EP3497069A1

EP3497069A1 - Dispersant composition for inorganic solid suspensions

Info

Publication number: EP3497069A1
Application number: EP17751071.6A
Authority: EP
Inventors: Torben Gaedt; Joachim Dengler; Oliver Mazanec
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-08-11
Filing date: 2017-08-04
Publication date: 2019-06-19
Also published as: RU2019106269A; US20200317905A1; RU2741290C2; WO2018029095A1; CN109562996A; RU2019106269A3

Abstract

The invention relates to a composition in the form of a solid, which composition is suitable as a dispersant for inorganic solid suspensions, comprising A) at least one water-soluble polymer, comprising polyether groups, and B) at least one water-soluble condensation product, which contains acid groups and/or salts thereof and which is based on monomers, wherein the monomers comprise at least α) a monomer having a ketone residue and β) formaldehyde. The invention further relates to a method for producing the composition according to the invention and to the use of the composition according to the invention in an inorganic binder composition.

Description

Dispersant composition for inorganic solid suspensions

The invention relates to a composition in the form of a solid, which is suitable as a dispersant for inorganic solid suspensions. Further disclosed is a process for preparing the composition and its use in an inorganic binder composition.

To improve processability, i. H. Kneadability, spreadability, sprayability, pumpability or flowability to achieve inorganic solid suspensions are often added to these additives in the form of dispersants or flow agents.

Such inorganic solids in the construction industry mostly comprise inorganic binders such as e.g. Cement based on Portland cement (EN 197), cement with special properties (DIN 1 164), white cement, calcium aluminate cement or

Alumina cement (EN 14647), calcium sulphoaluminate cement, special cements, calcium sulphate n-hydrate (n = 0 to 2), lime or building lime (EN 459) as well as pozzolans or latently hydraulic binders such as eg. As fly ash, metakaolin, silica fume, blastfurnace slag. Furthermore, the inorganic solid suspensions usually contain fillers, in particular aggregate consisting of z. As calcium carbonate, quartz or other natural rocks of various particle size and grain shape and other inorganic and / or organic additives (additives) for the targeted influence of properties of construction chemicals z. As hydration kinetics, rheology or air content. In addition, organic binders such. B. latex powder may be included.

In order to convert building material mixtures, in particular based on inorganic binders into a ready-to-use, processable form, substantially more mixing water is generally required than would be necessary for the subsequent hydration or hardening process. The void fraction in the structure formed by the excess, later evaporating water leads to a significantly deteriorated mechanical strength, durability and durability.

In order to reduce this excess water content at a given processing consistency and / or to improve processability at a given water / binder ratio, additives generally referred to in construction chemicals as water reducers or superplasticizers are used. As such agents, especially polycondensation products based on naphthalene or alkylnaphthalenesulfonic acids or sulfonic acid groups containing melamine formaldehyde resins are known.

DE 3530258 describes the use of water-soluble sodium naphthalenesulfonic acid-formaldehyde condensates as additives for inorganic binders and Building materials. These additives are used to improve the flowability of the binder such. As cement, anhydrite or gypsum and the building materials produced therewith. DE 2948698 describes hydraulic mortars for screeds which contain superplasticizers based on melamine-formaldehyde condensation products and / or sulfonated formaldehyde naphthalene condensates and / or lignin sulfonate and, as binders, Portland cement, clay-containing limestone marl, clay and weak clinker brick. In addition to the purely anionic flow agents, which essentially contain carboxylic acid and sulfonic acid groups, the newer group of flow agents are weakly anionic comb polymers which usually carry anionic charges on the main chain and contain nonionic polyalkylene oxide side chains. WO 01/96007 describes these weakly anionic flow and grinding auxiliaries for aqueous mineral suspensions which are prepared by free-radical polymerization of vinyl group-containing monomers and which contain polyalkylene oxide groups as a main component. DE 19513126 and DE 19834173 describe copolymers based on unsaturated dicarboxylic acid derivatives and oxyalkylene glycol alkenyl ethers and their use as additives for hydraulic binders, in particular cement.

The aim of adding flow agents in the construction industry is either to increase the plasticity of the binder system or to reduce the amount of water required under the same processing conditions.

It has been found that superplasticizers based on lignosulfonate, melamine sulfonate and polynaphthalenesulfonate are clearly inferior in their effectiveness to the weakly anionic polyalkylene oxide-containing copolymers. These copolymers are also referred to as polycarboxylate ethers (PCE). Polycarboxylate ethers not only disperse the inorganic particles by electrostatic charging due to the anionic groups (carboxylate groups, sulfonate groups) contained on the main chain, but additionally stabilize the dispersed particles by steric effects due to the polyalkylene oxide side chains which, by absorbing water molecules, form a stabilizing protective layer around the particles form.

As a result, either the required amount of water for setting a certain consistency compared to the conventional flow agents can be reduced or the plasticity of the wet building material mixture is reduced by the addition of polycarboxylate so far that self-compacting concrete or self-compacting mortar produced at low water / cement ratios can be. Also possible the use of the polycarboxylate ethers to produce ready-mixed concrete or transport mortar that remains pumpable for extended periods of time or to produce high strength concretes or high strength mortars by setting a low water / cement ratio.

In addition to the described polycarboxylate ethers, a number of derivatives with a modified activity profile are now known. For example, US 2009312460 describes polycarboxylate esters wherein the ester function is hydrolyzed after incorporation into a cementitious, aqueous mixture to form a polycarboxylate ether. Polycarboxylate esters have the advantage that they develop their effect only after some time in the cementitious mixture and thus the dispersing effect can be maintained over a longer period.

Dispersants based on polycarboxylate ethers and derivatives thereof are available either as a solid in powder form or as an aqueous solution. Powdered polycarboxylate ethers may, for example, be added to a dry mortar during its production. When mixing the dry mortar with water, the polycarboxylate ethers dissolve and can subsequently exert their effect. DE 199 05 488 discloses powdered polymer compositions based on polyether carboxylates, these comprising from 5 to 95% by weight of the water-soluble polymer and from 5 to 95% by weight of a finely divided mineral carrier material. The products are made by contacting the mineral support material with a melt or an aqueous solution of the polymer. The advantages of this product compared to spray-dried products, a significantly increased adhesion and caking resistance called.

Due to their physical properties, many polymeric dispersants are difficult to convert into powder form and are therefore offered in the form of their aqueous solution. For many applications, such as dry mortar, but it is essential to provide dispersants in solid form. In general, therefore, there was a need to provide a dispersant in solid form, which does not lead to a delay in the setting of the inorganic binder. WO 2013/020862 discloses a process for preparing a solid dispersant for a hydraulically setting composition, wherein a comb polymer comprising carboxyl groups and at least one second polymer selected from a condensate of an aromatic compound and formaldehyde or lignosulfonate are spray-dried together in the form of an aqueous composition , However, the dispersants thus obtained have the disadvantage that they lead to a delay in the setting process in the hydraulically setting compositions. Spray drying, also called atomization drying, is a process for drying solutions, suspensions or pasty masses. By means of a nozzle, which is usually operated by the liquid pressure, compressed air or inert gas or rotating atomizing disks (4,000-50,000 revolutions / min), the material to be dried is introduced into a hot air stream, which dries it to a fine powder in a very short time. Depending on the design or intended use, it is possible that the hot air flows in the direction of the spray jet, ie according to the direct current principle or against the spray jet, ie according to the countercurrent principle. The spraying device is preferably located at the upper part of a spray tower. The resulting dry material is separated in this case in particular by a cyclone separator from the air flow and can be removed there. It is also known to operate spray drier continuously or discontinuously.

It was therefore an object of the present invention to provide a dispersant in the form of a solid, which has very good powder properties, and these properties should be retained, in particular under thermal and mechanical stress. At the same time, the dispersant should avoid the disadvantages of the prior art, in particular delay the setting of the inorganic binder and have improved metering efficiency. This object has been achieved by a composition in the form of a solid, which is suitable as a dispersant for inorganic solid suspensions comprising

A) at least one water-soluble polymer comprising polyether groups and

B) at least one acid groups and / or salts thereof containing water-soluble condensation product based on monomers, wherein the monomers at least a) a monomer having a ketone radical and

ß) formaldehyde.

Surprisingly, it has been found that not only could the stated problem be solved in its entirety, but that the composition according to the invention has excellent application properties both in hydraulic binder compositions comprising, for example, Portland cement and in non-hydraulic binder compositions comprising, for example, gypsum.

The water-soluble polymers A) according to the invention, comprising polyether groups, preferably contain at least two monomer building blocks. However, it may also be advantageous to use copolymers with three or more monomer units. The water-soluble polymer A) according to the invention particularly preferably comprises at least one group from the series carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy groups. Most preferably, the polymer of the invention comprises an acid group. In the present application, the term "acid group" is understood as meaning both the free acid and its salts, and the acid may preferably be at least one of the series carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy In a further particularly preferred embodiment, the water-soluble polymer A) according to the invention comprises at least one carboxyester group, in particular a hydroxyalkyl ester The hydroxyalkyl ester preferably comprises 1 to 6, preferably 2 to 4, C atoms. "Water-soluble polymers" in the context of the present application are polymers which in water at 20 ° C. and normal pressure have a solubility of at least 1 gram per liter, in particular at least 10 grams per liter and more preferably at least 100 grams per liter. In a preferred embodiment, the polyether groups of the at least one water-soluble polymer A) are polyether groups of the structural unit (I),

^* -U- (C (0)) _k -X- (AlkO) nW (I) where

^* indicates the binding site to the polymer,

U is a chemical bond or an alkylene group with 1 to 8 carbon atoms

stands,

X represents oxygen, sulfur or a group NR ¹ ,

k is 0 or 1,

n is an integer whose average value, based on the polymer, is in the range from 3 to 300,

Alk is C ₂ -C ₄ -alkylene, where Alk within the group (Alk-0) _{n may be} identical or different,

W is a hydrogen, a C 1 -C 6 -alkyl or an aryl radical or

the group Y-F means, where

Y is a linear or branched alkylene group having 2 to 8 C atoms,

who can wear a phenyl ring,

F stands for a nitrogen-bonded 5- to 10-membered nitrogen heterocycle, which as ring members, next to the nitrogen atom and next

Carbon atoms, 1, 2 or 3 additional heteroatoms selected from May have oxygen, nitrogen and sulfur, wherein the nitrogen ring members may have a group R ² , and wherein 1 or 2 carbon ring members may be present as a carbonyl group,

R ^{1 is} hydrogen, C ¹ -C ⁴ -alkyl or benzyl, and

R ^{2 is} hydrogen, Ci-C ₄ alkyl or benzyl.

With regard to the present invention, it has proven to be particularly advantageous for structural unit (I) for n to have a value of from 5 to 135, in particular from 10 to 70 and particularly preferably from 15 to 50.

In a particularly preferred embodiment, the water-soluble polymer A) comprising polyether groups is a polycondensation product containing

(II) a structural unit having an aromatic or heteroaromatic group and the polyether group, and

(III) a phosphated an aromatic or heteroaromatic containing structural unit.

The structural units (II) and (III) are preferably represented by the following general formulas

(Ii) AU- (C (0)) _k -X- (AlkO) nW with

A is the same or different and is represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms in the aromatic system, the other radicals having the meaning given for structural unit (I);

With

D is identical or different and represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms in the aromatic system.

Further, E is the same or different and represented by N, NH or O, m = 2 if E = N and m = 1 if E = NH or O. R ³ and R ⁴ are each independently the same or different and represented by a branched or unbranched C 1 to C 10 alkyl radical, C 5 to C 8 cycloalkyl radical, aryl radical, heteroaryl radical or H, preferably by H, methyl, ethyl or phenyl, more preferably by H or methyl, and more preferably by H. Further, b is the same or different and represented by an integer of 0 to 300. If b = 0, E = O. More preferably, D = phenyl, E = O, R ³ and R ⁴ = H and b = 1.

The polycondensation product preferably contains a further structural unit (IV), which is represented by the following formula

With

Y are independently the same or different and represented by (II), (III) or the other constituents of the polycondensation product. R ⁵ and R ⁶ are the same or different and represented by H, CH 3, COOH or a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms. Here, R ⁵ and R ⁶ in structural unit (IV) independently of one another are preferably represented by H, COOH and / or methyl.

In a particularly preferred embodiment, R ⁵ and R ⁶ are represented by H.

The molar ratio of the structural units (II), (III) and (IV) of the phosphated polycondensation product according to the invention can be varied within wide limits. It has proved to be advantageous that the molar ratio of the structural units [(II) + (III)]: (IV) 1: 0.8 to 3, preferably 1: 0.9 to 2 and particularly preferably 1: 0.95 to 1, 2 is.

The molar ratio of the structural units (II): (III) is normally from 1:10 to 10: 1, preferably from 1: 7 to 5: 1 and more preferably from 1: 5 to 3: 1.

The groups A and D in the structural units (II) and (III) of the polycondensation product are usually replaced by phenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, naphthyl, 2-hydroxynaphthyl, 4-hydroxynaphthyl, 2-methoxynaphthyl, 4-methoxynaphthyl preferably represents phenyl, where A and D can be selected independently of one another and can also each consist of a mixture of the compounds mentioned. The groups X and E are independently represented by O, preferably. N in structural unit (I) is preferably represented by an integer from 5 to 280, in particular 10 to 160 and particularly preferably 12 to 120 and b in structural unit (III) by an integer from 0 to 10, preferably 1 to 7 and especially preferably 1 to 5. The respective radicals, the length of which is defined by n or b, can in this case consist of uniform assemblies, but it may also be expedient that they are a mixture of different assemblies. Furthermore, the radicals of the structural units (II) and (III) may each independently have the same chain length, n or b being each represented by a number. However, it will generally be expedient that they are each mixtures with different chain lengths, so that the radicals of the structural units in the polycondensation product have n and independently of b different numerical values. In a particular embodiment, the present invention further provides that it is a sodium, potassium, ammonium and / or calcium salt, and preferably a sodium and / or potassium salt, of the phosphated polycondensation product. Frequently, the phosphated polycondensation product according to the invention has a weight average molecular weight of 5000 g / mol to 150,000 g / mol, preferably 10,000 to 100,000 g / mol and particularly preferably 20,000 to 75,000 g / mol.

With regard to the phosphatized polycondensation products to be preferably used according to the present invention and their preparation, further reference is made to the patent applications WO 2006/042709 and WO 2010/040612, the content of which is hereby incorporated into the application.

In a further preferred embodiment, the water-soluble polymer A) is at least one copolymer which is obtainable by polymerization of a mixture of monomers comprising

(V) at least one ethylenically unsaturated monomer which is at least

a radical from the series carboxylic acid, carboxylic acid salt,

Carboxylic acid ester, carboxylic acid amide, carboxylic anhydride and

Carboxylic imide includes

and

(VI) at least one ethylenically unsaturated monomer comprising the

Polyether group, wherein the polyether group preferably by

the structural unit (I) is represented. The copolymers according to the present invention contain at least two monomer building blocks. However, it may also be advantageous to use copolymers with three or more monomer units.

In a preferred embodiment, the ethylenically unsaturated monomer (V) is represented by at least one of the following general formulas from the group (Va), (Vb) and (Vc):

In the mono- or dicarboxylic acid derivative (Va) and the cyclic monomer (Vb), wherein Z = O (acid anhydride) or NR ¹⁶ (acid imide), R ⁷ and R ^{8 are} independently hydrogen or aliphatic Hydrocarbon radical having 1 to 20 carbon atoms, preferably a methyl group. B is H, -COOM _a , -CO-O (C _q H _2q O) _r -R ⁹ , -CO-NH- (C _q H _2q O) _r R ⁹ .

M is hydrogen, a mono-, di- or trivalent metal cation, preferably sodium, potassium, calcium or magnesium ion, furthermore ammonium or an organic amine radical and a = 1/3, 1/2 or 1, as the case may be, whether M is a monovalent, divalent or trivalent cation. Substituted ammonium groups which are derived from primary, secondary or tertiary C 1-20 -alkylamines, C 1-20 -alkanolamines, C 3-5 -cycloalkylamines and C 6-14 -arylamines are preferably used as organic amine radicals. Examples of the corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form.

R ⁹ is hydrogen, an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an aryl radical having 6 to 14 C atoms, which may possibly be substituted, q = 2, 3 or 4 and r = 0 to 200, preferably 1 to 150. The aliphatic hydrocarbons here may be linear or branched and saturated or unsaturated. Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, and the preferred aryl radicals are phenyl or naphthyl radicals, which may in particular be substituted by hydroxyl, carboxyl or sulfonic acid groups.

Furthermore, Z is O or NR ¹⁶ , where R ^{16 is} independently the same or different and is represented by a branched or unbranched C 1 to C 10 alkyl radical, C 8 to C 8 cycloalkyl radical, aryl radical, heteroaryl radical or H. The following formula represents the monomer (Vc):

Q

12

R (Vc) Here R ¹⁰ and R ¹¹ 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, an optionally substituted aryl radical having 6 to 14 C atoms , Furthermore, R ^{12 is} identical or different and is replaced by (C _n H 2n) -SO 3 H with n = 0, 1, 2, 3 or 4, (C _n H ₂ n) -OH where n = 0, 1, 2, 3 or 4; (CnH ₂ n) -P0 ₃ H2 with n = 0, 1, 2, 3 or 4, (CnH ₂ n) -OPO ₃ H2 with n = 0, 1, 2, 3 or 4, (C ₆ H ₄ ) -S0 ₃ H, (C ₆ H ₄ ) -PO ₃ H ₂ , (C ₆ H ₄ ) -OPO ₃ H ₂ and (C _n H 2n) -NR ¹⁴ b with n = 0, 1, 2, 3 or 4 and b is represented by 2 or 3. R ¹³ is H, -COOM _a , -CO-O (C _q H _2q O) _r -R ⁹ , -CO-NH- (C _q H _2q O) _r R ⁹ , where M _a , R ⁹ , q and r have the meanings mentioned above.

R ¹⁴ is hydrogen, an aliphatic hydrocarbon radical having 1 to 10 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms, an optionally substituted aryl radical having 6 to 14 C atoms.

Furthermore, Q is identical or different and is represented by NH, NR ¹⁵ or O, where R ^{15 is} 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 6 to 14 carbon atoms.

In a particularly preferred embodiment, the ethylenically unsaturated monomer (VI) is represented by the following general formulas (VI)

s

RR ⁷

\

C C

\

H U- (C (OJ) ir -X- (AlkO) _n -W

wherein all radicals have the abovementioned meanings. In particular, the copolymer has an average molecular weight (Mw) between 5000 and 150,000 g / mol, more preferably 10,000 to 80,000 g / mol, and most preferably 15,000 to 60,000 g / mol, which is determined by gel permeation chromatography.

The polymers are analyzed by size exclusion chromatography for average molecular weight and conversion (column combinations: Shodex OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Showa Denko, Japan; Eluant: 80% by volume aqueous solution of HCO ₂ NH ₄ (0 , 05 mol / l) and 20 vol .-% MeOH, injection volume 100 μΙ, flow rate 0.5 ml / min)).

The copolymer according to the invention preferably meets the requirements of the industrial standard EN 934-2 (February 2002). Furthermore, the composition according to the invention comprises at least one water-soluble condensation product B) based on monomers, which contains at least one acid group and / or salt thereof

a) a monomer with a ketone radical and

ß) formaldehyde.

The acid groups of the condensation product B) are particularly preferably at least one from the series carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy group and / or their salts, which also is designated as structural unit γ).

In a preferred embodiment, the condensation product B) has a monomer ratio of the monomers a) to β) of 1 to 2 to 3. Particularly preferably, the condensation product B) has a ratio of the monomers a) to ß) to structural unit γ) of 1 to 2 to 3 to 0.33 to 1.

The monomer having a ketone residue a) of the condensation product B) is preferably at least one ketone from the series 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-methoxy-acetophenone, 4-acetylbenzenesulfonic acid, diacetyl, acetylacetone, benzoylacetone and cyclohexanone. Especially preferred are cyclohexanone and acetone.

In a preferred embodiment, the composition according to the invention comprises 5 to 95% by weight, preferably 25 to 60% by weight and particularly preferably 30 to 50% by weight of A) of the at least one water-soluble polymer comprising polyether groups and 5 to 95 Wt .-%, preferably 40 to 75 wt .-% and particularly preferably 50 to 70 wt .-% B) of the at least one acid group and / or salts thereof containing water-soluble condensation product.

The condensation product B) according to the invention comprises as monomer a) in particular cyclohexanone or acetone or a mixture thereof. As the monomer β), in particular formaldehyde is to be regarded as particularly preferred. With regard to the acid groups of the condensation product B), these can preferably be introduced by sulfite. The condensation product B) according to the invention is particularly preferably prepared from cyclohexanone, formaldehyde and sulfite. It should also be mentioned that the condensation product B) according to the invention does not comprise any polyether groups.

In particular, the condensation product B) has an average molecular weight (Mw) between 10,000 and 40,000 g / mol, in particular between 15,000 and 25,000 g / mol, which is determined by size exclusion chromatography, the measurement according to Section 2.3 of the publication " Cement and Concrete Research ", Volume 42, Issue 1, January 2012, page 1 18 to 123 (" Synthesis, working mechanism and effectiveness of a novel cycloaliphatic superplasticizer for concrete ", L. Lei, J. Plank).

With regard to the condensation product B) to be used in accordance with the present invention and its preparation, reference is made to patent applications DE 2341923, in particular page 3, last paragraph to page 5, third paragraph and page 7, example 1 A), the content of which is hereby incorporated into the application is recorded.

In particular, reference will be made to the patent applications EP 0163459, in particular page 7, last paragraph to page 9, second paragraph, the content of which is hereby incorporated into the application with respect to the preferred condensation product B) to be used according to the present invention.

In a further embodiment, with respect to the condensation product B) preferably to be used according to the present invention and its preparation, reference may be made to the publication "Cement and Concrete Research", Volume 42, Issue 1, January 2012, page 1 18 to 123 ("Synthesis, working mechanism and effectiveness of a novel cycloaliphatic superplasticizer for concrete ", L. Lei, J. Plank), in particular Sections 2.3 to 2.4 and 3.1, the content of which is hereby incorporated into the application.

A further subject of the present invention is a process for producing a composition according to the invention, the process comprising the following steps:

a) providing a water-soluble polymer A),

b) providing a water-soluble condensation product B),

c) Preparation of an aqueous mixture comprising at least one water-soluble polymer A), and the water-soluble condensation product B), d) spray-drying the aqueous mixture to obtain a solid.

In principle, all conventional spray-drying devices are suitable for carrying out the process according to the invention.

Suitable spray nozzles are single-fluid nozzles and multichannel nozzles such as two-component nozzles, three-channel nozzles or four-channel nozzles. Such nozzles may also be designed as so-called "ultrasonic nozzles." Such nozzles are commercially available.

Furthermore, depending on the type of nozzle and a sputtering gas can be supplied. As a sputtering gas, air or an inert gas such as nitrogen or argon can be used. The gas pressure of the atomizing gas may preferably be up to 1 MPa absolute, preferably 0.12 to 0.5 MPa absolute.

In a preferred embodiment, the preparation of the aqueous mixture comprising the at least one water-soluble polymer comprising polyether groups and the water-soluble condensation product B) is carried out before the spray-drying step d). In this case, the aqueous mixture used according to the invention is preferably prepared by mixing an aqueous solution of the polymer A) with an aqueous solution of the condensation product B).

According to a further embodiment, special nozzles are also suitable in which different liquid phases within the nozzle body are mixed and then atomized. In this case, an aqueous solution or an aqueous suspension comprising the at least one water-soluble polymer comprising polyether groups, hereinafter also referred to as component A), and an aqueous solution or an aqueous suspension comprising the water-soluble condensation product B), hereinafter also as a component B), the nozzle are first fed separately and then mixed together within the nozzle head.

An embodiment of the invention relates to ultrasonic nozzles. Ultrasonic nozzles can be operated with or without atomizing gas. In ultrasonic nozzles, the atomization takes place by causing the phase to be atomized to vibrate. Depending on the nozzle size and design, the ultrasonic nozzles can be operated with a frequency of 16 to 120 kHz.

The throughput of liquid phase to be sprayed per nozzle depends on the nozzle size. The throughput can be 500 g / h to 1000 kg / h solution or suspension. In the production of commercial quantities, the throughput is preferably in the range of 10 to 1000 kg / h. If no atomizing gas is used, the liquid pressure may be 0.2 to 40 MPa absolute. If an atomizing gas is used, the liquid can be fed without pressure.

Further, the spray drying apparatus is supplied with a drying gas such as air or one of the inert gases mentioned. The drying gas can be supplied in cocurrent or countercurrent to the sprayed liquid, preferably in cocurrent. The inlet temperature of the drying gas may be 120 to 300 ° C, preferably 150 to 230 ° C, the outlet temperature 60 to 135 ° C.

As already mentioned, the magnitudes of the spray parameters to be used, such as throughput, gas pressure or nozzle diameter, depend decisively on the size of the devices. The devices are commercially available and usually the manufacturer recommends corresponding orders of magnitude.

According to the invention, the spraying process is preferably operated such that the average droplet size of the sprayed phases is 5 to 2,000 μm, preferably 5 to 500 μm, particularly preferably 5 to 200 μm. The mean droplet size can be determined by laser diffraction or high-speed cameras coupled with an image analysis.

The above embodiments of the spraying method can be applied to all of the preferred and particularly preferred embodiments described below. Preferred spray parameters are also preferred in connection with the following embodiments.

A particular embodiment is a method in which the spray nozzle is a multi-channel nozzle. In an alternative embodiment, the spraying of the components takes place through a multi-channel nozzle, wherein the components are brought into contact with one another at the outlet of the spray nozzle.

Preferably, the multi-channel nozzle may be a three-channel nozzle or a two-channel nozzle. In the case of the three-channel nozzle, one of the three channels preferably uses a sputtering gas, more preferably air or nitrogen, the other two channels are for component A) or component B). In the case of a two-channel nozzle, the required atomization of the two components A) and B) is achieved either by the use of ultrasound or by the use of a centrifugal force nozzle. The use of a three-channel nozzle with a channel for the atomizing gas and two channels for the components A) and B) is preferred. The channels for the components A) and B) are separated both in the case of a two-channel nozzle, as well as a three-channel nozzle to avoid premature mixing of the components. The components A) and B) are brought into contact only at the outlet of the two channels for the components A) and B) of the spray nozzle. The nebulizer gas causes the formation of fine droplets, in particular in the form of a mist, from the components A) and B) which have been brought into contact with one another.

However, preference is given to a method in which the multichannel nozzle has two channels, the component A) and the component B) first being premixed with one another and then fed to the two-channel nozzle, the drying gas being introduced via the second channel.

In a further preferred embodiment of the invention, the aqueous mixture, prior to spray-drying, comprises 1 to 55% by weight, preferably 5 to 40% by weight and more preferably 15 to 25% by weight of the water-soluble polymer comprising polyether groups and 1 to 55 wt .-%, preferably 5 to 40 wt .-% and particularly preferably 25 to 35 wt .-% of the water-soluble condensation product B) and 20 to 80 wt .-%, preferably 35 to 75 wt .-% water ,

In the context of the present invention, it is preferred if the aqueous mixture in process step c) is prepared and preheated before it enters the spray dryer. In an alternative embodiment, components A) and B) may also be preheated independently prior to entering the spray dryer. The inlet temperature of component A) and independently thereof component B) or the inlet temperature of the mixture in the spray dryer may be between 50 and 200 ° C, preferably between 70 and 130 ° C. The resulting powdery solid may then be sieved to remove agglomerates. In a preferred embodiment, the solid obtained by the process according to the invention is obtained in the form of a dry powder having good flowability. However, the powder can also be converted, for example, by pressure into another solid form. Furthermore, it is possible to granulate the powders obtained by the usual methods. Thus, the process of the invention also includes solid compositions in the form of pellets or granules. The process according to the invention thus preferably provides that the solid obtained after spray-drying is present as powder or granules.

The aqueous mixture used in the process according to the invention may also contain further additives. In an alternative embodiment, components A) and B) may independently contain further additives. These may in particular be stabilizers or by-products from the manufacturing process. Furthermore, in particular antioxidants can be added as additives. The solid obtained by the process according to the invention, after incorporation into water (50% by weight mixture), preferably has a pH of between 2 and 9, preferably between 3.5 and 6.5. In a specific embodiment, it is also possible to adjust the pH of the aqueous mixtures used according to the invention before the spray-drying by adding an acid or a base.

Furthermore, the present invention provides for the use of the dispersant obtained by the process of the invention in an inorganic binder composition.

The inorganic binder is preferably at least one of the series based on Portland cement, white cement, calcium aluminate cement, calcium sulfoaluminate cement, calcium sulfate n-hydrate and latently hydraulic or pozzolanic binder.

The binder composition is preferably a dry mortar. The constant pursuit of extensive rationalization and improved product quality has meant that in the construction sector mortar for a variety of applications today is virtually no longer mixed together on the construction site itself from the starting materials. Today, this task is largely taken over by the building materials industry at the factory and the ready-mixed mixtures are provided as so-called dry mortar. In this case, finished mixtures, which are made on the construction site exclusively by the addition of water and Durchmi- seen processable, according to DIN 18557 referred to as work mortar, especially as dry mortar. Such mortar systems can fulfill a wide variety of building physics tasks. Depending on the task, the binder, which may contain, for example, cement and / or lime and / or calcium sulfate, further additives or additives are added to adjust the dry mortar to the specific application.

The dry mortar according to the invention may, in particular, be masonry mortar, plaster, mortar for thermal insulation composite systems, rendering plasters, joint mortar, tile adhesives, thin-bed mortar, screed mortar, grout, grout, leveling compounds, sealing slurries or lining mortar (eg for drinking water pipes).

Also included are factory mortars, which can be provided with other components, in particular liquid and / or powdery additives and / or with aggregate in the production on the site except with water (two-component systems). In the case of the binder composition according to the invention, which comprises at least one inorganic binder, the binder may in particular also be a binder mixture. In the present context, these are understood as meaning mixtures of at least two binders from the series cement, pozzolanic and / or latent hydraulic binder, white cement, special cement, calcium aluminate cement, calcium sulfoaluminate cement and the various hydrous and anhydrous calcium sulfates. These may possibly contain further additives. The following examples are intended to explain the invention in more detail.

Examples

Preparation of the polymers The acetone resin was prepared in accordance with polymer 6 of W015039890 (see Table 1 on page 13 i.V.m. page 15, specification C))

The cyclohexanone resin was prepared according to Polymer 14 of W015039890 (see Table 1 on page 13, i.V., page 15, Specification B)) Polymer A is a copolymer of ethoxylated vinyloxybutanol with a chain length of 23 ethylene oxide units and acrylic acid. The copolymer was prepared as follows: A glass reactor equipped with several feeds, 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 heated to 13 ° C. To this was added 0.01 g of ferrous sulfate heptahydrate and 5.5 g of Brxgolit FF6. Subsequently, 57.9 g of acrylic acid and 5 g of 30% hydrogen peroxide solution were added. The reaction mixture was stirred for 0.5 h at 25 to 35 ° C. It was then neutralized with sodium hydroxide solution to pH = 5. The molecular weight determined by GPC is 22,000 g / mol.

Polymer B is a copolymer of hydroxyethyl acrylate and ethoxylated isoprenol with 23 ethylene oxide units (EO). The copolymer was prepared as follows: A glass reactor was equipped with a stirrer, pH meter and metering units and filled with 267 g of water. 330 g of the molten ethoxylated isoprenol were mixed with the water. The temperature was adjusted to 13 ° C, the pH by adding 25% sulfuric acid to about 7. To this was added 4 mg of iron (II) sulfate heptahydrate, 8.25 g of mercaptoethanol and 3.2 g of hydrogen peroxide. Subsequently, a solution of 200 g of water and 136 g of hydroxyethyl acrylate and 5 g of Brüggolit E01 and 32 g of water was added over a period of 20 minutes. During the reaction, the pH was kept at pH = 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.

Polymer C is a copolymer of methacrylic acid and methyl polyethylene glycol methacrylate ester with 23 ethylene oxide units (EO). The polymer was prepared as follows: 330 g of the methacrylic ester 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 h. The resulting polymer was mixed with 500 ml of water and then neutralized with 50% sodium hydroxide solution to pH = 7. The molecular weight of the resulting polymer was 28,000 g / mol. The auxiliary polymer was prepared analogously to page 18, Synthesis Example 1 of WO 03/097721.

The lignosulfonate used was a commercially available lignosulfonate Bretax from Burgos.

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

The molecular weight was determined by means of gel permeation chromatography (GPC) using the following method: Column combination: Shodex OH-Pak SB 804 HQ and OH-Pak SB 802.5 HQ from Showa Denko, Japan; Eluent: 80% by volume aqueous solution of HCO 2 NH 4 (0.05 mol / L) and 20% by volume MeOH; Injection volume 100 μΙ; Flow rate 0.5 ml / min). The calibration of the molecular weight was carried out with standards from PSS Polymer Standard Service, Germany. Poly (styrene sulfonate) standards were used for the UV detector, and poly (ethylene oxide) standards were used for the RI detector. To determine the molecular weight, the results of the R1 detector were used.

Spray Drying An aqueous mixture of the respective carrier material was prepared according to the ratios according to Table 3. With vigorous stirring, the polymer was added as an aqueous solution.

To dry the mixtures, a spray drier from GEA Niro of the Mobile Minor type MM-I was used. It was dried with the help of a two-fluid nozzle in the head of the tower. The drying was done with nitrogen, which was co-current with the

Drying material was blown from top to bottom was dried. Was dried with 80 kg / h of drying gas. The temperature of the drying gas was 220 ° C at the tower entrance. The feed rate of the material to be dried was adjusted so that the starting temperature of the drying gas at the tower outlet was 100 ° C. The discharged from the drying tower, with the drying gas, powder was separated by means of a cyclone from the drying gas.

Spray dryness was evaluated as follows:

Table 1

The particle size was determined with a "Mastersizer 2000" from Malvern Instruments which is the Volumetric Grain Diameter The thermal-mechanical properties of the powder were tested as follows: All required metal parts were heated to 80 ° C. before use in a drying oven Tube with a length of 70 mm and an inner diameter of 50 mm with a wall thickness of 2.5 mm was placed on a brass base plate with a 7 mm high tube attachment at 55 mm inner diameter., In the tube 2 g of powder were added, a A brass cylinder weighing 1558 g was then inserted into the tube, this cylinder was rotated 360 times without pressure, then the cylinder and tube were removed and the sample was ranked according to the following factors: Table 2

The following powders were prepared:

Table 3

PulPolyFst. Mass Carrier [% Fst. Mass BeurteBeurteiver mer (Grams) of Ge (Gramm) lung B total weight]

1 A 40.5 123.5 cyclohe-41, 1 365.0 2 2

xanonharz

[75%]

2 A 40.5 246.9 cyclohe-41, 1 243.3 2 2

xanonharz

[50%]

3 A 40.5 370.4 Cyclohe-41, 1 121, 7 2 2

xanonharz

[25%]

4 B 52 153.8 Cyclohe-41, 1 292.0 2 2

xanonharz

[60%]

5 B 52 153.8 acetone 41, 6 288.5 2 2

resin [60%]

6 C 39.2 306.1 Cyclohe-41, 1 194.6 2 2

xanonharz

[40%]

7 A 40.5 216.6 acetone 41, 6 136 2 2

resin [40%]

V1 A 2 4

V2 A 40.5 246.9 Auxiliary poly36.3 275.5 1-2 1 -2 mer [50%]

V3 A 40.5 246.9 Ligninsul 45.5 219.8 2 2

sulfonate

[50%] V4 cyclohe- 2 2

xanonharz

V5 acetone 2

resin

V6 B not

dryable

V7 C 2 3-4

V8 C 39.2 306.1 sulfonating 39.1 204.6 2 2

melamine-formaldehyde condensation product

[40%]

Fst. = Solids content of the aqueous mixture

Assessment A: spray dryness

Assessment B: after thermal / mechanical stress

The dispersing properties were determined by a mortar test.

The cement mortar was composed of 40.0% by weight of Portland cement (CEM I 52.5 N, Milke) and 60.0% by weight of standard sand (DIN EN 196-1). The water cement value (weight ratio of water to cement) was 0.35. To liquefy the cement mortar, a polymer powder according to Table 3 was added. The content of the polymer powder is shown in Table 4 and is based on the amount of cement.

The cement mortar was produced in accordance with DIN EN 196-1: 2005 in a mortar mixer with a capacity of approx. 5 liters. For mixing, water, polymer powder, 0.45 g of the powdery defoamer Vinapor DF 9010 F (available from BASF Construction Solutions GmbH) and cement were added to the mixing vessel. Immediately thereafter, the low-speed mixing of the vortex (140 revolutions per minute (rpm)) was started. After 30 seconds, the standard sand was added evenly over 30 seconds to the mixture. Thereafter, the mixer was switched to a higher speed (285 rpm) and mixing continued for a further 30 seconds. Subsequently, the mixer was stopped for 90 seconds. For the first 30 seconds, the cement mortar stuck to the wall and bottom of the bowl was removed with a rubber raspper and placed in the center of the bowl. After Pause the cement mortar was mixed for a further 60 seconds at the higher mixing speed. The total mixing time was 4 minutes.

Immediately after the end of the mixing process, the flow was measured with the Hägermann cone of all samples without the application of compaction energy in accordance with the SVB directive of the German Committee for reinforced concrete (see: German Committee for Reinforced Concrete Construction (ed.): DAfStb - Directive Self-compacting concrete (SVB Directive) Berlin, 2003). The Hägermann cone (d top = 70 mm, d bottom = 100 mm, h = 60 mm) was placed in the middle on a dry glass plate with a diameter of 400 mm and filled to the intended height with cement mortar. Immediately after buffing, or 5 minutes after the first contact of cement and water, the Hägermann cone was withdrawn, held for 30 seconds over the dewatering cement mortar, and then removed. As soon as the flow gauge came to a standstill, the diameter was determined with a measuring slide on two axes at right angles to each other and the mean value calculated. In order to characterize the temporal evolution of the flow rate, the test of the flow rate was repeated after 10, 20, 30, 45, 60, 90 and 120 minutes. Before each test, the cement mortar was mixed for 10 seconds in a mortar mixer at a speed of 140 revolutions per minute (rpm).

The solidification times were determined according to DIN EN 196, Part 3.

The results of these tests are shown in Table 4.

Table 4

Flow rate / cm Vicat solidification

Powder dosage 5 min 10 30 60 120 EB / min EE /

% bwoc min min 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

V1 0.18 30.4 29.5 27.5 26.8 394 466

V2 0.3 28.6 27.8 26.4 24.9 654 699

V3 0.38 28 23.4 20.8 19.3 507 544

V4 0.7 Not

flowable

V5 0.6 Not

flowable

V7 0.17 26.8 24.6 23.3 23.1 366 458 V8 0.45 27.6 27.7 27.5 27.3 398 543

EB: start of solidification

EE: solidification end As can be seen from the experiments, only powders 1 to 7 according to the invention have both good powder properties and at the same time good dispersing properties in mortars and enable a low setting time of the mortar.

Powder V8 was prepared analogously to the disclosure of WO 2013/020862 and can be compared directly with the powder 6 according to the invention. This shows that the powder 6 according to the invention causes a significantly lower delay in the setting of the inorganic binder compared to powder V8 and furthermore has a significantly better dosing efficiency.

Claims

claims

A composition in the form of a solid which is suitable as a dispersant for inorganic solid suspensions, comprising

A) at least one water-soluble polymer comprising polyether groups and

B) at least one acid groups and / or salts thereof containing water-soluble condensation product based on monomers, wherein the monomers are at least

a) a monomer with a ketone radical and

ß) formaldehyde.

Composition according to Claim 1, characterized in that the polyether groups of the at least one water-soluble polymer A) are polyether groups of the structural unit (I),

-U- (C (0)) _k -X- (AlkO) nW (I) where

^* indicates the binding site to the polymer,

U is a chemical bond or an alkylene group having 1 to 8 carbon atoms,

X represents oxygen, sulfur or a group NR ¹ ,

k is 0 or 1,

Alk is _C2-C4 alkylene, wherein Alk in the group (Alk-0) _n

may be the same or different,

W represents a hydrogen, a C 1 -C 6 -alkyl or an aryl radical or the group Y-F, where

Y is a linear or branched alkylene group having 2 to 8 C atoms, which may carry a phenyl ring,

F for a nitrogen-linked 5- to 10-membered

Nitrogen heterocycle having as ring members, in addition to the nitrogen atom and in addition to carbon atoms, 1, 2 or 3 additional heteroatoms selected from oxygen, nitrogen and sulfur, wherein the nitrogen ring members may have a group R ² , and wherein 1 or 2 carbon ring members as the carbonyl group R ^{1 is} hydrogen, C ¹ -C ₄ -alkyl or benzyl, and

R ^{2 is} hydrogen, C 1 -C ₄ -alkyl or benzyl,

is.

3. The composition of claim 1 or 2, characterized in that the polymer A), further at least one group from the series carboxyester, carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, Sul - finoalkyloxy and phosphonooxy group.

4. The composition according to any one of claims 1 to 3, characterized in that the polymer A) is a polycondensation product comprising a structural unit having an aromatic or heteroaromatic and the polyether group, a phosphated an aromatic or heteroaromatic containing structural unit.

Composition according to Claim 4, characterized in that the structural units (II) and (III) are represented by the following general formulas

(Ii)

AU- (C (0)) kX- (AlkO) _n -W

(H l)

With

D is identical or different and represented by a substituted or unsubstituted aromatic or heteroaromatic compound having 5 to 10 C atoms in the aromatic system E is the same or different and represented by N, NH or O with

m = 2 if E = N and m = 1 if E = NH or O with

R ³ and R ⁴ are each independently the same or different and represented by a branched or unbranched d- to Cio-alkyl radical, Cs to Cs cycloalkyl radical, aryl radical, heteroaryl radical or H with b

the same or different and represented by an integer from 0 to 300.

A composition according to claim 4 or 5, characterized in that the polycondensation product contains a further structural unit (IV), which is represented by the following formula

(IV)

Y independently of one another are identical or different and represented by (II), (III) or further constituents of the polycondensation product, wherein R ⁵ and R ^{6 are} identical or different and are represented by H, CH ₃ , COOH or a substituted or unsubstituted aromatic or heteroaromatic Compound with 5 to 10 carbon atoms.

A composition according to claim 1 or 2, characterized in that the water-soluble polymer A) is at least one copolymer obtainable by polymerization of a mixture of monomers comprising

(V) at least one ethylenically unsaturated monomer which contains at least one radical from the series carboxylic acid, carboxylic acid salt,

Carboxylic acid ester, carboxylic acid amide, carboxylic anhydride and

Carboxylic imide includes

and

(VI) at least one ethylenically unsaturated monomer comprising the

Polyether group.

Composition according to Claim 7, characterized in that the ethylenically unsaturated monomer (V) is represented by at least one of the following general formulas selected from the group consisting of (Va), (Vb) and (Vc) in which

R ⁷ and R ^{8 are} independently hydrogen or an aliphatic

Hydrocarbon radical having 1 to 20 carbon atoms

B is H, -COOMa, -CO-O (C _q H _2q O) _r R ⁹ , -CO-NH- (C _q H _2q O) _r -R ⁹

M is hydrogen, a monovalent, divalent or trivalent metal cation, ammonium ion or an organic amine radical

a for 1/3, 1/2 or 1

R ^{9 is} hydrogen, an aliphatic hydrocarbon radical having 1 to

20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, an optionally substituted aryl radical having 6 to 14 carbon atoms

q independently of each other for each (C _q H2 _q O) unit is equal or

different 2, 3 or 4 and

r for 0 to 200

Z is O, NR ¹⁶

R ¹⁶ independently of one another are identical or different and represented by a branched or unbranched C 1 - to C 10 -alkyl radical, C 5 - to C 6 -cycloalkyl radical, aryl radical, heteroaryl radical or H,

Q

12

R (Vc)

with R ¹⁰ and R ^{11 are} independently hydrogen or an aliphatic

Hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic see hydrocarbon radical having 5 to 8 carbon atoms, an optionally substituted aryl radical having 6 to 14 carbon atoms

R ^{12 is the} same or different and represented by (C _n H 2n) -SO 3 H where n = 0, 1, 2, 3 or 4, (C _n H ₂ n) -OH where n = 0, 1, 2, 3 or 4; (C _n H _2n ) -

PO 3 H ₂ with n = 0, 1, 2, 3 or 4, (C n H ₂ n) -OPO ₃ H ₂ with n = 0, 1, 2, 3 or 4, (C ₆ H ₄ ) -SO ₃ H, ( C ₆ H ₄ ) -PO ₃ H ₂ , (C ₆ H ₄ ) -OPO ₃ H ₂ and

(C _n H _2n ) -NR ¹⁴ b with n = 0, 1, 2, 3 or 4 and b = 2 or 3 R ¹³ for H, -COOMa, -CO-O (C _q H _2q O) r R ⁹ , -CO-NH- (C _q H _2q O) r R ⁹ ,

wherein M _a , R ⁹ , q and r have the meanings mentioned above

R ^{14 is} hydrogen, an aliphatic hydrocarbon radical having 1 to

10 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 carbon atoms, an optionally substituted aryl radical having 6 to 14 carbon atoms.

Q is the same or different and represented by NH, NR ¹⁵ or O;

where R ^{15 is} 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 carbon atoms.

9. Composition according to one of claims 1 to 8, characterized in that it is the acid groups of the condensation product B) at least one of the series carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy-, Sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy group and / or salts thereof. 10. The composition according to any one of claims 1 to 9, characterized in that the condensation product B) has a monomer ratio of the monomers a) to ß) of 1 to 2 to 3.

1 1. A composition according to any one of claims 1 to 10, characterized in that the monomer having a ketone residue a) of the condensation product B) is at least one ketone selected from 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-methoxy-acetophenone, 4-acetylbenzenesulfonic acid, diacetyl, acetylacetone, benzoylacetone and cyclohexanone.

12. The composition according to any one of claims 1 to 1 1, marked thereby, that the composition is present as a powder or granules.

13. A composition according to any one of claims 1 to 12, characterized in that the composition

From 5 to 95% by weight of A), of the at least one water-soluble polymer, comprising polyether groups and

5 to 95% by weight B) of the water-soluble condensation product containing at least one acid group and / or its salts.

14. A process for preparing a composition according to any one of claims 1 to 13, characterized in that the process comprises the following steps:

a) providing a water-soluble polymer A),

b) providing a water-soluble condensation product B),

c) preparing an aqueous mixture comprising the at least one water-soluble polymer A), and the water-soluble condensation product B), d) spray-drying the aqueous mixture to obtain a solid.

Use of a composition according to any one of claims 1 to 13, in an inorganic binder composition.