a mixture thereof.

4: The composition according to claim 3, wherein the ketone is cyclohexanone.

5: The composition according to claim 1, wherein the at least one acidic group is a phosphono, sulfite, sulfino or sulfo group.

6: The composition according to claim 5, wherein the at least one acidic group is a sulfite group.

7: The composition according to claim 1, wherein the ketone-formaldehyde condensation product is a cyclohexanone/formaldehyde/sulfite condensation product.

8: The composition according to claim 1, wherein component (b) comprises at least one anionic or nonionic surfactant.

9: The composition according to claim 8, wherein the surfactant is selected from the group consisting of a C.sub.8-C.sub.18 alkyl sulfate, a C.sub.8-C.sub.18 alkyl ether sulfate, a C.sub.8-C.sub.18 alkylsulfonate, a C.sub.8-C.sub.18 alkylbenzenesulfonate, a C.sub.8-C.sub.18 -olefinsulfonate, a C.sub.8-C.sub.18 sulfosuccinate, an -sulfo C.sub.8-C.sub.18 fatty acid disalt, a C.sub.8-C.sub.18 fatty acid salt, a C.sub.8-C.sub.18 fatty alcohol ethoxylate, a block copolymer of ethylene oxide and propylene oxide, a C.sub.8-C.sub.18 alkylpolyglycoside, and a mixture thereof.

10: The composition according to claim 1, wherein component (b) comprises at least one thickener.

11: The composition according to claim 10, wherein the thickener is selected from the group consisting of a polysaccharide derivate and a (co)polymer having a weight-average molecular weight M.sub.w of more than 500 000 g/mole.

12: The composition according to claim 11, wherein the thickener is selected from the group consisting of a cellulose ether, a starch ether, and a (co)polymer comprising a structural unit of at least one nonionic (meth)acrylamide monomer and/or at least one sulfonic acid monomer.

13: The composition according to claim 1, comprising at least one thickener and at least one anionic or nonionic surfactant as component (b).

14: The composition according to claim 1, wherein the weight ratio of component (a) to component (b) is in the range from 3:1 to 1:5.

15: The composition according to claim 14, wherein the weight ratio of component (a) to component (b) is in the range from 1:2 to 1:5.

16: The composition according to claim 1, which is in powder and/or granule form.

17: The composition according to claim 16, obtained by co-spray drying of a mixture comprising components (a) and (b).

18: A building material mixture, comprising the composition according to claim 1 and an inorganic binder.

19: The building material mixture according to claim 18, wherein the inorganic binder is a hydraulic or latent hydraulic binder or a mixture thereof.

20. (canceled)

21: A method of improving application properties of a building material formulation, the method comprising: adding the composition according to claim 1 to the building material mixture comprising an inorganic binder.

Description

[0037] The examples which follow illustrate the invention without limiting it.

[0038] A cyclohexanone resin (CHR) was used which was prepared as follows (corresponding to polymer 5 in table 1 of WO 2015/039890):

a reaction vessel was charged with 40 g of water and the pH was adjusted to 10. Added to this initial charge was 0.25 mol of sodium sulfite and, lastly, 0.51 mol of cyclohexanone was added dropwise with stirring, the temperature climbing to 30-32 C. This was followed by heating to around 60 C. 1.5 Mol of formaldehyde was slowly added dropwise, at a rate such that the temperature did not exceed 70 C. After the end of addition, the temperature was raised to 90 C. and the mixture was heated for a further 3 hours until the molecular weight M.sub.w reached 18 000. The molecular weight was determined by GPC and viscosimetry. The residual formaldehyde content was <10 ppm.

[0039] Thickener: methylhydroxyethylcellulose (MC) Tylose FL 15002

Surfactants:

[0040] Surfactant 1: C14/C16 -olefinsulfonate sodium salt (Hostapur OSB)
Surfactant 2: sodium lauryl sulfate (Texapon K12P)
Surfactant 3: disodium alpha-sulfo-C12/14 fatty acid (Texapon SFA).
Surfactant 4: ethylene/propylene copolymer (Pluronic PE 9400)
Surfactant 5: alkyl ether sulate (Vinapor Gyp 2620)

[0041] The compositions listed in table 1 were produced by mixing the corresponding aqueous solutions of the components. The solutions were dried using a Mobile Minor MM-I spray drier from GEA Niro. Drying took place by means of a two-fluid nozzle at the top of the tower. Drying was carried out with nitrogen, which was blown from top to bottom in cocurrent with the material for drying, using 80 kg/h drying gas. The temperature of the drying gas at the tower entry was 220 C. The feed rate of the material being dried was adjusted such that the output 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.

TABLE-US-00001 TABLE 1 CHR:surfactant Composition No. Component a) Component b) ratio 1 CHR Surfactant 1 1/1 2 CHR Surfactant 1 1/2 3 CHR Surfactant 1 1/4 4 CHR Surfactant 2 1/1 5 CHR Surfactant 2 1/2 6 CHR Surfactant 2 1/4 7 CHR Surfactant 3 1/1 8 CHR Surfactant 3 1/2 9 CHR Surfactant 3 1/4 10 CHR 1/0 C1 Surfactant 1 0/1 C2 Surfactant 2 0/1 C3 Surfactant 3 0/1 C4 Melment F10

[0042] Melment F10 is a sulfonated melamine-formaldehyde resin (DE1671017A1).

[0043] The compositions were used in a test mixture whose formula was as follows:

Milke cement CEM I 52.5 N 20%
Strobel fused silica BCS 319 80%

Water 20%

[0044] The mixture was prepared by stirring as per DIN EN 998-1: cement, silica, thickener, and the mixtures listed in table 1 were charged to a mortar mixture (Rilem mixer) according to DIN EN 196-1 and admixed with the stated amount of water. Stirring then took place at a low setting (140 rpm) for 90 seconds, followed by a 90-second pause and then by further stirring at a high setting (285 rpm) for 60 seconds.

[0045] The resulting mortar was tested for air pore content (by DIN EN 998-1), flow properties (by DIN EN 998-1) and fluffiness. Fluffiness referred to a loose, easy, soft, and silky tactile quality to the mortar. The fluffiness is also manifested in particularly easy spreadability of the mortar. The fluffiness was assessed by a parallel and direct comparison with the prior art. Here, two mixtures were produced simultaneously and spread by trowel onto a wooden plate. Based on the fluffiness of the material, the person applying it rates its quality in a range from 3 to +3. A rating of 0 here corresponds to characteristics identical to those of the comparison specimen. A rating of up to +3 corresponds to improvement; a rating of down to 3 corresponds to a deterioration. FIG. 1 (standard without CHR) and 2 (improved mortar with CHR) visualize the rheological properties. At relatively high fluffiness, the surface texture is more attractive and more even. Break-up on the trowel is significantly reduced in FIG. 2. As a result, it becomes much easier to spread the mortar.

[0046] The evaluation is made immediately after stirring and after 30 minutes. The difference in the value after 30 minutes is described in the table as stability over time. As the comparative example and prior art resin, Melment F10 is used.

TABLE-US-00002 TABLE 2 Change Amount Amount of in added Tylose FL density [% based 15002 Air after Stability Experiment on dry [methylhydroxy- content 30 min Overall over # Composition mortar] ethylcellulose [%] [%] impression Fluffiness time Comparison None 0.1 29 8.5 0 0 0 specimen 1 C3 0.028 0.1 43 4.4 0.5 0.5 0 2 C4 0.03 0.1 27 5.5 1 1 1 3 C4 0.1 0.1 27 4.1 1 1 1 4 2 0.03 0.1 37 3.6 1.5 1 1 5 7 0.06 0.1 38 4.8 2.5 2.5 2 6 9 0.036 0.1 42 2.6 3 3 2 7 10 0.03 0.1 29 6.1 0.5 0.5 0 8 10 + C3 0.03 + 0.06 0.1 42 2.6 2.5 2.5 1.5 9 10 + C3 0.03 + 0.03 0.1 39 4.8 2 2 0.5 10 4 0.3 0.1 32 5.0 1.0 1 1 11 1 0.03 0.1 43 4.0 1.0 1 1 12 3 0.03 0.1 41 3.7 2.5 2 1.5 13 5 0.03 0.1 46 5.4 1.5 1 2 14 6 0.03 0.1 40 4 1.5 1 2.5 15 8 0.03 0.1 40 4.0 2.5 2.5 2 16 7 0.03 0 23 0.3 1 1 0 17 9 0.03 0 22 0.7 1 1 0 18 1 0.03 0 29 1.2 1 1 0.5

[0047] It is evident that the compositions of the invention result in a higher air content and a lower mortar density. Furthermore, mortar fluffiness and stability are improved. All in all, the overall impression is improved.

[0048] The next examples show the advantage of formulations of the ketone resin with two different surfactants.

[0049] The mortar composition and mixing procedure was the same as above.

[0050] The Additive mix is summarized in Table 3. The haptic measurements in this series of experiment summarized in Table 4 are referenced against experiment 19

TABLE-US-00003 TABLE 3 Experiment CHR Surfactant 3 Surfactant 4 Surfactant 5 19 1 1 20 1 1 0.4 21 1 1 0.4

TABLE-US-00004 TABLE 4 Amount added Air Stability Experiment [% based on content Overall over # dry mortar] [%] impression Fluffiness time 19 0.36 16.8 0 0 0 20 0.36 18.5 1.5 2 1.5 21 0.36 17.3 0.75 1 0.75

[0051] Further application suitability was tested in a TICS reinforcing mortar whose composition was as follows:

Milke cement CEM I 52.5 N 25%
Fused silica BCS 319 75%

MHEC 15 000 0.08%

Baerophob ECO 0.35%

Starvis SE 35 F 0.050

Starvis S 5514 F 0.34%

Water 20%

[0052] Starvis SE 35 is a starch ether available commercially from BASF SE. Starvis S 5514 F is a water-swellable, high molecular mass polymer (superabsorbent) and is likewise available from BASF SE. Baerophob ECO is a complex metal soap for hydrophobizing, available from Barlocher GmbH. The reinforcing mortar was mixed as a dry mortar and applied with a PFT-G4 render machine; application suitability was evaluated visually and on a tactile basis. The results are reported in table 3 (rating of +3 to 3 as indicated above, reference=0).

TABLE-US-00005 TABLE 5 Fresh mortar properties With G4 machine tests, Reference Reference + water quantities constant without CHR 0.03 CHR Immediate evaluation in pail: 0 2 smoothness, stickiness, overall appearance, after-thickening Evaluation in pail after 30 min: 0 2 smoothness, stickiness, overall appearance, initial thickening Initial spray behavior/spray pattern/holdout 0 3 Evaluation after initial spraying: 0 2 ease of working, stickiness on tooling Evaluation of mesh insertion after 30 min 0 2 Evaluation of reworking/initial working after 0 2 30 min Stickiness after 30 min 0 3 Overall evaluation 0 2.3

[0053] Table 5 shows that the composition of the invention composed of cyclohexanone-formaldehyde resin and thickener (MHEC) leads to a significant improvement in application suitability.

[0054] Further application suitability is shown using a hand-applied plaster render. The composition selected was as follows:

750 g of FGD -hemihydrate Schwarze Pumpe
210 g of crushed limestone sand 0-3 mm (Heck Wallsystems)

10 g of Bachl PZ1 Perlite (0-1 mm)

[0055] 30 g of lime hydrate
2 g of BCZ tartaric acid

0.15 g of Texapon K12P

1.9 g of Culminal C4053

0.2 g of Starvis SE35F

[0056] 490 g of water

[0057] The plaster render dry mortar was prepared by stirring with water in a Kitchen Aid, and the application suitability was evaluated visually. The results are shown in table 6.

TABLE-US-00006 TABLE 6 Reference + Fresh mortar properties Reference CHR Immediate evaluation in pail.sup.1) 0 2 Evaluation in pail after 30 min.sup.1) 0 2 Ease of working, stickiness on the 0 3 tooling Evaluation of after working/initial working 0 2 after 30 min Stickiness after 30 min 0 3 Overall evaluation 0 2.4 .sup.1)smoothness, stickiness, overall appearance, after-thickening

[0058] Table 6 as well shows that the composition of the invention composed of cyclohexanone-formaldehyde resin and thickener (MHEC) leads to a significant improvement in application suitability.