EP1263854A1

EP1263854A1 - Powdery composition based on water-soluble polymers

Info

Publication number: EP1263854A1
Application number: EP01907511A
Authority: EP
Inventors: Steffen Wache; Mathias Degenkolb; Klaus HÖTZL; Jana Kellermann
Original assignee: BASF Construction Polymers GmbH
Current assignee: Master Builders Solutions Deutschland GmbH
Priority date: 2000-02-09
Filing date: 2001-02-08
Publication date: 2002-12-11
Also published as: US20030004246A1; WO2001058994A1; DE10005707B4; JP2003522091A; DE10005707A1

Abstract

The invention relates to a powdery composition based on water-soluble polymers which essentially contains: a) 50 to 95 wt. % of a water-soluble polymer which is synthesized from sulfonates of lignin and/or sulfonated melamine formaldehyde, naphthalene formaldehyde and/or ketone formaldehyde condensation products, and; b) 5 to 95 wt. % of a fine particle mineral supporting material with a preferred specific surface ranging from 0.01 to 500 m2/g. Calcium carbonate, dolomite, clays, fly ashes, Portland cements, and gypsum are suitable typical supporting materials and, to this end, should preferably comprise a particle size ranging from 0.1 to 1,000 νm. The invention also relates to a method for producing said composition, whereby the water-soluble polymer is first of all worked into the respective supporting material, which is carried out, in particular, in the form of an aqueous solution during at least one step and can additionally involve intermediate drying steps. These compositions are used in quantities ranging from 0.05 to 5 wt. % of polymer in building materials such as bituminous products, cement, calcium-based building materials and/or oil field building materials, whereby they can also be combined with other building material additives and with filling material mixtures. The powdery compositions are characterized by, among other things, their very good pourability, they are tack-free, extremely easy to dose and to process, and they positively influence product properties such as flowability.

Description

Powdery composition based on water-soluble polymers

description

The present invention relates to a powdery composition, processes for its preparation and its use in building materials.

Polymer admixtures for building materials, such as. B. bitumen, mortar and

Filling compounds are well known and widely used. Corresponding polymers or polymer mixtures can be added to these products, for example in solid or in liquid and then mostly aqueous form.

In particular, the use of aqueous polymer solutions is associated with considerable disadvantages, since e.g. B. their storage is not unproblematic; namely they must not come into contact with corrosion-sensitive metals and are also sensitive to excessive heating and frost. In addition, aqueous polymer solutions must be protected against infestation by microorganisms, which means the addition of

Preservatives and possibly complex measures for tank hygiene.

The use of aqueous polymer solutions for the modification of hot building materials, such as bitumen or asphalt, is particularly problematic since an aqueous polymer solution can only be incorporated very slowly due to the spontaneous development of water vapor that occurs. There is also an increased risk of accidents due to spraying and delay in boiling.

The use of aqueous polymer solutions can be completely ruled out in areas of application in which the polymers are required in factory-made dry mixtures. For the reasons mentioned, it is therefore often sensible to incorporate polymers or polymer mixtures in solid form, usually as a powder, into the building materials to be modified.

In addition to logistical and economic advantages (transport of water), powders also have a number of technical advantages over aqueous preparations. The stabilization before infestation with microorganisms by adding biocides is eliminated, as is the u. U. elaborate measures for tank hygiene.

It is known to produce polymer powder by spraying aqueous polymer solutions in a hot air stream (spray drying), with spray aids advantageously being added.

However, the temperatures used for spray drying (up to 200 ° C) have a disadvantageous effect on the polymers to be dried in this way. For example, temperature instability of the polymers can be observed under the conditions of spray drying, which under certain circumstances leads to insoluble residues when the powders are redissolved in water.

In addition, due to the process, the spray drying process can lead to different particle size distributions of the powders produced in this way, which has a disadvantageous effect on the dissolving behavior of these powders in aqueous building material systems and can thus negatively influence the product quality of building material mixtures.

When spray drying sulfonated melamine formaldehyde

Condensation products can cause high temperatures at a corresponding pH value to cause resin changes, e.g. B. lead alkaline further condensation. The by-products formed in this way have a disadvantageous effect when such powders are used in building material mixtures. However, these disadvantages, as well as the high energy requirement of spray drying, are still accepted in order to obtain the polymers in the form of free-flowing, tack-free powders.

The invention was therefore based on the object, a powder

To provide a composition which does not have the disadvantages mentioned above and which is particularly suitable for long storage and transport times, which is largely insensitive to extreme temperatures, such as frost and heat, which does not require any preservative additives, and which moreover is faster and less dangerous than conventional spray-dried polymer compositions can be incorporated into a hot template. The composition should also be able to be produced using as little energy as possible and should ultimately not adversely affect the properties of products to which the composition is added.

This object was achieved with a powdery composition based on water-soluble polymers, which is characterized in that it a) 5 - 95 wt .-% of a water-soluble polymer consisting of sulfonates of lignin and / or sulfonated melamine, naphthalene and / or ketone-formaldehyde condensation products is built up, and b) contains 5 to 95% by weight of a finely divided mineral carrier material.

Surprisingly, it was found that with the help of this combination of a water-soluble polymer and a finely divided mineral carrier material, free-flowing, tack-free and very easy-to-use powdery compositions are obtained, which are also easy to manufacture and simple and inexpensive to pack without great technical effort and which are easy to pack Particularly suitable for long transport and storage times, since no preservatives are required and there is no risk of frost. In addition, they are easy and quick even in hot documents, such as. B. in a hot bitumen melt, can be incorporated. The water-soluble polymers contained in the powdery composition according to the invention are not subject to any particular restriction within the scope of their definition. The only important thing is that they can be easily applied to the carrier materials used according to the invention and, in this carrier-bound form, still develop the desired effect after incorporation into the matrix.

Lignin sulfonates and melamine, naphthalene and / or ketone-formaldehyde condensation products, which are sulfonated for the purpose of water solubility, are known flow agents for inorganic binders and in particular cement-based building materials; but they are also added by building materials to reduce water loss (as so-called "fluidloss additives"), especially when extracting oil.

For the purposes of the present invention, a finely divided mineral carrier material which has a specific surface area of 0.01 to 500 m ² / g (according to BET in accordance with DIN 66 131) and which is selected in particular from the group of calcium carbonate has proven itself as component b) , Dolomite, quartz powder, quartz sand, silica dust, cristoballite, silica, clays, clay minerals, aluminum silicates (such as bentonites, talc, mica, kaolins, slate powder), pumice powder, brick powder, titanium dioxide, clays, barium sulfate, fly ash, blast furnace slag / slag furnace slag , Portland cement, Portland cement with additives (CEM II and CEM III), alumina cements, gypsum, anhydrite, hemihydrate, lime and mixtures of these materials.

The type of these carrier materials is therefore not subject to any particular restriction. It is important that the respective material (mixture) is compatible with the water-soluble polymer, does not have a negative effect on the effect of the polymer and results in powdery, adhesive and packaging-resistant compositions even in small quantities. In addition, the invention also provides for the mineral carrier materials to be used in combination with organic additives such as cellulose powders or fibers and powders or fibers of organic polymers (polyacrylonitrile, polystyrene, etc.).

The finely divided carrier material has a preferred particle size of 0.1 to 1,000 μm.

The invention also relates to a method for producing the powdery composition, which is characterized in that the water-soluble polymer (mixture) is incorporated into the respective mineral carrier material (mixture), which is preferably carried out immediately after the polymerization production process. In this case, the polymer should be introduced into the mineral support material which has been introduced and, if appropriate, preheated, in as finely divided a form as possible, the polymer being incorporated into the mineral carrier material in at least one step in the form of an aqueous solution, which, according to the invention, is also optionally carried out after intermediate drying can.

It is also envisaged that the aqueous solution of the polymer should be dried before the incorporation step (s).

According to a preferred embodiment, the respective water-soluble polymer is sprayed onto a preheated mineral carrier material (for example of the silica type) in the temperature range from 70 to 150 ° C., which should ideally take place in a mixer.

A particularly effective incorporation, which is associated with a very low consumption of mineral carrier material, can be achieved by atomizing the water-soluble polymer onto the preheated carrier material. The effectiveness drops when the polymer sprays onto the carrier material, is dripped or poured because the surface of the substance to be incorporated becomes smaller in the order given.

Of particular interest is also the mixing technique during incorporation, which is very much based on the type of carrier material used.

Carrier materials with a pronounced porous structure, such as. B. silicas have a particularly high adsorption capacity.

Mixers, on the mixing tools of which high shear forces act, can destroy the porous structure, as a result of which the polymers held in the cavities are pressed out again. The present invention therefore recommends using mixing devices with low shear forces such as drum mixers, V mixers, tumble mixers or other representatives from the group of free-fall mixers for this type of carrier.

In addition, cone mixers, ploughshare mixers or spiral mixers with vertically or horizontally arranged mixing tools are also suitable for porous carrier materials. For mineral carriers, the structure of which cannot be disturbed by the mixing process, all other types of apparatus can also be used, such as dissolvers, screw mixers, twin-screw mixers and air-mix mixers.

As already mentioned, the present invention provides for one or more drying processes to be carried out during the incorporation of the polymer into the carrier in order to increase the productivity of the carrier material; however, a drying process is also possible, which follows the actual familiarization steps.

Another object of the invention is the use of at least one powdery composition according to the present invention in building materials, with bitumen products as building materials on hydraulically setting binders such as building materials based on cement or latent hydraulic binders, building materials based on gypsum, anhydrite or other calcium sulfate, ceramic materials, refractory materials and oil field materials. Finally, the compositions according to the invention can also be used in dispersion-based building materials such as dispersion tile adhesive, elastic sealing slurries, primers, mortar additives and in powdery interior and exterior wall paints.

However, the powdery compositions according to the invention can also be used in combination as above. Building material groups are used, e.g. B. in bituminous cementitious screeds, grout etc.

The incorporation of the powdery composition into the building material is usually carried out together with other building material additives and filler mixtures, building material additives in particular being those which are suitable for

Additives such as B. rock flour, pozzolanic and / or latent hydraulic additives, and additives such. B. plastic dispersions, water retention agents, thickeners, retarders, accelerators, air entraining agents, defoamers and wetting agents. According to the invention, the proportion of the composition in the building materials should be 0.05 to 5% by weight, based on the total weight of the building material.

The powdered compositions according to the invention have a number of advantages over compositions obtained in a conventional manner in powder form. This is particularly evident in the likewise claimed building material mixture, which is preferably a dry mixture for flowable mortar, and that a) 10 to 50% by weight of the powdery composition according to claims 1 to 5, b) 20 to 60 % By weight of additives, c) 30 to 70% by weight of additives, d) optionally up to 25% by weight of additives, e) optionally up to 10% by weight of a plastic dispersion and f) optionally up to 25% by weight of an inorganic binder.

The following examples demonstrate the advantages of the present invention.

Examples of invention:

example 1

Dry mix for flowable mortar

01.01:

A finely divided mineral carrier material mixture consisting of 250 g of cement (CEM I 52.5 R, Milke) and 120 g of limestone powder (CalcicoU W 12) was placed in a dissolver and preheated to 40 ° C. Then 20 g of Melment L 17 G as a water-soluble polymer (40% solution, SKW Trostberg AG; corresponding to 3.2% solids based on CEM I) were incorporated at 2,000 rpm and the mixing process was continued at 2,000 rpm for 25 minutes. This gave a dry, free-flowing powdery composition which was processed with 0.5 g of Tylose H 20 P as an additive and 700 g of sand as an additive to form a finished dry mix for flowable mortar. L2.

A finely divided mineral carrier material mixture consisting of 250 g cement (CEM I 52.5 R, Milke) and 120 g limestone powder (CalcicoU W 12) and 700 g sand as an additive were preheated to 45 ° C and placed in a tumble mixer (Bachofen AG, Basel). 32 g of Melment L 10 as a water-soluble polymer (25% strength aqueous solution, SKW Trostberg AG; corresponding to 3.2% solids based on CEM I) were then metered into this mixture and the mixing process continued for 75 minutes. The dry, free-flowing mixture obtained in this way was treated with 15 g of plastic dispersion powder.

Example 2

Standard mortar mix

450 g of cement (CEM I 42.5 R, manufactured by Schwenk) as the carrier material were placed in a dissolver and at 2,000 rpm with 22.5 g of Melment L 17 G as a water-soluble polymer (40% aqueous solution, SKW Trostberg AG; corresponding to 2.0% solids based on CEM I). The mixing process, which was continued for 25 minutes at 2,000 rpm, gave a dry, free-flowing powdery composition, to which 1,350 g of standard sand were finally mixed.

Comparative Examples

Example 1 Dry mortar mixture consisting of: 250 g CEM I 52.5 R, Milke 120 g limestone powder (CalcicoU W 12) 700 g sand 8 g Melment F 17 G (corresponds to 3.2% based on CEM I) 0.5 g Tylose H 20 P Example 2

Dry mortar mixture consisting of: 250 g CEM I 52.5 R, Milke 120 g limestone powder (CalcicoU W 12) 700 g sand 8 g Melment F 10 (corresponds to 3.2% based on CEM I) 15 g plastic dispersion powder Example 3

Standard mortar mixture according to EN-196 consisting of: 450 g CEM I 42.5 R, from Schwenk 1350 g standard sand 9 g Melment F 17 G (corresponds to 2.0% based on CEM I)

Findings:

The dry mixtures according to the invention for flowable mortars (inventive examples 1.1 and 1.2) and the standard mortar mixture (inventive example 2) and comparative examples 1 to 3 were examined for their application properties. For this purpose, a flow rate was determined for dry mortar mixes based on the UEATC (French standard) and for the standard mortar mixes (inventive example 2 and comparative example 3) the slump according to EN-196:

W / Z = 0.61

^{* 1} W / Z = 0.39 (slump without flow agent 15.5 cm at W / Z = 0.5)

Claims

Expectations

1. Powdery composition based on water-soluble polymers, characterized in that it a) 5 to 95 wt .-% of a water-soluble polymer consisting of sulfonates of lignin and / or sulfonated melamine, naphthalene and / or ketone formaldehyde Condensation products is built up, and b) contains 5 to 95 wt .-% of a finely divided mineral carrier material.

2. Composition according to claim 1, characterized in that the finely divided mineral carrier material has a specific surface area of 0.01 to 500 m ² / g (according to BET according to DIN 66 131).

3. Composition according to claim 1 or 2, characterized in that the carrier material is selected from the group calcium carbonate, dolomite, quartz powder, quartz sand, silica fume,

Cristoballite, silica, clays, clay minerals, aluminum silicates (such as bentonite, talc, mica, kaolins, slate flour), pumice, brick flour, titanium dioxide, clays, barium sulfate, fly ash, blast furnace slag / blast furnace slag, Portland cement, Portland cement with additives (CEM II and CEM III), alumina cements, gypsum, anhydrite,

Hemihydrate, lime and mixtures of these materials.

4. Composition according to one of claims 1 to 3, characterized in that the mineral carrier material in combination with organic additives such as cellulose powder or fibers and

Powders or fibers of organic polymers are used.

5. Composition according to one of claims 1 to 4, characterized in that the carrier material has an average particle size of 0.1 to 1000 / m.

6. The method for producing the composition according to one of claims 1 to 5, characterized in that the water-soluble polymer, preferably immediately after the polymerization production process, is introduced into the mineral carrier material.

7. The method according to claim 6, characterized in that the polymer in the form of an aqueous solution in at least one step, optionally after intermediate drying, is incorporated into the mineral carrier material.

8. The method according to claim 7, characterized in that the aqueous solution of the polymer is dried before the incorporation step (s).

9. The method according to any one of claims 6 to 8, characterized in that the water-soluble polymer is sprayed onto a preheated mineral carrier material at 70 to 150 ° C.

10. The method according to any one of claims 6 to 9, characterized in that one with a carrier material with a porous structure mixer with low shear forces, such as. B. Free fall mixer.

11. Use of a composition according to any one of claims 1 to 5 in building materials, in an amount of 0.05 to 5 wt .-% of polymer based on the total weight of the building material.

12. Use according to claim 11, characterized in that as building materials bitumen products, building materials based on hydraulically setting binders such as cement or latent hydraulic binders, gypsum, anhydrite or other calcium sulfate-based building materials, ceramic materials, refractory materials,

Oilfield building materials and dispersion-based building materials or mixtures thereof.

13. Use according to one of claims 11 and 12, characterized in that the powdery composition is combined with other building material additives and filler mixtures.

14. Use according to claim 13, characterized in that the other building material additives from additives such. B. rock flour, pozzolanic and / or latent hydraulic additives, and

Additives such as B. plastic dispersions, water retention agents, thickeners, retarders, accelerators, air entraining agents, defoamers and wetting agents.

15. Building material mixture, preferably dry mixture for flowable mortar, containing a) 10 to 50 wt .-% of the powdery composition according to one of claims 1 to 5, b) 20 to 60 wt .-% of additives, c) 30 to 70 wt. % of additives, d) optionally up to 25% by weight of additives, e) optionally up to 10% by weight of a plastic dispersion and f) optionally up to 25% by weight of an inorganic binder.