WO2018177908A1

WO2018177908A1 - Two-component stabilizer for inorganic suspensions

Info

Publication number: WO2018177908A1
Application number: PCT/EP2018/057398
Authority: WO
Inventors: Erik Gubbels; Meik Ranft; Nina Susanne HILLESHEIM
Original assignee: Basf Se
Priority date: 2017-03-30
Filing date: 2018-03-23
Publication date: 2018-10-04

Abstract

The invention relates to a composition comprising at least one water-soluble polymer and an associative thickener based on monomers having specific polyether side chains, monomers comprising acid groups and at least one crosslinking agent. The invention further relates to a mixture comprising an inorganic binder and the composition of the invention, as well as to the use of the composition of the invention as a rheological additive.

Description

Two-component stabilizer for inorganic suspensions

The present invention relates to a composition comprising at least one water-soluble polymer and an associative thickener based on monomers having specific polyether side chains, monomers comprising acid groups and at least one crosslinking agent. Furthermore, the present invention relates to a mixture comprising an inorganic binder and the composition of the invention and the use of the composition according to the invention as a rheological additive. In order to improve processability, i. 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 sulfoaluminate cement, special cements, calcium sulfate n-hydrate (n = 0 to 2), lime or building lime (EN 459) and pozzolans or latent hydraulic binders such. As fly ash, metakaolin, silica fume, blastfurnace slag. In order to convert building material mixtures, in particular based on inorganic binders in a ready-to-use, processable form, much more mixing water is usually required, as 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, inter alia, polycondensation products based on naphthalene or alkylnaphthalenesulfonic acids or sulfonic acid groups containing melamine-formaldehyde resins are known. In addition to the purely anionic flow agents, which contain essentially 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 aids for aqueous mineral suspensions which are prepared by free-radical polymerization of vinyl-containing monomers and which contain polyalkylene oxide groups as a main component.

It has been found that superplasticizers based on lignosulfonate, melamine sulfonate and polynaphthalene sulfonate 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 electrostatic charge due to the anionic groups contained on the main chain (carboxylate groups, sulfonate groups), but additionally stabilize the dispersed particles by steric effects due to the polyalkylene oxide side chains, which form a stabilizing protective layer around the particles by absorption of water molecules. 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 mortar can be prepared at low water / binder ratios. Dispersants based on polycarboxylate ethers and derivatives thereof are offered 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.

Alternatively, it is also possible to add polycarboxylate ethers or derivatives thereof to the inorganic solid suspension in dissolved form. In particular, the dispersant is metered directly into the mixing water. In the case of highly fluid mixtures, however, the tendency to segregate heavier constituents (sand and possibly gravel) and to separate off blood water on the surface is markedly increased. This has negative effects on the processability and the solid-state properties of the hardened building material mixture. Therefore, stabilizers (also referred to as anti-segregants, anti-blebs, or viscosity modifiers) are used to prevent these undesirable effects. Water-soluble non-ionic derivatives of polysaccharides, especially cellulose and starch derivatives, are commonly used in aqueous building material mixtures to prevent the undesirable evaporation of the water required for hydration and processability as well as segregation, sedimentation and bleeding (settling of water on the surface) of the system.

According to Ullmann's Enzyklopadie der Technischen Chemie (4th edition, volume 9, pages 208-210, Verlag Chemie Weinheim), the most common rheological additives are synthetically produced nonionic cellulose and starch derivatives such as methylcellulose (MC), hydroxyethylcellulose (HEC), methylhydroxyethylcellulose ( MHEC), methyl hydroxypropyl cellulose (MHPC). However, microbially produced polysaccharides such as welan gum, diutan gum and naturally occurring extractively isolated polysaccharides (hydrocolloids), such as alginates, xanthans, carrageenans, galactomannans, etc., are used according to the prior art for controlling the rheology of aqueous building material and paint systems used. Many chemically distinct classes of polymers are known which can be used as rheological additives in aqueous inorganic building material mixtures. An important class of stabilizing polymers are the so-called hydrophobically associating polymers. By this the skilled person means water-soluble polymers which or terminally hydrophobic groups, such as longer alkyl chains. In aqueous solution, such hydrophobic groups can associate with themselves or with other hydrophobic group-containing substances. This forms an associative network that stabilizes the medium.

EP 705 854 A1, DE 100 37 629 A1 and DE 10 2004 032 304 A1 disclose water-soluble, hydrophobically associating copolymers and their use, for example in the field of construction chemistry. The copolymers described include acidic monomers such as acrylic acid, vinylsulfonic acid, acrylamidomethylpropanesulfonic acid, neutral monomers such as acrylamide, dimethylacrylamide or monomers comprising cationic groups, such as monomers containing ammonium groups. Such monomers impart water solubility to the polymers. As hydrophobically associating monomers, the disclosed copolymers each contain monomers of the following type: H 2 C = C (R ^x ) -COO - (- CH 2 -CH 2 -O-) _q -Ry or also

wherein R ^{x is} typically H or CH ₃ and Ry is a major hydrocarbon radical, typically hydrocarbon radicals of 8 to 40 carbon atoms. For example, the literature mentions longer alkyl groups or a tristyrylphenyl group.

Furthermore, US Pat. No. 8,362,180 relates to water-soluble copolymers which contain hydrophobically associating monomers. The monomers include an ethylenically unsaturated group and a polyether group having a block structure of a hydrophilic polyalkylene oxide block consisting essentially of ethylene oxide groups and a terminal hydrophobic polyalkylene oxide block consisting of alkylene oxides having at least 4 carbon atoms, preferably at least 5 carbon atoms.

Furthermore, the use of these hydrophobically associating copolymers in aqueous building material compositions is disclosed.

The synthetic hydrophobically associating copolymers known from the prior art are very good stabilizers for aqueous inorganic building material compositions. However, they have the disadvantage that they must be used in large quantities to prevent the undesirable secretion of blood water on the surface of the suspension. This leads to a significant increase in the viscosity of the suspension, which in turn can degrade the processability of the mixture.

Therefore, there is a need for a more efficient stabilizer that also has a high degree of intrinsic viscosity.

It is an object of the present invention to provide additives for inorganic solid suspensions which can be used in small amounts without precipitation of blood water.

This problem was solved by a composition comprising i) at least one water-soluble polymer (P), and

ii) at least one associative thickener (A) comprising a copolymer based on

a) from 0.1 to 35.0% by weight of at least one monomer of the formula (I) H ₂ C =C (R ¹ ) -R ² -O - (- CH ² -CH ² -O) k - (--CH 2 -) CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O-) _m -R ⁴ (I) where the units - (- CH ₂ -CH ₂ -O) _k -, - (- CH ₂ -CH (R ³ ) -O-) i- and - (CH ₂ -CH ₂ -O-) _m -, if present, are arranged in block structure in the order shown in formula (I) and wherein

k for a number from 10 to 150,

I for a number from 1 to 25, and

m is a number from 0 to 16,

R ^{1 is} independently hydrogen or methyl,

R ^{2 is} independently a direct bond or a divalent linking group selected from the group of - (CnF n) -, -O- (Ο _η Ή2η) - and -C (0) -O-

(Cn "H2n") -, where n, n 'and n "are each a natural number from 1 to 6,

R ^{3 is} a linear C 1-4 -alkyl radical or an ether group of the general formula --CH 2 -OR ^{3 '} , where R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms and where R ^{3 is selected from} the group - (- CH 2 -CH (R ³ ) -0-) i- may be the same or different,

R ⁴ independently of one another is hydrogen or a hydrocarbon radical having 1 to 24 carbon atoms, and

b) 10.0 to 99.9 wt .-% of at least one of monomer (a) different hydrophilic monomer and

c) from 0.0001 to 1.0% by weight of at least one monomer other than monomer (a) and monomer (b) which has at least two ethylenically unsaturated groups,

based on the total weight of the associative thickener (A). Surprisingly, it has been found here that an associative thickener which comprises a monomer which contains at least two ethylenically unsaturated groups and is thus crosslinked can be used in substantially lower dosages than a non-crosslinked associative thickener. This also has the positive effect that a solid suspension containing the associative thickener according to the invention has a correspondingly lower viscosity.

According to another preferred embodiment of the present invention, the associative thickener (A) has a higher average molecular weight than the water-soluble polymer (P), wherein

i) the average molecular weight of the associative thickener (A) is determined according to the Mark-Houwink relationship (1),

where K = 0.0049, α = 0.8, [η] the intrinsic viscosity and M the average molecular weight, and

ii) the average molecular weight of the water-soluble polymer (P) by means of gel permeation

Chromatography is determined.

It is particularly preferred that the associative thickener (A) has an average molecular weight of 200,000 g / mol to 30,000,000 g / mol and / or the water-soluble polymer (P) has an average molecular weight of 5,000 to 100,000 g / mol.

According to another preferred embodiment of the present invention, the radicals of the at least one monomer of the formula (I) have the meaning that

k is a number from 23 to 26,

I a number from 14 to 22,

m is a number from 2 to 5,

R ^{1 is} hydrogen,

R ^{2 is} a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4,

R ^{3 is} a hydrocarbon radical having 2 carbon atoms, and

R ^{4 is} hydrogen.

According to a preferred embodiment of the present invention, the at least one monomer having at least two ethylenically unsaturated groups is selected from the group consisting of Ν, Ν'-methylenebisacrylamide, N, N'Methylenbismethacrylamid, ethyl englykoldivinylether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, triallylamine, tetra allylammonium chloride, tetraallyloxyethane, pentaerythritol triallyl ether, divinylbenzene, triallyl isocyanurate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethoxylated bisphenol A; diacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, Tripropylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, cyclopentadiene diacrylate, triallyl terephthalate, diallyl maleate, diallyl fumarate, trivinyl trimellitate, divinyl adipate, dialyl succinate and mixtures of these.

According to a preferred embodiment of the present invention, the at least one hydrophilic M monomer of the formula (II) in which Y is -O- or -NH-,

R ^{5 is} hydrogen or methyl,

R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, OH, C 1 -C 6 -alkyl or C 6 -C 14 -alkyl

aryl,

n for 0 or 1,

M is hydrogen, a metal cation or an ammonium cation and a is 1 or 1 / valency of the metal cation.

The sulfonic acid-containing monomer of the formula (II) is particularly preferably selected from the group consisting of sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or Mixtures of these.

According to a preferred embodiment of the present invention, the at least one associative thickener (A) comprises at least one amide-containing monomer of the formula

in which

R ^{9 is} hydrogen or methyl and

R ¹⁰ and R ¹¹ independently of one another represent hydrogen, linear or branched C 1 -C 20 -alkyl,

C 6 -C 5 cycloalkyl or C 6 -C 14 aryl,

or N-vinylformamide.

Particularly preferably, the at least one amide-containing monomer is selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, Ν, Ν-dimethylacrylamide, N-ethylacrylamide, Ν, Ν-diethylacrylamide, N-cyclohexylacrylamide, N- Benzylacrylamide, N-tert-butylacrylamide, N-vinylformamide or mixtures of these.

According to another preferred embodiment of the present invention, the at least one water-soluble polymer (P) is a copolymer of

e) at least one monomer of the formula (IV)

Z-R ₂ O - (- CH ₂ -CH ₂ -O) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O-) _m -R ⁴ (IV) where the units - (- CH ₂ -CH ₂ -O) _k -, - (- CH ₂ -CH (R ³ ) -O-) i- and - (CH ₂ -CH ₂ -O-) _m -, if present are arranged in block structure in the order shown in formula (IV), Z is an organic radical having at least one polymerizable assembly, and the remaining radicals have the meanings given in formula (I), and

f) at least one monomer comprising the monomer of the formula (IV) different acid groups. The acid group of the monomer comprising at least one acid group is particularly preferably at least one selected from the group consisting of carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy groups ,

According to a preferred embodiment of the present invention, the water-soluble polymer (P) contains

a) 5.0 to 40.0 wt .-% of the at least one monomer of the formula (IV) and

b) from 5.0 to 95.0% by weight of the monomer comprising at least one acid group, based on the total weight of the water-soluble polymer (P).

According to a preferred embodiment of the present invention, the composition contains 5.0 to 95.0% by weight of the at least one associative thickener (A) and 5.0 to 95.0% by weight of the at least one water-soluble polymer (P) on the total weight of the composition.

The present invention further relates to a mixture comprising an inorganic binder and 0.01 to 10.0 wt .-% of the composition described above, based on the dry mass of the mixture.

Moreover, the present invention relates to the use of the composition described above as a rheological additive.

In the following, the present invention will be described in more detail.

The associative thickener (A)

The composition according to the invention contains at least one associative thickener (A), which is a copolymer based on

a) at least one monomer of the formula (I)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O-) _m -R ⁴ (I) where the units - (- CH ₂ -CH ₂ -O) _k -, - (- CH ₂ -CH (R ³ ) -O-) i- and - (CH ₂ -CH ₂ - 0-) _m -, if any, are arranged in a block structure in the order shown in formula (I), and wherein

k for a number from 10 to 150,

I for a number from 1 to 25, and

m is a number from 0 to 16,

R ^{1 is} independently hydrogen or methyl, R ² independently represents a direct bond or a divalent linking group selected from the group of - (CnF n) -, -O- (Ο _η Ή2η) - and -C (O) -O- (Cn "H2n") -, where n, n 'and n "are each a natural number from 1 to 6, R ^{3 is} a linear C 1-4 -alkyl radical or an ether group of the general formula --CH 2 -OR ^3' , where R ^{3 'is} for is a hydrocarbon radical having at least 2 carbon atoms and wherein R ³ may be the same or different within the group - (- CH 2 -CH (R ³ ) -O-) i-,

b) at least one hydrophilic monomer other than monomer (a) and

c) at least one monomer other than monomer (a) and monomer (b) which has at least two ethylenically unsaturated groups,

is. In the monomers (a) of the general formula (I), the vinyl group is H 2 C = C (R ¹ ) - via a divalent, linking group -R ² -O- with a block-structured polyalkyleneoxy radical - (- CH ₂ -CH ₂ -O) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O-) _m -R ⁴ wherein the blocks - (- CH ₂ - CH ₂ -O-) _k , - (- CH ₂ -CH (R ³ ) -O-) i and - (- CH ₂ -CH ₂ -O-) m, if present, are arranged in the order shown in formula (I). The monomer (a) has either a terminal OH group or a terminal ether group OR ⁴ .

R ² is a single bond or a divalent linking group selected from the group - (CnF n) -, -O- (Ο _η Ή2η ') - and -C (O) -O- (C _n "H2n") In said formulas n, n 'and n''stand for a natural number from 1 to 6. In other words, the linking group is straight-chain or branched aliphatic hydrocarbon groups having 1 to 6 carbon atoms, either directly or via an ether group -O- or a carboxylester group -C (O) -O- are linked to the group H2C =C (R ¹ ) - Preferably the groups - (CnF n) -, -O- (C _n 1-l2n ') - and -C (0) -0- (C _n "H2n") - to linear aliphatic hydrocarbon groups.

Preferably, the group R ² = - (CnF n) - is a group selected from -CH ² -, -CH ² -CH ² - and -CH ² -CH ² -CH ² -, more preferably a methylene group -CH 2 -.

Preferably, the group R ² = -O- (Ο _η Ή2η) - is a group selected from -O-CH ² -CH ² -, -O-CH ² -CH ² -CH ² - and -O-CH 2 -CH 2 -CH 2 -CH2-, more preferably one

Group -O-CH 2 -CH 2 -CH 2 -CH 2 -.

Preferably, the group R ² = -C (O) -O- (C _n "H 2n") - is a group selected from -C (O) -O-CH ₂ -, -C (O) -O -CH ₂ -CH ₂ - and -C (O) -O-CH ₂ -CH ₂ -CH ₂ -, more preferably -C (O) -O-CH ₂ -CH ₂ -.

Particularly preferably, the group R ² is a group -O- (Ο _η Ή2η) - With particular preference, R ² is a group selected from -CH ₂ - or -O-CH ₂ -CH ₂ -CH ₂ -CH ₂ - or -C (O) -O-CH ₂ -CH ₂ -, very particularly preferably - O-CH2

The monomers (a) of the formula (I) furthermore have a polyalkyleneoxy radical which consists of the units - (- CH ₂ -CH ₂ -O-) _k , - (- CH ₂ -CH (R ³ ) -O-) i and - (- CH ₂ -CH ₂ -O-) _m , wherein the units are arranged in block structure in the order shown in formula (I). The transition between the blocks can be abrupt or continuous. The number of ethyleneoxy units k is a number from 10 to 150, preferably from 12 to 50, particularly preferably from 15 to 35 and particularly preferably from 20 to 30. The number of ethyleneoxy units k is very particularly preferably around a number from 23 to 26. These numbers are always averages of distributions.

In the second block - (- CH 2 -CH (R ³ ) -O-) i-, the radicals R ³ independently of one another represent a linear C 1-4 -alkyl radical, preferably with 2 to 4 and particularly preferably with 2 or 3 carbon atoms. It may be an aliphatic and / or aromatic, linear or branched carbon radical. Preference is given to aliphatic radicals. It is particularly preferably an aliphatic, unbranched hydrocarbon radical having 2 or 3 carbon atoms. The said block is preferably a polybutyleneoxy block or a polypentyleneoxy block. Examples of suitable radicals R ³ include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl, n-dodecyl, n-tetradecyl and phenyl.

Examples of suitable radicals R ³ include ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl or n-decyl and also phenyl. Examples of preferred radicals include n-propyl, n-butyl, n-pentyl, particularly preferably an ethyl radical or an n-propyl radical. The radicals R ³ may furthermore be ether groups of the general formula -CH 2 -OR ^{3 '} , where R ^3' is an aliphatic and / or aromatic, linear or branched hydrocarbon radical having at least 2 carbon atoms, preferably 2 to 10 Carbon atoms and more preferably at least 3 carbon atoms. Examples of radicals R ^{3 '} include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or phenyl. Examples of radicals R ^{3 '} include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl or phenyl.

The block - (- CH 2 -CH (R ³ ) -O-) i- is therefore a block which consists of alkyleneoxy units with at least 4 carbon atoms, preferably with 4 or 5 carbon atoms and / or glycidyl ethers with an ether group of at least 2, preferably at least 3 carbon atoms. Preferred radicals R ³ are the hydrocarbon radicals mentioned; the building blocks of the second block are particularly preferably at least 4 Carbon atoms comprising alkyleneoxy, such as butyleneoxy and Pentylenoxyeinheiten or units of higher alkylene oxides, most preferably are butylene oxide or Pentylenoxyeinheiten. In a further preferred embodiment, the radicals R ³ independently of one another are hydrocarbon radicals having at least 6 carbon atoms, preferably having 6 to 20 carbon atoms, particularly preferably 8 to 18 and particularly preferably 8 to 16 carbon atoms. It may be an aliphatic and / or aromatic, linear or branched carbon radical. Preference is given to aliphatic radicals. Particularly preferred is an aliphatic, unbranched hydrocarbon radical having 10, 12, 14 or 16 carbon atoms.

In particular, the radicals R ³ independently of one another represent hydrocarbon radicals having at least 6 carbon atoms, when I assumes a number from 1 to 12.

It will be clear to one skilled in the art of polyalkylene oxides that the orientation of the hydrocarbon radicals R ³ may depend on the conditions of the alkoxylation, for example the catalyst chosen for the alkoxylation. The alkyleneoxy groups can thus be incorporated into the monomer both in the orientation - (- CH 2 -CH (R ³ ) -O -) or in the inverse orientation - (- CH (R ³ ) -CH 2 -O -) -. The representation in formula (I) should therefore not be regarded as being restricted to a specific orientation of the group R ³ . The number of alkyleneoxy units I is a number from 1 to 25, in particular from 1 to 23, particularly preferably from 7 to 20, very particularly preferably from 12 to 17. The sum of the carbon atoms in all hydrocarbon radicals R ³ is preferably within the group - (- CH 2 -CH (R ³ ) -O-) i from 10 to 50, preferably from 12 to 40, particularly preferably from 25.5 to 34.5. If the radicals R ³ are an ether group -CH 2 -OR ^{3 '} , the proviso that the sum of the hydrocarbon radicals of R ^3' within the

Group - (- CH 2 -CH (R ^{3 '} ) -O-) i is from 10 to 50, preferably from 12 to 40, particularly preferably from 25.5 to 34.5, where the carbon atom of the linking -Ch -O- Group in -CH2-O-R ^{3 'is} not considered.

A preferred embodiment relates to an associative thickener described above comprising a monomer (a), wherein R ^{3 is} ethyl and I is a number from 12 to 25, preferably from 14 to 25, particularly preferably from 14 to 23, for example 14, 16, 18 or 22 is.

The number of alkyleneoxy units I in a preferred embodiment is a number from 12 to 20, in particular with the proviso that the sum of the carbon atoms in all hydrocarbon radicals R ^{3 is} in the range from 30 to 45. When the radicals R ³ are an ether group -CH 2 -OR ^{3 '} , in particular the proviso that the sum of the hydrocarbon radicals R ^{3' is} in the range from 30 to 45, wherein the carbon atom of the linking -CH 2 - O group in -CH2-OR ^{3 'is} not taken into account. A preferred embodiment relates to a water-soluble polymer described above comprising a monomer (a), wherein R ^{3 is} ethyl and I is a number from 14 to 20, in particular from 14 to 18, for example 14 or 16, is. A further preferred embodiment relates to a water-soluble polymer described above comprising a monomer (a), wherein R ^{3 is} n-propyl and I is a number from 8.5 to 1 1, 5, preferably from 9 to 1 1, for example 10 or 1 1 , is. As already mentioned, the numbers mentioned are mean values of distributions.

The block - (- CH 2 -CH 2 O-) _m is a polyethyleneoxy block. The number of ethyleneoxy units m is a number from 0 to 15, preferably from 0.1 to 10, particularly preferably from 0.1 to 5, particularly preferably from 0.5 to 5 and very particularly preferably from 2 to 5 Again, these numbers are averages of distributions.

The radical R ⁴ is H or a preferably aliphatic hydrocarbon radical having 1 to 24 carbon atoms. R ⁴ is preferably H, methyl or ethyl, particularly preferably H or methyl and very particularly preferably H.

It will be apparent to those skilled in the art of polyalkyleneoxy block copolymers that the transition between blocks, if present, may be abrupt or continuous, depending on the nature of the preparation. In a continuous transition, there is still a transition zone between the blocks, which comprises monomers of both blocks. If one sets the block boundary to the center of the transition zone, which may corresponding to the first block - (- CH2-CH2-0-) k small amounts of units - (- CH 2 CH (R ³⁾ -0 -) - and second block - (- CH 2 -CH (R ³ ) -O-) i small amounts of units - (- CH 2 -CH 2 -O -) - have, but these units are not distributed statistically over the block, but in said Transition zone are arranged. In particular, the third block (-CH 2 -CH 2 -O-) _m may contain small amounts of units - (- CH 2 -CH (R ³ ) -O -) -. Block structure in the sense of the present invention means that the blocks are composed of at least 85 mol%, preferably at least 90 mol%, particularly preferably at least 95 mol%, based on the total amount of substance of the respective block from the corresponding units are. This means that the blocks in addition to the corresponding units can have small amounts of other units (in particular other polyalkyleneoxy units). In particular, the polyethyleneoxy block - (- CH 2 -CH 2 -O-) _{m contains} at least 85 mol%, preferably at least 90 mol%, based on the total amount of substance of the block, of the unit (-CH 2 -CH 2 -O-). More preferably, the polyethyleneoxy block - (- CH ₂ -CH ₂ -O-) _m consists of 85 to 95 mol% of the unit (-CH ₂ -CH ₂ -O-) and from 5 to 15 mol% of the unit - (- CH ₂ -CH (R ³ ) -0-).

The invention particularly preferably relates to a polymer (a) in which the radicals in monomer (a) according to formula (I) have the following meanings: k: is a number from 20 to 150

I: is a number from 1 to 25 m: is a number from 0 to 15

R ² : is independently a single bond or a divalent linking group selected from the group consisting of - (CnF n) - and -O- (Ο _η Ή2η) - and -C (0) -O- (Cn "H2n ") - where n, n 'and n" is a natural number from 1 to 6;

R ³ : is a hydrocarbon radical having at least 2 carbon atoms or an ether group of the general formula -CH 2 -OR ^{3 '} , wherein R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms and wherein R ³ within the group - (- CH 2 -CH (R ³ ) -0-) i may be the same or different;

R ⁴ : is independently H or a hydrocarbon radical having 1 to 4 carbon atoms The invention preferably relates to an associative thickener (A) in which the radicals in monomer (a) according to formula (I) have the following meanings: k: is a number from 15 to 35, preferably from 20 to 28, in particular from 23 to 26; I: is a number from 14 to 25, preferably from 14 to 23, in particular from 14 to 20; m: is a number from 0 to 15, preferably from 0.5 to 10;

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4;

R ³ : is a hydrocarbon radical having 2 carbon atoms; in particular ethyl; R ⁴ : is H. The invention furthermore preferably relates to an associative thickener (A) in which the radicals in monomer (a) of the formula (I) have the following meanings: k: is a number from 15 to 35, preferably from 20 to 28, more preferably from 23 to 26; I: is a number from 1 to 14, preferably from 1 to 12, particularly preferably from 1 to 10, for example 1, 2 or 3; m: is a number from 0 to 15, preferably from 0.5 to 10; R ¹ : is H;

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4; R ³ : is, independently of one another, a hydrocarbon radical having 8 to 20 carbon atoms; R ⁴ : is H. The invention preferably relates to an associative thickener (A) in which the radicals in monomer (a) according to formula (I) have the following meanings: k: is a number from 15 to 35, preferably from 20 to 28 preferably from 23 to 26; I: is a number from 14 to 25, preferably from 16 to 25, more preferably from 18 to 25; more preferably from 18 to 23, for example 14, 16 or 22; m: is a number from 0.1 to 10, preferably from 0.5 to 10, particularly preferably from 2 to 5; R: is H;

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4;

R ³ : is, independently of one another, a hydrocarbon radical having at least 2 carbon atoms; in particular ethyl;

R ⁴ : is H.

The invention particularly preferably relates to an associative thickener (A) in which the radicals in monomer (a) of the formula (I) have the following meanings: k: is a number from 23 to 26;

I: is a number from 14 to 22; m: is a number from 0 to 15; preferably from 0.5 to 10; R: is H; R ² : is, independently of one another, a hydrocarbon radical having at least 2 carbon atoms; in particular ethyl;

R ⁴ : is H. Furthermore, the invention relates in particular to an associative thickener (A) in which the radicals in monomer (a) according to formula (I) have the following meanings: k: is a number from 23 to 26; I: is a number from 10 to 18; m: is a number from 0 to 15, preferably from 0.5 to 10;

R: is H;

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4; R ³ : is a hydrocarbon radical having 3 carbon atoms, in particular n-propyl; R ⁴ : is H.

In a particularly preferred embodiment, the invention relates to an associative thickener (A) in which the radicals in monomer (a) according to formula (I) have the following meanings: k: is a number from 23 to 26;

I: is a number from 14 to 18; m: is a number from 2 to 5; R: is H; R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4; R ³ : is a hydrocarbon radical having 2 carbon atoms; R ⁴ : is H.

In a further particularly preferred embodiment, the invention relates to an associative thickener (A) in which the radicals in monomer (a) according to formula (I) have the following meanings: k: is a number from 10 to 150 I: is a number from 1 to 2 m: is 0

R: is H; R ² : is independently a single bond or a divalent linking group selected from the group consisting of - (C _n -n) -, -O- (C _n H 2n) - and - C (O) -O- (Cn) H2n ") - where n, n 'and n" for a natural number of 1 to 6; R ³ is a hydrocarbon radical having 8 to 24 carbon atoms;

R ⁴ : is H.

In a preferred embodiment, the invention relates to associative thickener (A) according to the invention, wherein the radical k in monomer (a) according to formula (I) is a number from 23 to 26.

In a further preferred embodiment, the invention relates to associative thickeners (A), wherein the radical I in monomer (a) according to formula (I) is a number from 14 to 25.

The associative thickener (A) according to the invention is a polymer which has hydrophobic groups. In aqueous compositions, without being bound by theory, the hydrophobic groups may associate with themselves or with the hydrophobic groups of other materials, particularly the at least one water-soluble polymer (P), and thicken the aqueous composition through these interactions.

It is known to the person skilled in the art that the solubility of hydrophobically associating polymers in water can be more or less dependent on the pH, depending on the nature of the monomers used. For the purposes of the present application, "water-soluble polymer" means polymers which, in water at 20 ° C. and normal pressure and at least one pH from the series 2, 7 or 12, have a solubility of at least 1 gram per liter of water, in particular at least 10 grams per liter of water, and more preferably at least 100 grams per liter of water, wherein the at least one hydrophilic monomer (b) is preferably a sulfonic acid-containing monomer of the formula (II)

in which

Y is -O- or -NH-,

for hydrogen or methyl,

R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, OH, C ¹ -C ⁶ -alkyl or C ₆ -C ₄ -aryl,

n for 0 or 1,

M is hydrogen, a metal cation or an ammonium cation and a is 1 or 1 / valency of the metal cation. In a preferred embodiment, the radicals in the monomer (b) of the formula (II) have the following meaning: Y: is -NH-;

R ⁵ : is hydrogen or methyl;

R ⁶ , R ⁷ and R ⁸ are independently hydrogen or C ¹ -C ⁶ -alkyl; n: is 0;

M: is hydrogen or Na; a: is 1.

Particularly preferred is 2-acrylamido-2-methylpropanesulfonic acid (AMPS).

The associative thickener (A) according to the invention furthermore comprises at least one monomer (c) which has at least two ethylenically unsaturated groups. The incorporation of such monomers, which are also referred to as crosslinkers, gives the associative thickener (A) a slightly branched or crosslinked structure.

Examples of suitable crosslinker components are Ν, Ν'-methylenebisacrylamide, N, N'-methyl-enbismethacrylamide or monomers having at least one maleimide group, preferably hexamethylenebismaleimide, monomers having more than one vinyl ether group, preferably ethylene glycol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, Allylamino or allylammonium compounds having more than one allyl group, preferably triallylamine or a tetraallylammonium salt such as tetraallylammonium chloride, or allyl ethers having more than one allyl group, such as tetraallyloxyethane and pentaerythritol triallyl ether, or monomers having vinylaromatic groups, preferably divinylbenzene and triallyl isocyanurate, or diamines, triamines , Tetramines or higher-order amines, preferably ethylenediamine and diethylenetriamine, di-, tri- or tetra (meth) acrylates, such as 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3. Butylenglykoldimethac ethylene glycol dimethacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol. lenglykoldimethacrylat, triethylene glycol diacrylate, triethylene glycol dimethacrylate, Tripropylengly- diacrylate, taacrylat tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, Dipentaerythritpen-, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethyl olpropantrimethacrylat, cyclopentadiene, tris (2-hydroxyethyl) isocyanurate and / o the tris (2-hydroxy) isocyanurate trimethacrylate containing more than one vinyl ester or allyl ester group with corresponding carboxylic acids such as divinyl esters of polycarboxylic acids, diallyl esters of polycarboxylic acids, triallyl terephthalate, diallyl maleate, diallyl fumarate, trivinyl trimellitate, divinyl adipate and / or diallyl succinate. Preference is given to at least one monomer (c) which has at least two ethylenically unsaturated groups selected from the group consisting of triallylamine, tiallylmethylammonium chloride, tetraallylammonium chloride, Ν, Ν'-methylenebisacrylamide, tirethyleneglycol bismethacrylate, triethylene glycol bisacrylate, polyethylene glycol (400) bismethacrylate , Polyethylene glycol (400) bis-acrylate and mixtures of these.

Particularly preferred is tetraallylammonium chloride.

However, the crosslinkers may only be used in amounts such that a water-soluble associative thickener (A) is still obtained.

Accordingly, the associative thickener (A) according to the invention contains 0.1 to 35.0 wt .-%, more preferably 0.5 to 10.0 wt .-%, particularly preferably 1, 0 to 2.5 wt .-% of the at least one Monomers (a) of the formula (I), 10.0 to 99.9 wt .-%, more preferably 20.0 to 70.0 wt .-%, particularly preferably 30.0 to 55.0 wt .-% of at least one hydrophilic monomer (b) and 0.0001 to 1, 0 wt .-%, more preferably 0.0001 to 0.1 wt .-%, particularly preferably

0.001 to 0.01 wt .-%, particularly preferably 0.0025 to 0.005 wt .-% of the at least one monomer (c) which has at least two ethylenically unsaturated groups, based on the total weight of the associative thickener (A). In addition to the at least one monomer (a) of the formula (I), the at least one hydrophilic monomer (b) and the at least one monomer (c) which has at least two ethylenically unsaturated groups, the associative thickener (A) preferably contains at least one amide containing monomer (d). The at least one amide-containing monomer (d) is preferably a monomer of the formula (III)

in which

R ^{9 is} hydrogen or methyl and R ¹⁰ and R ^{11 are} independently of one another hydrogen, linear or branched C 1 -C 20 -alkyl, C 5 -C 8 -cycloalkyl or C 6 -C 14 -aryl,

or N-vinylformamide. Particularly preferably, the at least one amide-containing monomer (d) is a monomer selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, Ν, Ν-dimethylacrylamide, N-ethylacrylamide, N , N-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-tert-butylacrylamide, N-vinylformamide or mixtures of these.

Particularly preferred is acrylamide. Accordingly, the associative thickener (A) according to the invention, more preferably consists of 0.1 to 35.0 wt .-%, more preferably 0.5 to 10.0 wt .-%, particularly preferably 1, 0 to 2.5 wt .-% of the at least one monomer (a) of the formula (I), 10.0 to 99.9 wt .-%, more preferably 20.0 to 70.0 wt .-%, particularly preferably 30.0 to 55, 0 wt .-% of the at least one hydrophilic monomer (b), 0.0001 to 1, 0 wt .-%, more preferably 0.0001 bis

0.1 wt .-%, particularly preferably 0.001 to 0.01 wt .-%, particularly preferably 0.0025 to 0.005 wt .-% of the at least one monomer (c) which has at least two ethylenically unsaturated groups, and 30, 0 to 70.0% by weight, more preferably 35.0 to 65.0% by weight, particularly preferably 40.0 to 55.0% by weight of the at least one amide-containing monomer (d), based on the total weight of the associative thickener (A).

In a preferred embodiment, the preparation of the associative thickener (A) by means of gel polymerization is carried out in an aqueous phase, provided that all monomers used have sufficient water solubility. For the purposes of the present invention, gel polymerization is a special case of solution polymerization and is therefore included in this term. For gel polymerization, a mixture of the monomers, initiators and other excipients with water or an aqueous solvent mixture is first provided. Suitable aqueous solvent mixtures include water and water-miscible organic solvents, the proportion of water being generally at least 50% by weight, preferably at least 80% by weight and more preferably at least 90% by weight. To name as organic solvents are here in particular water-miscible alcohols such as methanol, ethanol or propanol. Acidic monomers can be completely or partially neutralized prior to polymerization.

The concentration of all components except the solvents is usually 25 to 60 wt .-%, preferably 30 to 50 wt .-%. The mixture is then polymerized photochemically and / or thermally, preferably at -5 ° C to 50 ° C. If thermally polymerized, preference is given to using polymerization initiators which start even at a comparatively low temperature, for example redox initiators. The thermal polymerization can be carried out at room temperature or by heating the mixture, preferably at temperatures of not more than 50.degree. The photochemical polymerization is usually carried out at temperatures of -5 to 10 ° C. Particularly advantageous photochemical and thermal polymerization can be combined with each other by the mixture admits both initiators for the thermal and for the photochemical polymerization. The polymerization is first started photochemically at low temperatures, preferably -5 to + 10 ° C. The liberated heat of reaction heats up the mixture, which additionally initiates thermal polymerization. By means of this combination, a turnover of more than 99% can be achieved.

The gel polymerization is usually carried out without stirring. It can be carried out batchwise by irradiating and / or heating the mixture in a suitable vessel at a layer thickness of 2 to 20 cm. The polymerization produces a solid gel. The polymerization can also be continuous. For this purpose, use is made of a polymerization apparatus which has a conveyor belt for receiving the mixture to be polymerized. The conveyor belt is equipped with means for heating or for irradiation with UV radiation. After this, the mixture is poured on by means of a suitable device at one end of the strip, in the course of transport in the direction of the strip, the mixture polymerizes and at the other end of the strip, the solid gel can be removed.

The gel is comminuted and dried after the polymerization. The drying should preferably be carried out at temperatures below 100 ° C. To avoid sticking together, one can use a suitable release agent for this step. The associative thickener (A) according to the invention is obtained as a powder.

Further details for carrying out a gel polymerization are disclosed, for example, in DE 10 2004 032 304 A1, Sections [0037] to [0041]. Associative thickeners (A) according to the invention in the form of alkali-soluble, aqueous dispersions can preferably be prepared by means of emulsion polymerization. The performance of an emulsion polymerization using hydrophobically associating monomers is disclosed, for example, in WO 2009/019225 page 5, line 16 to page 8, line 13. With regard to the associative thickener (A) preferably to be used according to the present invention and its preparation, reference is further made to patent applications WO 2014/095621, the content of which is hereby fully incorporated into this application.

The at least one associative thickener (A) has an average molecular weight of 200,000 to 30,000,000 g / mol, more preferably 250,000 to 15,000,000 g / mol, and most preferably 300,000 to 8,000,000 g / mol. The mean molecular weight M _{w of} the associative thickener (A) according to the invention was determined by the Mark-Houwink relationship (1).

The Water-Soluble Polymer (P) According to a preferred embodiment of the present invention, the at least one water-soluble polymer (P) is a copolymer of e) at least one monomer of the formula (IV) Z-R ₂ O - (- CH ₂ -CH ₂ -O) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O-) _m -R ⁴ (IV) where the units - (- CH ₂ -CH ₂ -O) _k -, - (- CH ₂ -CH (R ³ ) -O-) i- and - (CH ₂ -CH ₂ -O-) _m -, if present are arranged in block structure in the order shown in formula (IV), Z is an organic radical having at least one polymerizable assembly, and the remaining radicals have the meanings given in formula (I), and

f) at least one monomer comprising the monomer of the formula (IV) different acid groups.

With respect to the monomer (e) of the formula (IV), the radicals R ² , R ³ and R ⁴ and also k, I, and m have the same meanings as in formula (I). The blocks - (- CH ₂ -CH ₂ -O) _k -, - (- CH ₂ -CH (R ³ ) -O-) i- and - (CH ₂ -CH ₂ -0-) _m - also correspond to the blocks of the formula (I) described above. Accordingly, reference should be made here to the abovementioned definitions with regard to the orientation of the hydrocarbon radicals R ³ and the transition between the blocks.

In a preferred embodiment, the water-soluble polymer (P) is a copolymer of

e) at least one monomer of the formula (IV), wherein Z is an ethylenically unsaturated radical and

f) wherein the monomer (f) has at least one ethylenically unsaturated radical.

In a further preferred embodiment, the ethylenically unsaturated monomer (f) is represented by at least one of the following general formulas from the group (V), (VI) and (VI I):

In the mono- or dicarboxylic acid derivative (V) and the cyclic monomer (VI) wherein W = O (acid anhydride) or NR ¹⁴ (acid imide), R ¹² and R ^{13 are} independently hydrogen or an aliphatic one 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 ⁵ , -CO-NH- (C _q H _2q O) r R ¹⁵ .

M is hydrogen, a monovalent, divalent or trivalent metal cation, preferably sodium, potassium, calcium or magnesium, furthermore ammonium or an organic amine radical and a = 1/3,> 2 or 1, depending on whether M is a one, two or trivalent cation. As organic amine radicals are preferably substituted ammonium groups constitutes einge- derived from primary, secondary or tertiary Ci _-2 o-alkylamines, Ci _-2 o-alkali nolamines, Cs-s-cycloalkylamines and C6-14-arylamines. Examples of the corresponding amines are methylamine, dimethylamine, trimethylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, cyclohexylamine, dicyclohexylamine, phenylamine, diphenylamine in the protonated (ammonium) form.

R ¹⁵ 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 as well as saturated or unsaturated. Preferred cycloalkyl radicals are cyclopentyl or cyclohexyl radicals, preferred phenyl radicals being phenyl or naphthyl radicals, which may in particular be substituted by hydroxyl, carboxyl or sulfonic acid groups.

Furthermore, W is O or NR ¹⁴ , wherein R ^{14 is} independently the same or different and is represented by a branched or unbranched C 1 to C 10 alkyl, C to C cycloalkyl, aryl, heteroaryl or hydrogen.

The following formula represents the monomer (VII):

(VII)

Here, R ¹⁶ and R ¹⁷ independently of one another are hydrogen or an aliphatic hydrocarbon radical having 1 to 20 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 8 C atoms or an optionally substituted aryl radical having 6 to 14 C atoms.

Furthermore, R ^{18 is the} same 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 (CnH ₂ n) -NR ²⁰ _b with n = 0, 1, 2, 3 or 4 and b represented by 2 or 3.

R ¹⁹ is H, -COOM _a , -CO-O (C _q H _2q O) _r -R ¹⁵ , -CO-NH- (C _q H _2q O) _r R ¹⁵ where M _a , R ¹⁵ , q and r have the meanings mentioned above. R ²⁰ is hydrogen, an aliphatic hydrocarbon radical having 1 to 10 C atoms, a cydoaliphatic 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 ²¹ or O, where R ^{21 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. Examples of suitable monomers (f) are, in particular, monomers comprising COOH groups, such as acrylic acid or methacrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid, monomers comprising sulfonic acid groups, such as vinylsulfonic acid, allylsulfonic acid, sulfofylymethacrylate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-Methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidobutanesulfonic acid, 3-acrylamido-3-methyl-butanesulfonic acid or 2-acrylamido-2,4,4-trimethylpentanesulfonic acid or phosphonic acid monomers such as vinylphosphonic acid, allylphosphonic acid, N- (meth) acrylamidoalkylphosphon - acids or (meth) acryloyloxyalkylphosphonsäuren.

In a particularly preferred embodiment, Z in formula (IV) is represented by at least one radical of formula (VIII)

_R 12 _R 13 (VIII) wherein R ¹² and R ^{13 have} the meanings given above.

In a preferred embodiment, the invention relates to a water-soluble polymer (P) in which the radicals in monomer (e) according to formula (IV) have the following meanings: k: is a number from 23 to 26;

I: is a number from 14 to 22; m: is a number from 0 to 5;

Z is a radical of formula (VIII) wherein R ¹² and R ^{13 are} hydrogen; R ² is a divalent linking group -O- (Ο _η Ή 2η) -, wherein n 'is 4; R ³ : is a hydrocarbon radical having 1 or 2 carbon atoms; R ⁴ : is H.

In a particularly preferred embodiment, the invention relates to a water-soluble polymer (P) in which the radicals in monomer (e) according to formula (IV) have the following meanings: k: is a number from 23 to 26;

I: is a number from 14 to 18; m: is a number from 2 to 5;

Z is a radical of the formula (VIII) in which R ¹² and R ^{13 are} hydrogen,

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4; R ³ : is a hydrocarbon radical having 2 carbon atoms; R ⁴ : is H.

In a further particularly preferred embodiment, the invention relates to a water-soluble polymer (P) in which the radicals in monomer (e) according to formula (IV) have the following meanings: k: is a number from 20 to 24; I: is a number from 18 to 22 meters: is 0

Z is a radical of the formula (VIII) in which R ¹² and R ^{13 are} hydrogen,

R ² : is a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4;

R ³ : is methyl; R ⁴ : is H. The water-soluble polymers (P) according to the present invention contain at least two monomer building blocks. In a preferred embodiment, the total sum of the monomers (e) and (f) in the water-soluble polymer (P) according to the invention is

100 wt .-%, based on the total weight of the water-soluble polymer (P). However, it may also be advantageous to use polymers with three or more monomer units. In a further preferred embodiment, the water-soluble polymer (P) thus further comprises, in addition to the monomer units (e) and (f), from 5 to 90% by weight, preferably from 30 to 90% by weight, particularly preferably from 50 to 80% by weight. %, at least one further monomer component. In particular, the further monomer building blocks of the water-soluble polymer (P) may possibly be at least one compound of the formula (IVa):

ZR ^2a -O - (- CH ₂ -CH ₂ -O-) ka-R ^4a (IVa) where the radicals have the following meanings:

Z: is an organic radical having at least one polymerizable assembly; ka: is a number from 10 to 300;

R ^2a : is independently a single bond or a divalent linking group selected from the group consisting of - (CnF n) - and -O- (C _n 'H2n) - and -C (O) -O- (Cn) H2 _n ") - where n, n 'and n" are a natural number from 1 to 6;

R ^4a : independently of one another is H or a hydrocarbon radical having 1 to 4 carbon atoms.

With particular preference, the radicals of the monomer building block according to formula (IVa) have the following meanings:

Z is an ethylenically unsaturated radical, in particular a radical of the formula (VII) and particularly preferably vinyl; ka: is a number from 10 to 150, in particular 12 to 75 and particularly preferably 15 to 45;

R ^2a : is independently a divalent linking group selected from the group consisting of -O- (C _n 'H2n) - and -C (O) -O- (C _n ' H2n) - _> where n 'and n "is a natural number from 1 to 4, particularly preferably is -0- (C _n 1H2n ') - with n' equal to 4;

R ^4a : independently of one another is H or a hydrocarbon radical having 1 to 4 carbon atoms, more preferably H or a methyl radical. In a preferred embodiment, the total sum of the monomers (e), (f) and the monomer component of the formula (IVa) in the water-soluble polymer (P) according to the invention is 100% by weight, based on the total weight of the water-soluble polymer (P).

Accordingly, it is preferred that the water-soluble polymer (P) according to the invention contains no further monomers apart from the monomers (e) and (f) and the monomer unit of the formula (IVa).

In particular, in a preferred embodiment, the water-soluble polymer (P) does not contain a monomer having more than one ethylenically unsaturated group.

As the solvent in the preparation of the water-soluble polymers (P) according to the invention which have ethylenic radicals as the polymerizable group, in particular water suitable. However, it is also possible to use a mixture of water and an organic solvent, wherein the solvent should be largely inert with respect to radical polymerization reactions. In particular, the organic solvent may be at least one solvent from the series ethyl acetate, n-butyl acetate, 1-methoxy-2-propyl acetate, ethanol, i-propanol, n-butanol, 2-ethylhexanol, 1-methoxy-2 -propanol, ethylene glycol, propylene glycol, acetone, butanone, pentanone, hexanone, methyl ethyl ketone, ethyl acetate, butyl acetate, amyl acetate, tetrahydrofuran, diethyl ether, toluene, xylene or higher-boiling alkylbenzenes act. Furthermore, it may be polyethylene glycol ethers or polypropylene glycol ethers or random ethylene oxide / propylene oxide copolymers having an average molar mass of from 200 to 2000 g / mol, mono-, di- or triethylene glycol, mono-, di- or tripropylene glycol, methyl, ethyl-propyl , Butyl or higher alkylpolyalkylene glycol ethers having 1, 2, 3 or more ethylene glycol and / or propylene glycol units, for example methoxypropanol, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethyl glycol monobutyl ether, diethylene glycol monobutyl ether, butyl polyethylene glycol ethers, propyl polyethylene glycol ethers, ethyl polyethylene glycol ethers, methyl polyethylene glycol ethers, dimethylpo- lyethyleneglycol ethers, dimethylpolypropylene glycol ethers, glycerol ethoxylates having a molecular weight of from 150 to 20,000 g / mol, pentaerythritol alkoxylates, ethylene carbonate, propylene carbonate, glycerol carbonate, glycerol formal and 2,3-O-isopropylidene glycerol. Particular preference is given to alkylpolyalkylene glycol ethers and particularly preferably methyl polyethylene glycol ethers and also polyethylene glycol ethers, polypropylene glycol ethers and random ethylene oxide / propylene oxide copolymers having an average molar mass of from 150 to 2000 g / mol. Also preferred are solvents based on carbonates, in particular ethylene carbonate, propylene carbonate and glycerol carbonate. The polymerization reaction preferably takes place in the temperature range between 0 and 180.degree. C., more preferably between 10 and 100.degree. C., both at atmospheric pressure and under elevated or reduced pressure. Optionally, the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.

To initiate the polymerization, high-energy, electromagnetic radiation, mechanical energy or chemical polymerization initiators such as organic peroxides, for. B. benzoyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, cumyl peroxide, dilauroyl peroxide or azo initiators such. As azobisisobutyronitrile, azobisamidopropyl hydrochloride and 2,2'-azobis (2-methylbutyronitrile) can be used. Also suitable are inorganic peroxy compounds, such as. For example, ammonium peroxodisulfate, potassium peroxodisulfate or hydrogen peroxide, if appropriate in combination with reducing agents (for example sodium hydrogen sulfite, ascorbic acid, iron (II) sulfate) or redox systems which contain as reducing component an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid ) contain.

In particular, it is preferably a mixture of at least one sulfinic acid with at least one iron (III) salt and / or a mixture of ascorbic acid with at least one iron (III) salt. As molecular weight regulator, the usual compounds are used. Suitable known regulators are z. As alcohols, such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol and amyl alcohols, aldehydes, ketones, alkylthiols, such as. As dodecylthiol and tert-dodecylthiol, thioglycolic acid, isooctylthioglycolate, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid and some halogen compounds, such as. As carbon tetrachloride, chloroform and methylene chloride, and sodium hypophosphite and formic acid. In an alternative alternative embodiment, the process for preparing the copolymers according to the invention can also be carried out in an organic solvent or in a mixture of a plurality of organic solvents. In particular, the organic solvents already mentioned above are particularly suitable for this purpose.

The average molecular weight M _{w of} the water-soluble polymer (P) according to the invention as determined by gel permeation chromatography (GPC) is 5,000 to 100,000 g / mol, more preferably 7,000 to 75,000 g / mol, and most preferably 10,000 to 45,000 g / mol. The polymers were analyzed for average molecular weight M _w by size exclusion chromatography. Column combinations: Shodex OHpak SB 804HQ from Showa, Japan (polyhydroxy methacrylate gel, particle size 10 μηη, pore size 2000 Å, plate number> 16,000, diameter and length of column 8 mm × 300 mm) and Shodex OHpak 802.5HQ from Showa, Japan ( Polyhydroxy methacrylate gel, particle size 6 μm, pore size 200 Å, plate number> 16,000, diameter and length of the column 8 mm × 300 mm); Eluent: 0.05 M ammonium formate / methanol (80/20% by volume), pH 6.5; Flow rate: 0.5 ml / min; Column temperature: 50 ° C; Detection: R1; Calibration: PEG / PEO standards in the range 10e6 - 10e2 g / mol.

The polymer according to the invention preferably meets the requirements of the industrial standard EN 934-2 (February 2002).

In a preferred embodiment, the composition according to the invention comprises 5 to 95% by weight, preferably 20 to 95% by weight, particularly preferably 80 to 95% by weight of the at least one water-soluble polymer (P) and 5 to 95% by weight. , preferably 5 to 60 wt .-%, particularly preferably 5 to 20 wt .-% of the at least one associative thickener (A). The composition according to the invention is preferably in the form of a powder.

Another object of the present application is a mixture comprising an inorganic binder and 0.01 to 10 wt .-% of the composition according to the invention, based on the dry mass of the mixture.

In particular, the mixture according to the invention, based on its dry mass, comprises at least 20% by weight, preferably at least 40% by weight, in particular from 30 to

99.99 wt .-% and particularly preferably from 35 to 55 wt .-% of the at least one inorganic Angan- gan and 0.01 to 10 wt .-%, preferably 0.01 to 2 wt .-%, particularly preferably 0 , 02 to 1 wt .-% of the composition of the invention based on the at least one water-soluble polymer (P) and the at least one associative thickener (A). In a preferred embodiment, the inorganic binder according to the invention is at least one from the series calcium sulfate n-hydrate (n = 0-2), Portland cement, white cement, Calciumaluminatzement, Calciumsulfoaluminatzement, geopolymer and latent hydraulic or pozzolanic binder such. B. fly ash, metakaolin, silicon castaub and blastfurnace slag. Particular preference is given to cement based on Portland cement, calcium sulfate hemihydrate, calcium sulfate anhydrite and calcium aluminate cement. The mixture according to the invention may in particular be pulverulent mixtures which are subsequently mixed with water.

In a further preferred embodiment, the mixture according to the invention comprises an inorganic filler. The inorganic filler may preferably be at least one of quartz sand, quartz powder, limestone, barite, calcite, dolomite, talc, kaolin, mica and chalk.

In a specific embodiment, the mixture according to the invention, based on its dry mass, comprises at least 80% by weight, in particular at least 90% by weight, and particularly preferably more than 95% by weight, of an inorganic binder and an inorganic filler ,

In a particularly preferred embodiment, the mixture according to the invention is a dry mortar, in particular masonry mortar, plaster, mortar for thermal insulation systems, Sanierputze, grout, tile adhesive, Dünnbettmörtel, screed mortar, grout, grout, leveling compounds, sealing slurries or lining 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 processable on site only by adding water and mixing, 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 further additives or additives are added to adjust the dry mortar to the specific application. These may, for example, be shrinkage reducers, expansion agents, accelerators, retarders, dispersants, defoamers, air entraining agents and corrosion inhibitors. In a particular embodiment, the mixture according to the invention may also be a self-leveling leveling compound. In particular, the mixture according to the invention can thus be present in the form of a dry mortar. The present application also encompasses a process for the preparation of the mixture according to the invention, wherein the composition according to the invention comprises the at least at least one inorganic binder and possibly other components is brought into contact by mixing. In particular, the composition according to the invention is present in the form of a powder. For dry mortar applications, the composition according to the invention is preferably used in powder form. It is preferred that the size distribution of the particles is selected such that the mean particle diameter is less than 100 μm and the proportion of particles having a particle diameter greater than 200 μm is less than 2% by weight. Preference is given to those powders whose mean particle diameter is less than 60 μm and the proportion of particles having a particle diameter greater than 120 μm is less than 2% by weight. Particular preference is given to those powders whose average particle diameter is less than 50 μm and the proportion of particles having a particle diameter greater than 100 μm smaller than

2 wt .-% is. The particle diameter of the composition according to the invention in powder form can be brought to the preferred size distributions, for example by grinding.

In a preferred embodiment, the inorganic binder may be calcium sulfate n-hydrate (n = 0 to 2), hereinafter also referred to as gypsum. The term "gypsum" is used synonymously with calcium sulphate in the present context, the calcium sulphate being able to be present in its different anhydrous and hydrated forms with and without water of crystallization Natural gypsum essentially comprises calcium sulphate dihydrate ("dihydrate"). The natural anhydrous form of calcium sulfate is covered by the term "anhydrite." In addition to its natural appearance, calcium sulfate is a typical by-product of technical processes, which is understood to mean "synthetic gypsum". A typical example of synthetic gypsum from technical processes is flue gas desulphurisation. However, synthetic gypsum can equally arise as a by-product of phosphoric acid or hydrofluoric acid production processes. Typical plaster

(CaSC x 2 H2O) can be calcined by separating the water of crystallization. Products of the most varied calcination processes are o or ß-hemihydrate. ß-hemihydrate results from a rapid heating in open vessels, with a simultaneous rapid evaporation of water to form cavities. A hemihydrate is produced by draining gypsum in closed autoclaves. The crystal form in this case is relatively dense, which is why this binder requires less water for liquefaction than β-hemihydrate. On the other hand, hemihydrate rehydrates with water to form dihydrate crystals. Typically, the hydration of gypsum requires a time of a few minutes to hours, resulting in a shortened pot life compared to cements requiring several hours to days for complete hydration. These properties make gypsum a viable alternative to cements as binders in a wide variety of applications. In addition, cured gypsum products show a pronounced hardness and compressive strength. Ss-hemihydrate is selected for a wide variety of applications because it is more readily available and has many advantages from an economic point of view. However, these advantages are partially offset by the fact that ß-hemihydrate during processing has a higher water requirement to achieve ever flowable suspensions. In addition, the dried gypsum products made therefrom tend to have some weakness due to residual amounts of water remaining in the crystal matrix upon curing. For this reason, corresponding products have a lower hardness than gypsum products which have been prepared with smaller amounts of mixing water.

For the purposes of the present invention, calcium sulfate-n-hydrate is therefore particularly preferably β-calcium sulfate hemihydrate. In this case, the inventive β-calcium sulfate hemihydrate is particularly suitable for use in gypsum-based liquid screed. Further preferably, the inorganic binder may be a geopolymer. Geopolymers are inorganic binder systems based on reactive water-insoluble compounds based on S1O2 in combination with Al2O3, which cure in an aqueous alkaline medium. Specific geopolymer compositions are e.g. in US 4,349,386, WO 85/03699 and US 4,472,199. As a reactive oxide or oxide mixture u.a. Microsilica, metakaolin, aluminosilicates, fly ashes, activated clay, pozzolans or mixtures thereof. The alkaline medium for activating the binders usually consists of aqueous solutions of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides, alkali metal aluminates and / or alkali metal silicates, such as e.g. soluble water glass. Compared to Portland cement, geopolymers can be cheaper and more durable, especially with respect to acids and a more favorable CO 2 emission balance. The mixture according to the invention may in particular also comprise a binder mixture. These are understood in the present context in particular mixtures of at least two binders from the series cement, pozzolanic and / or latent hydraulic binder, white cement, special cement, Calciumaluminatzement, Calciumsulfoaluminatzement, geopolymer and the various hydrous and anhydrous calcium sulfates.

In the context of the present invention, the mixture according to the invention can be in dry form, it being understood that this has a Karl Fischer water content of less than 5% by weight, preferably less than 1% by weight, and particularly preferably of less than 0.1% by weight.

It is preferred if the mixture according to the invention has an average particle size between 0.1 and 1000 μm, particularly preferably between 1 and 200 μm. The particle size is determined by laser diffractometry.

Another object of the present application is the use of the composition according to the invention in a mixture comprising an inorganic binder and 0.01 to 10 wt .-% of the composition according to the invention, based on the dry mass of the mixture, as a rheological additive. In particular, the composition of the present invention can be used to reduce segregation, sedimentation and bleeding of the composition during the quiescent phase of the mixing, while at the same time achieving good flowability during processing. The following examples are intended to explain the invention in more detail.

Examples

Preparation of monomer M1 135.3 g (1.16 mol) of hydroxybutyl vinyl ether (HBVE) (stabilized with 100 ppm of potassium hydroxide (KOH)) were introduced into a 2 l pressure autoclave with anchor stirrer and the stirrer was started up. 1, 06 g of potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH), equivalent to 0.0048 mol of potassium) were fed and the stirred vessel to a pressure of less than 10 mbar evacuated, heated to 80 ° C and 70 min at 80 ° C and a pressure of less than 10 mbar. MeOH was distilled off.

In an alternative procedure, the potassium methoxide (KOMe) solution (32% KOMe in methanol (MeOH)) was fed and the stirred tank to a pressure of 10 - 20 mbar evacuated, heated to 65 ° C, 70 min at 65 ° C and a Pressure of 10 - 20 mbar operated. MeOH was distilled off.

It was rinsed three times with N 2 (nitrogen). Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set and heated to 120 ° C. It was relaxed to 1 bar absolute and metered 1 126 g (25.6 mol) of ethylene oxide (EO) to p _ma x 3.9 bar absolute and Tmax 150 ° C. After addition of 300 g of EO, the dosage was stopped (about 3 hours after the start), maintained for 30 minutes and relaxed to 1, 3 bar absolute. Thereafter, the remaining EO was added. The addition of EO lasted 10 hours including relaxation.

It was stirred to constant pressure at about 145-150 ° C (1 h), cooled to 100 ° C and freed at a pressure of less than 10 mbar for 1 h of low boilers.

Here, a Hydroxybutylvinyletheralkoxylat was obtained with 22 EO units.

588.6 g (0.543 mol) of hydroxybutylvi- nyl ether alkoxylate containing 22 EO units were initially charged in a 2 l pressure autoclave with anchor stirrer and the stirrer was switched on. Thereafter, 2.39 g of 50% NaOH solution (0.030 mol NaOH, 1.19 g NaOH) was added, vacuum of

<10 mbar, heated to 100 ° C and held for 80 min to distill off the water.

One rinsed three times with N2. Thereafter, the container was tested for pressure tightness, 0.5 bar overpressure (1, 5 bar absolute) set, heated to 127 ° C and then the pressure to 1, 6 bar absolute. There were 59.7 g (1.358 mol) of EO added at 127 ° C, p _ma x was 3.9 bar absolute. It was maintained for 30 min until the pressure remained stable, after which it was completely depressurized to 1, 0 bar.

There were 625.5 g (8.688 mol) BuO (butylene oxide) is metered at 127 ° C, p _ma x was 3.1 solut bar off. An intermediate relaxation due to Füllgradzunahme became necessary. The BuO dosage was stopped, allowed to react for 1 h until pressure was constant and relaxed to 1, 0 bar absolute. Thereafter, the addition of BuO was continued. P _ma x was still 3.1 bar (first relaxation after 610 g BuO, total dosage time BuO 8 h incl. Relaxation break). After the end of the BuO dosage was allowed to react for 8 h and then heated to 135 ° C. Thereafter, 83.6 g (1.901 mol) of EO were metered in at 135 ° C., p _ma x was 3.1 bar absolute. After the end of the EO dosage was allowed to react for 4 h. It was cooled to 100 ° C, withdrawn residual oxide until the pressure for at least 10 minutes below 10 mbar. Then the addition of 0.5% water at 120 ° C and subsequent removal took place until the pressure for at least 10 minutes below 10 mbar. The vacuum was released with N2 and 100 ppm of butylhydroxytoluene (BHT) was added. The bottling was carried out at 80 ° C under N2.

There was obtained a Hydroxybutylvinyletheralkoxylat with 24.5 EO units, 16 BuO units and 3.5 EO units (monomer M1). The analysis (mass spectrum, GPC, ¹ H-NMR in CDCIs, ¹ H-NMR in MeOD) confirmed the structure.

Example 1 (Water-soluble polymer)

In a glass reactor equipped with stirrer, pH electrode, thermometer, redox electrode, 141.0 g of deionized water and 148.50 g of vinyloxybutylpolyethylene glycol-1 100 (VOBPEG 1 100) and 37.50 g of HBVE-24.5EO-16BuO were added. 3.5EO (monomer M1) and cooled to a polymerization start temperature of 15 ° C (template).

In a separate feed vessel 32.59 g of acrylic acid (99.5%) were mixed homogeneously with 97.12 g of deionized water and 13.69 g of 50% KOH (solution A).

In parallel, a 3% solution of a mixture of sodium sulfite, the disodium salt of 2-hydroxy-2-sulfinatoacetic acid and the disodium salt of 2-hydroxy-2-sulfonatoacetic acid (Brüggolit FF6 Brüggemann GmbH) was prepared in water (solution B). With stirring and cooling, initially 47.1 g of solution A were added to the initial charge, and then 1.22 g of 3-mercaptopropionic acid (MPS) were added to the remaining solution A. Subsequently, 0.30 g of 3-mercaptopropionic acid and 0.047 g of ferrous sulfate heptahydrate (FeSO ₄ ) were successively added to the original solution. This was then adjusted with NaOH (50%) to a starting pH of 5.7. 0.3 ml of solution B was added to the template.

With the addition of 2.87 g of hydrogen peroxide (30% solution in water) to the initial mixture, the reaction was started. At the same time, the addition of solution A and solution B to the stirred original was started. Solution A was added over 45 minutes. Solution B was added in parallel at a constant metering rate of 18 ml / h until no more peroxide could be detected in the solution. Subsequently, the obtained polymer solution was adjusted to a pH of 6.5 with 50% sodium hydroxide solution. The resulting copolymer was obtained in a solution having a solids content of 40.9% by weight. The weight average molecular weight of the copolymer is 33,200 g / mol, the polydispersity 2.10.

Examples 2 and 3 were carried out analogously to Example 1, the amounts used are given in Tables 1 and 2. Table 1: Amounts used for the template for the synthesis of the water-soluble polymers of the invention.

Table 2: Amounts used for the synthesis of the water-soluble polymers of the invention.

[g] = grams; [ml] = milliliters; AS = acrylic acid 99.5%;

MPS = 3-mercaptopropionic acid; H ₂ 0 ₂ = 30%

Table 3: Overview of the analytical data.

^* Mw (average molecular weight) and PD (polydispersity) determined by gel permeation chromatography (GPC): Column combinations: Shodex OHpak SB 804HQ from Showa, Japan (polyhydroxy methacrylate gel, particle size 10 μm, pore size 2000 Å, plate count> 16,000, diameter and column length 8 mm x 300 mm) and Shodex OHpak 802.5HQ from Showa, Japan (polyhydroxy methacrylate gel, particle size 6 μηη, pore size 200 Å, plate number> 16,000, diameter and length of the column 8 mm × 300 mm); Eluent: 0.05 M ammonium formate / methanol (80/20% by volume), pH 6.5; Flow rate: 0.5 ml / min; Column temperature: 50 ° C; Detection: R1; Calibration: PEG / PEO standards in the range 10e6 - 10e2 g / mol. Example T1 (associate thickener):

189.9 g of Exsoll D100 (oil phase) were placed in a beaker and 12.2 g Span80 (Sigma-Aldrich) were dissolved therein. At the same time, in a second beaker, 219.8 g of a 50% strength aqueous solution of acrylamido-2-methylpropanesulfonic acid, Na salt were introduced and, subsequently, 4.1 g of HBVE-24.5EO-16BuO-3.5EO (monomer M1), 206, 9 g of acrylamide (50% solution in water), 0.5 g of tetraallyl ammonium chloride (2% solution in water), 0.8 g of a commercially available silicone-based defoamer (Dow Corning® Xiameter AFE-0400), and 0, 5 g of a 50% aqueous solution of diethylenetriaminepentaacetic acid, pentasodium salt added. After adjusting to pH 6.7 with a 10% sodium hydroxide solution and adding the remaining water to reach the monomer target concentration of 29% (on total water) was divided into 5 portions. These 5 portions were then independently homogenized in the oil phase on Silverston LM5-A (high shear emulsifier) first at 4000 rpm and in a second step at 8000 rpm. After emulsification, the emulsion was placed in a double wall reactor equipped with a stirrer , Thermometer and nitrogen inlet, filled and the emulsion was adjusted to the starting temperature of 15 ° C. The thermistor for temperature recording was attached and the emulsion was purged with nitrogen for 60 minutes. In each case 9 g of a 0.1% strength sodium bisulfite and a 0.1% strength tert-butyl hydroperoxide (tBHP) solution were prepared as an initiator and simultaneously metered in with a metering pump. The dosing rate was chosen so that a temperature increase of 1 ° C / min was reached up to a maximum temperature of 40 ° C, which was kept constant until the reaction was completed. At the end of the reaction, the emulsion was cooled to room temperature and a large amount of acetone was added, whereby a powder was obtained. This powder was separated and dried in an oven at 50 ° C. This gave a white powder, which could be used without further workup.

Examples T2 to T3 were carried out analogously to Example T1, wherein the amounts used in Tables 4 and 5 are shown. Comparative Examples P1 and P2 were as in WO

2016/079213 (WO 2016/079213, page 30, line 14 to page 31, line 8).

Table 4. Amounts used for the dispersed phase from the synthesis of thickeners of the invention.

a> 50% NaAMPS solution is used ^b> Xiameter AFE 0400, ^c> Dow Corning Anti-foam emulsion RD

AM = acrylamide

NaAMPS = sodium 2-acrylamido-2-methylpropanesulfonate

TAAC = tetra allyl ammonium chloride

HBVE = hydroxybutyl vinyl ether

Table 5. Use levels for the template for the synthesis of associative thickeners.

Average molecular weight of the associative thickener: 7,000,000 g / mol

The average molecular weight of the associative thickener was determined by the Mark-Houwink relationship (1), as already shown. The parameters K and α are not known for the present polymer-solvent pair. Therefore, the parameters for pure polyacrylamide in water were used (after J. Klein, K-D Conrad, Makromol Chem., 1980, 18, 227), i. K = 0.0049 and α = 0.8.

For the determination of intrinsic viscosity [η], a 0.5% solution of the copolymer in water was prepared. This was mixed with a buffer (1 g NaCl 16.66 + 32.26 g _Na2 HP04 ^* 12H ₂ 0 + 1, 795 g of Na2HP04 ^* H20 demineralized into 2 liters of water) diluted to a c = 0.01% polymer solution to obtain. This solution was analyzed with an Ubbelohde viscometer (at 20 ° C, Ubbelohde type 1 capillary). The intrinsic viscosity was over the turnaround time of the 0.01% polymer solution, using as reference the solvent without polymer.

The throughput time (t (polymer)) of the polymer solution was determined in comparison to the pure solvent (tuvi) as a reference (At = t (polymer) -ti_M). The intrinsic viscosity [η] can be calculated from this according to Solomon-Ciuta:

_ v 2 (v _re i _at i _v 1) 2Z v _reiat j ₁₇ ) _/ ^/

c V _re iativ - exv _reduced + 1

and Vreduced ⁼ / (cxt _LM )

The network formation of the associative thickener was tested on an Anton Paar rheometer, type MCR 302 with a plate-and-plate measuring cell. For this, 1% thickener solutions were prepared in the synthetic pore solution, which was then measured immediately afterwards. All samples were each measured by two methods, a displacement-dependent measurement to determine the "linear viscoelastic region", and a three-step measurement to test the network structure as a function of time, wherein in the first stage with low deflection (240 sec) Behavior under rest is studied, in the second stage under higher shear rate (10 or 100 or 1000 s ^_1 for 300 sec) the behavior under shear studied and in the last stage at deflection (30 min).

The compositions according to the table were tested as thickeners in pore solution with the rheometer. These solutions were used to determine the network parameters (memory and loss modulus), as these could be of interest for later network building in the application tests. FIG. 1 shows the memory modules of the associative thickeners T1, T2 and T3 according to the invention and those of the comparative examples P1 and P2. It can be seen that the non-linear thickeners show improved thickening performance. application testing

The application test was carried out in inert inorganic suspensions, the test system contained CaSC anhydrite. The water content was 23.1 wt .-%, based on the total weight of the suspension, which corresponds to a water binder value of 0.3. To liquefy the calcium sulfate flow line, a water-soluble polymer according to Table 3 was added. The content of the water-soluble polymer was selected based on the anhydrite content so that the calcium sulfate flow line without the addition of an associative thickener 5 min after addition of water, a flow rate at the SLU cone of 140 ± 5 mm.

The calcium sulfate mixture was prepared by mixing the anhydrite with the mixing water with the aid of an IKA stirrer. In the mixing water, the water-soluble polymers and thickeners were first dissolved. Thereafter, the anhydrite was treated with this water. and immediately thereafter, the low-speed mixing operation (240 revolutions per minute (rpm)) is started. After 30 seconds, the mixer was switched to a higher speed (600 rpm) and mixing continued for a further 30 seconds. Then the mixer was stopped for 30 seconds. After the break, the mixture was stirred for an additional 180 seconds at the higher mixing speed.

Immediately after the end of the mixing process, the flow was measured with the SLU 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 SLU cone (d top and bottom = 40 mm, h = 50 mm) was placed in the middle on a dry glass plate with a diameter of 200 mm and filled to the intended height with calcium sulfate anhydrite. Immediately after buffing, or 5 minutes after the initial contact of anhydrite and water, the SLU cone was withdrawn, held for 30 seconds over the divergent calcium sulfate anhydride, and then removed. Once the flow gauge came to a standstill, the diameter was determined with a caliper gauge on two orthogonal axes and the average calculated. The flow was tested to adjust all samples to the same flowable consistency by varying the level of water-soluble polymer as described above.

In addition, the yield strength and the behavior at rest and shear were determined with a rheometer from Anton Paar, type MCR 302, using a Vane measuring cell. The determination of the yield point should give information about a possible flocculation of the anhydrite particles. For this purpose, after mixing, the calcium sulfate anhydrite was introduced into the measuring vessel parallel to the test of the flow rate and this was inserted into the rotary rheometer. Immediately thereafter, the rheometer's measuring head was shut down, the internal rigid sensor of the measuring cell immersed in the sample in the measuring vessel, and the rheological measurement started at the age of 3 min. To degrade the rest structure, the sample was pre-treated for 30 s with a shear input of 200 Pa. The yield strength was determined by means of a shear stress-dependent measurement, whereby the deflection of the sample was measured over a shear stress range of 0.1 to 500 Pa, the yield point was then determined by the "Yield Stress II" method installed in the Anton Paar Rheometer The behavior at rest and under shear was tested by a three-step method, whereby in the first stage with low shear rate (10 S ^"1 ) the behavior is studied at rest. In the second stage, the shear behavior is studied with higher shear rates (500 s ^_1 ) and in the last stage the network reconstruction is tested with a low shear rate (10 s ^_1 ). Figures 2 and 3 show the apparent viscosity of the compositions.

To characterize the influence of the combination of the water-soluble polymer and the associative thickener on the robustness of the calcium sulfate anhydrite against sedimentation and bleeding (settling of water on the surface), 200 ml of the calcium sulfate flow-sheet after mixing into a glass cylinder having a diameter filled by 35 mm (See: A. Perrot et al., Cement and Concrete Research 42 (2012) p. 937-944). After resting for 30, 60 and 120 minutes, the height of the water film (blood water) on the surface of the calcium sulfate floating screed was measured. The higher the water film on the surface of the mortar, the lower the stabilizing effect of the associative thickener used. The results are summarized in Table 6.

Table 6: Results of the performance tests with PCE types

It can be seen that the combination of the associative thickeners T1 or T2 according to the invention and the various water-soluble polymers offers dosing advantages over the non-inventive associative thickeners P1 and P2. Table 7. Compositions of rheological measurements.

In addition, the viscosity difference between a calcium anhydrite suspension stabilized with a composition of the water-soluble polymer 1 and associative thickener T1 and a calcium anhydrite suspension stabilized compared with a composition of the water-soluble polymer 1 and associative thickener P1. It is important that under shear, the viscosity is as low as possible, because this ensures good processability. The measurements were carried out with 0.06% associative thickener with the same consistency (flow rate). The compositions are shown in Table 7, the results are shown in Figures 2 and 3.

It can be clearly seen that the viscosity of the suspension containing water-soluble polymer 1 and associative thickener T1 has a much lower viscosity (FIG. 2). A similar picture can be seen when associative thickener T1 was combined with the water-soluble polymer 3 (Figure 3).

Therefore, the use of non-linear associative thickeners not only provides a metering advantage, but also improved processability.

Claims

claims

Composition comprising

i) at least one water-soluble polymer (P), and

ii) at least one associative thickener (A) comprising a copolymer based on a) 0.1 to 35.0% by weight of at least one monomer of the formula (I)

H ₂ C = C (R ¹ ) -R ² -O - (- CH ₂ -CH ₂ -O) k - (- CH ₂ -CH (R ³ ) -O-) i - (- CH ₂ -CH ₂ -O-) _m -R ⁴ (I) where the units - (- CH ₂ -CH ₂ -O) _k -, - (- CH ₂ -CH (R ³ ) -O-) i- and - (CH ₂ -CH ₂ -O- ) m, if present, are arranged in block structure in the order shown in formula (I) and wherein

k for a number from 10 to 150,

I for a number from 1 to 25, and

m is a number from 0 to 16,

R ^{1 is} independently hydrogen or methyl,

R ² independently represents a direct bond or a divalent linking group selected from the group of - (C _n H ₂ n) -, -O- (Cn'H ₂ n ') - and -C (0) -O- (Cn "H ₂ n") -, where n, n 'and n "are each a natural number from 1 to 6,

R ^{3 is} a linear C 1-4 -alkyl radical or an ether group of the general formula -CH 2 -OR ^{3 '} , where R ^{3' is} a hydrocarbon radical having at least 2 carbon atoms and wherein R ^{3 is selected from} within the group - (-CH 2 -CH (R ³ ) -0-) i- may be the same or different,

based on the total weight of the associative thickener (A).

2. Composition according to claim 1, characterized in that the associative thickener (A) has a higher average molecular weight than the water-soluble polymer (P), wherein

i) the average molecular weight of the associative thickener (A) after the Mark Houwink

Relationship (1) is determined

where K = 0.0049, α = 0.8, [η] the intrinsic viscosity and M the average molecular weight, and ii) the average molecular weight of the water-soluble polymer (P) is determined by gel permeation chromatography.

Composition according to one of the preceding claims, characterized in that the radicals of the at least one monomer of the formula (I) have the meaning that k is a number from 23 to 26,

I a number from 14 to 22,

m is a number from 2 to 5,

R ^{1 is} hydrogen,

R ^{2 is} a divalent linking group -O- (Ο _η Ή2η) -, where n 'is 4,

R ^{3 is} a hydrocarbon radical having 2 carbon atoms, and

R ^{4 is} hydrogen.

Composition according to one of the preceding claims, characterized in that the at least one monomer having at least two ethylenically unsaturated groups is selected from the group consisting of N, N'-methylenebisacrylamide, N, N'Methylenbismethacrylamid, ethylene glycol divinyl ether, triethylene glycol divinyl ether, Cyclohexandioldivinylether, triallylamine , Tetraallylammonium chloride, tetraallyloxyethane, pentaerythritol triallyl ether, divinylbenzene, triallyl isocyanurate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, ethoxylated bisphenol A; diacrylate, ethoxylated bisphenol A dimethacrylate, ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate t, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, cyclopentadiene diacrylate, triallyl terephthalate, diallyl maleate, diallyl fumarate, trivinyl trimellitate, divinyl adipate, diallyl succinate and mixtures of these.

Composition according to any one of the preceding claims, characterized in that the at least one hydrophilic monomer is a sulphonic acid-containing monomer of the formula (II)

in which

Y is -O- or -NH-,

for hydrogen or methyl,

aryl,

n for 0 or 1, M is hydrogen, a metal cation or an ammonium cation and a is 1 or 1 / valency of the metal cation.

Composition according to one of the preceding claims, characterized in that the sulfonic acid-containing monomer of the formula (II) is selected from the group consisting of sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropylsulfonsäure, 2-acrylamido 2-methylpropanesulfonic acid (AMPS) or mixtures of these.

Composition according to one of the preceding claims, characterized in that the at least one associative thickener (A) at least one amide-containing monomer of the formula (III),

in which

R ^{9 is} hydrogen or methyl and

R ¹⁰ and R ¹¹ independently of one another represent hydrogen, linear or branched C 1

C 2 -C 6 -alkyl, C 6 -C -cycloalkyl or C 6 -C 14 -aryl, or N-vinylformamide.

Composition according to one of the preceding claims, characterized in that the at least one amide-containing monomer is selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N-ethylacrylamide, Ν , Ν-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-tert-butylacrylamide, N-vinylformamide or mixtures of these.

Composition according to any one of the preceding claims, characterized in that the at least one water-soluble polymer (P) is a copolymer of e) at least one monomer of the formula (IV)

10. The composition according to any one of the preceding claims, characterized in that it is in the acid group of at least one acid group comprising mono- mers is at least one of the group consisting of carboxy, phosphono, sulfino, sulfo, sulfamido, sulfoxy, sulfoalkyloxy, sulfinoalkyloxy and phosphonooxy group.

1 1. Composition according to any one of the preceding claims, characterized in that the water-soluble polymer (P)

a) 5.0 to 40.0 wt .-% of the at least one monomer of the formula (IV) and b) 5.0 to 95.0 wt .-% of at least one acid group comprising monomers, based on the total weight of the water-soluble polymer (P), contains.

Composition according to any one of the preceding claims, characterized in that it contains from 5.0 to 95.0% by weight of the at least one associative thickener (A) and from 5.0 to 95.0% by weight of the at least one water-soluble polymer ( P), based on the total weight of the composition.

13. A mixture comprising an inorganic binder and 0.01 to 10.0 wt .-% of a composition according to any one of claims 1 to 12, based on the dry mass of the mixture. 14. Use of a composition according to any one of claims 1 to 12 as a theological additive.