WO2018177908A1 - Stabilisateur bi-composant pour des suspensions inorganiques - Google Patents

Stabilisateur bi-composant pour des suspensions inorganiques Download PDF

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Publication number
WO2018177908A1
WO2018177908A1 PCT/EP2018/057398 EP2018057398W WO2018177908A1 WO 2018177908 A1 WO2018177908 A1 WO 2018177908A1 EP 2018057398 W EP2018057398 W EP 2018057398W WO 2018177908 A1 WO2018177908 A1 WO 2018177908A1
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monomer
water
formula
group
composition according
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PCT/EP2018/057398
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German (de)
English (en)
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Erik Gubbels
Meik Ranft
Nina Susanne HILLESHEIM
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C04B28/16—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements containing anhydrite, e.g. Keene's cement
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0061—Block (co-)polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0045—Polymers chosen for their physico-chemical characteristics
    • C04B2103/0062—Cross-linked polymers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0079—Rheology influencing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0082—Segregation-preventing agents; Sedimentation-preventing agents
    • C04B2103/0083—Bleeding-preventing agents

Definitions

  • 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,
  • fly ash metakaolin, silica fume
  • polycondensation products based on naphthalene or alkylnaphthalenesulfonic acids or sulfonic acid groups containing melamine-formaldehyde resins are known.
  • 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.
  • polycarboxylate ethers or derivatives thereof to the inorganic solid suspension in dissolved form.
  • the dispersant is metered directly into the mixing water.
  • stabilizers also referred to as anti-segregants, anti-blebs, or viscosity modifiers
  • Water-soluble non-ionic derivatives of polysaccharides 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.
  • rheological additives are synthetically produced nonionic cellulose and starch derivatives such as methylcellulose (MC), hydroxyethylcellulose (HEC), methylhydroxyethylcellulose (MHEC), methyl hydroxypropyl cellulose (MHPC).
  • polysaccharides such as welan gum, diutan gum and naturally occurring extractively isolated polysaccharides (hydrocolloids), such as alginates, xanthans, carrageenans, galactomannans, etc.
  • hydrocolloids such as alginates, xanthans, carrageenans, galactomannans, etc.
  • 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.
  • 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.
  • R x is typically H or CH 3
  • Ry is a major hydrocarbon radical, typically hydrocarbon radicals of 8 to 40 carbon atoms.
  • the literature mentions longer alkyl groups or a tristyrylphenyl group.
  • 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.
  • 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.
  • composition comprising i) at least one water-soluble polymer (P), and
  • At least one associative thickener (A) comprising a copolymer based on
  • n 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) - and -C (0) -O-
  • 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
  • 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.
  • the associative thickener (A) has a higher average molecular weight than the water-soluble polymer (P), wherein
  • 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.
  • 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
  • n is a number from 2 to 5
  • R 1 is hydrogen
  • R 2 is a divalent linking group -O- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, where n 'is 4,
  • R 3 is a hydrocarbon radical having 2 carbon atoms
  • R 4 is hydrogen
  • the at least one monomer having at least two ethylenically unsaturated groups is selected from the group consisting of ⁇ , ⁇ '-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, ethylene glycol dimethacrylate,
  • 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
  • n 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.
  • the at least one associative thickener (A) comprises at least one amide-containing monomer of the formula
  • R 9 is hydrogen or methyl
  • R 10 and R 11 independently of one another represent hydrogen, linear or branched C 1 -C 20 -alkyl
  • the at least one amide-containing monomer is selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, ⁇ , ⁇ -dimethylacrylamide, N-ethylacrylamide, ⁇ , ⁇ -diethylacrylamide, N-cyclohexylacrylamide, N- Benzylacrylamide, N-tert-butylacrylamide, N-vinylformamide or mixtures of these.
  • the at least one water-soluble polymer (P) is a copolymer of
  • 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 ,
  • the water-soluble polymer (P) contains
  • 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.
  • the present invention relates to the use of the composition described above as a rheological additive.
  • composition according to the invention contains at least one associative thickener (A), which is a copolymer based on
  • 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
  • n 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) - 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-,
  • R 4 independently of one another is hydrogen or a hydrocarbon radical having 1 to 24 carbon atoms
  • 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- ( ⁇ ⁇ ⁇ 2 ⁇ ') - and -C (O) -O- (C n "H2n")
  • n, n 'and n'' stand for a natural number from 1 to 6.
  • 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 -, more preferably -C (O) -O-CH 2 -CH 2 -.
  • the group R 2 is a group -O- ( ⁇ ⁇ ⁇ 2 ⁇ ) -
  • 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.
  • 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.
  • 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.
  • 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.
  • suitable radicals include n-propyl, n-butyl, n-pentyl, particularly preferably an ethyl radical or an n-propyl radical.
  • 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.
  • R 3 ' include n-propyl, n-butyl, n-pentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, n-decyl or phenyl.
  • 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 Pentylenoxy knewen or units of higher alkylene oxides, most preferably are butylene oxide or Pentylenoxyteilen.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • transition between blocks 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.
  • 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.
  • 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.
  • the blocks in addition to the corresponding units can have small amounts of other units (in particular other polyalkyleneoxy units).
  • 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-).
  • 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) - 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, 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.
  • 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, where n 'is 4; R 3 : is a hydrocarbon radical having 3 carbon atoms, in particular n-propyl; R 4 : is H.
  • 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, where n 'is 4; R 3 : is a hydrocarbon radical having 2 carbon atoms; R 4 : is H.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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-
  • 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 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 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.
  • 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.
  • APMS 2-acrylamido-2-methylpropanesulfonic acid
  • the associative thickener (A) furthermore comprises at least one monomer (c) which has at least two ethylenically unsaturated groups.
  • monomers which are also referred to as crosslinkers, gives the associative thickener (A) a slightly branched or crosslinked structure.
  • crosslinker components are ⁇ , ⁇ '-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 amine
  • 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
  • At least one monomer (c) which has at least two ethylenically unsaturated groups selected from the group consisting of triallylamine, tiallylmethylammonium chloride, tetraallylammonium chloride, ⁇ , ⁇ '-methylenebisacrylamide, tirethyleneglycol bismethacrylate, triethylene glycol bisacrylate, polyethylene glycol (400) bismethacrylate , Polyethylene glycol (400) bis-acrylate and mixtures of these.
  • tetraallylammonium chloride is particularly preferred.
  • crosslinkers may only be used in amounts such that a water-soluble associative thickener (A) is still obtained.
  • the associative thickener (A) 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
  • 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)
  • 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,
  • the at least one amide-containing monomer (d) is a monomer selected from the group consisting of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, ⁇ , ⁇ -dimethylacrylamide, N-ethylacrylamide, N , N-diethylacrylamide, N-cyclohexylacrylamide, N-benzylacrylamide, N-tert-butylacrylamide, N-vinylformamide or mixtures of these.
  • 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
  • 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).
  • 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.
  • gel polymerization is a special case of solution polymerization and is therefore included in this term.
  • 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.
  • 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.
  • 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.
  • 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.
  • a suitable release agent for this step.
  • the associative thickener (A) according to the invention is obtained as a powder.
  • 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.
  • 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 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
  • 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.
  • the water-soluble polymer (P) is a copolymer of
  • the ethylenically unsaturated monomer (f) is represented by at least one of the following general formulas from the group (V), (VI) and (VI I):
  • 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 .
  • organic amine radicals are preferably substituted ammonium groups constitutestik- 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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) acryloyloxyalkylphosphonklaren.
  • COOH groups such as acrylic acid or methacrylic
  • 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.
  • 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, wherein n 'is 4; R 3 : is a hydrocarbon radical having 1 or 2 carbon atoms; R 4 : is H.
  • 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, where n 'is 4; R 3 : is a hydrocarbon radical having 2 carbon atoms; R 4 : is H.
  • 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- ( ⁇ ⁇ ⁇ 2 ⁇ ) -, where n 'is 4;
  • 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
  • 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.
  • the further monomer building blocks of the water-soluble polymer (P) may possibly be at least one compound of the formula (IVa):
  • 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.
  • 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.
  • 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).
  • 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).
  • the water-soluble polymer (P) does not contain a monomer having more than one ethylenically unsaturated group.
  • 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.
  • water suitable 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.
  • 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.
  • 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, dimethylpolyprop
  • 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.
  • 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.
  • the polymerization can also be carried out under a protective gas atmosphere, preferably under nitrogen.
  • high-energy, electromagnetic radiation, mechanical energy or chemical polymerization initiators such as organic peroxides, for.
  • organic peroxides for.
  • azobisisobutyronitrile azobisamidopropyl hydrochloride and 2,2'-azobis (2-methylbutyronitrile) can be used.
  • inorganic peroxy compounds such as.
  • 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.
  • reducing agents for example sodium hydrogen sulfite, ascorbic acid, iron (II) sulfate
  • redox systems which contain as reducing component an aliphatic or aromatic sulfonic acid (eg benzenesulfonic acid, toluenesulfonic acid ) contain.
  • 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.
  • molecular weight regulator the usual compounds are used. Suitable known regulators are z.
  • alcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol and amyl alcohols, aldehydes, ketones, alkylthiols, such as.
  • 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.
  • 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.
  • the polymer according to the invention preferably meets the requirements of the industrial standard EN 934-2 (February 2002).
  • 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.
  • 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
  • the mixture according to the invention may in particular be pulverulent mixtures which are subsequently mixed with water.
  • 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.
  • 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 ,
  • 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.
  • 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 binder further additives or additives are added to adjust the dry mortar to the specific application.
  • additives or additives may, for example, be shrinkage reducers, expansion agents, accelerators, retarders, dispersants, defoamers, air entraining agents and corrosion inhibitors.
  • the mixture according to the invention may also be a self-leveling leveling compound.
  • 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.
  • the composition according to the invention is present in the form of a powder.
  • the composition according to the invention is preferably used in powder form.
  • the size distribution of the particles is selected such that the mean particle diameter is less than 100 ⁇ m and the proportion of particles having a particle diameter greater than 200 ⁇ m is less than 2% by weight.
  • Particular preference is given to those powders whose average particle diameter is less than 50 ⁇ m and the proportion of particles having a particle diameter greater than 100 ⁇ m smaller than
  • 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.
  • 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.”
  • 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.
  • synthetic gypsum can equally arise as a by-product of phosphoric acid or hydrofluoric acid production processes.
  • gypsum 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • alkali metal carbonates 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.
  • 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.
  • 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.
  • the mixture according to the invention has an average particle size between 0.1 and 1000 ⁇ m, particularly preferably between 1 and 200 ⁇ m.
  • the particle size is determined by laser diffractometry.
  • composition according to the invention is used 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.
  • 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 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.
  • KOMe potassium methoxide
  • BuO butylene oxide
  • Example 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.
  • Exsoll D100 oil phase
  • Span80 Sigma-Aldrich
  • 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.
  • Example 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
  • NaAMPS sodium 2-acrylamido-2-methylpropanesulfonate
  • TAAC tetra allyl ammonium chloride
  • HBVE hydroxybutyl vinyl ether
  • 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 intrinsic viscosity [ ⁇ ] can be calculated from this according to Solomon-Ciuta:
  • 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).
  • 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.
  • a water-soluble polymer according to Table 3 was added to liquefy the calcium sulfate flow line. 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • non-linear associative thickeners not only provides a metering advantage, but also improved processability.

Abstract

La présente invention concerne une composition comprenant au moins un polymère hydrosoluble et un épaississant associatif à base de monomères ayant des chaînes latérales polyéther spécifiques, des monomères comprenant des groupes acides et au moins un réticulant. La présente invention concerne en outre un mélange qui comprend un liant inorganique et la composition selon l'invention ainsi que l'utilisation de la composition selon l'invention comme additif rhéologique.
PCT/EP2018/057398 2017-03-30 2018-03-23 Stabilisateur bi-composant pour des suspensions inorganiques WO2018177908A1 (fr)

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WO1985003699A1 (fr) 1984-02-22 1985-08-29 Pyrament, Inc. Polymere mineral a forte resistance precoce
EP0705854A1 (fr) 1994-10-03 1996-04-10 Rhone-Poulenc Inc. Polymères utilisables comme agent épaississant sensible au Ph et monomères pour cela
WO2001096007A1 (fr) 2000-06-15 2001-12-20 Coatex S.A. Utilisation de copolymeres faiblement anioniques comme agent dispersant et/ou d'aide au broyage de suspension aqueuse de matieres minerales
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WO2014095621A1 (fr) 2012-12-17 2014-06-26 Basf Se Copolymères hydrosolubles à association hydrophobe comprenant de nouveaux monomères à association hydrophobe
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WO1985003699A1 (fr) 1984-02-22 1985-08-29 Pyrament, Inc. Polymere mineral a forte resistance precoce
EP0705854A1 (fr) 1994-10-03 1996-04-10 Rhone-Poulenc Inc. Polymères utilisables comme agent épaississant sensible au Ph et monomères pour cela
WO2001096007A1 (fr) 2000-06-15 2001-12-20 Coatex S.A. Utilisation de copolymeres faiblement anioniques comme agent dispersant et/ou d'aide au broyage de suspension aqueuse de matieres minerales
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WO2009019225A2 (fr) 2007-08-03 2009-02-12 Basf Se Dispersion d'épaississant associatif
US8362180B2 (en) 2009-05-20 2013-01-29 Basf Se Hydrophobically associating copolymers
WO2014095621A1 (fr) 2012-12-17 2014-06-26 Basf Se Copolymères hydrosolubles à association hydrophobe comprenant de nouveaux monomères à association hydrophobe
WO2015071584A1 (fr) * 2013-11-15 2015-05-21 Coatex Agent retenteur de fluidite pour compositions hydrauliques compatible avec agent reducteur d'eau de type polymere peigne
WO2016079213A1 (fr) 2014-11-20 2016-05-26 Basf Se Modificateur rhéologique pour suspensions minérales

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