WO2024051931A1 - Amino compound-containing dispersion powder compositions - Google Patents

Amino compound-containing dispersion powder compositions Download PDF

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WO2024051931A1
WO2024051931A1 PCT/EP2022/074769 EP2022074769W WO2024051931A1 WO 2024051931 A1 WO2024051931 A1 WO 2024051931A1 EP 2022074769 W EP2022074769 W EP 2022074769W WO 2024051931 A1 WO2024051931 A1 WO 2024051931A1
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ethylenically unsaturated
powder compositions
water
dispersion powder
acrylate
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PCT/EP2022/074769
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German (de)
French (fr)
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Markus Bannwarth
Benjamin ROSSBACH
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Wacker Chemie Ag
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Priority to PCT/EP2022/074769 priority Critical patent/WO2024051931A1/en
Publication of WO2024051931A1 publication Critical patent/WO2024051931A1/en

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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
    • C04B40/0042—Powdery mixtures
    • 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
    • C04B28/02—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 hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • 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
    • C04B2103/0057—Polymers chosen for their physico-chemical characteristics added as redispersable powders
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00025—Aspects relating to the protection of the health, e.g. materials containing special additives to afford skin protection
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials

Definitions

  • Dispersion powder compositions containing amino compounds Dispersion powder compositions containing amino compounds
  • the invention relates to water-redispersible dispersion powder compositions containing amino compounds, processes for their production and their use, in particular in coatings or adhesives, for example for the construction sector.
  • Water-redispersible polymer powders are generally obtained by drying aqueous polymer dispersions. Drying often takes place in the presence of drying aids, whereby a coating of drying aids can form around the polymer particles. During the drying process, drying aids can prevent the polymer particles from sticking together irreversibly during production, storage, transport and use in dry formulations. When dispersion powders are dispersed in water, the drying aid matrix dissolves again, so that the polymer particles are released again in the aqueous dispersion and are present in it with the particle size distribution of the initial dispersion.
  • dispersion powders are used in many construction chemical products, for example in coatings or adhesives, such as tile adhesives, fillers, leveling compounds, thermal insulation composite systems or joint mortars.
  • coatings or adhesives such as tile adhesives, fillers, leveling compounds, thermal insulation composite systems or joint mortars.
  • the advantage is that dispersion powders can be used in prefabricated, storable dry mixtures, if necessary together with hydraulic binders such as cement, which are only converted into the ready-to-use product immediately before use by adding water and mixing.
  • building material formulations are generally modified with a number of additives, for example polymer powders, thickeners, plasticizers, retarders, setting agents. accelerators, defoamers, air entraining agents or many others.
  • additives for example polymer powders, thickeners, plasticizers, retarders, setting agents. accelerators, defoamers, air entraining agents or many others.
  • aldehydes such as: B. Formaldehyde, acetaldehyde, propionaldehyde or higher homologues of the group of alkanals.
  • Such carbonyl compounds are generally reactive and are often classified as carcinogenic, which is why the emission of aldehyde and ketone compounds should be avoided in the formulation if possible. Otherwise, aldehydes or ketones can be released during the processing or use of the building material products and endanger the health of users on the construction site or consumers, especially indoor users in private and commercial environments.
  • aldehydes can be released in a fresh mortar with a high pH value by hydrolysis of residual vinyl ester monomers of long-chain carboxylic acids, which, due to their low volatility, are not always completely separated using conventional processes such as stripping.
  • dispersion powders per se do not represent a significant source of aldehyde or ketone, since any aldehyde or ketone components formed or introduced during their production by means of emulsion polymerization, for example from initiators such as sodium formaldehyde sulfoxylate, at the latest when the polymer dispersions are dried resulting dispersion powder composition can be removed.
  • the task was to provide measures with which the aldehyde or ketone concentration of building material formulations can be reduced during or after application.
  • water-redispersible dispersion powder compositions based on copolymers of a) vinyl acetate, b) ethylene, c) optionally auxiliary monomers and d) optionally further ethylenically unsaturated monomers, characterized in that certain amino compounds are contained and the auxiliary monomers c) and also the other ethylenically unsaturated monomers d) are each selected from specific groups.
  • US 6080806 recommends dispersion powder compositions of styrene-butadiene copolymers and amino acids to improve mechanical properties such as impact strength, flexibility or adhesive tensile strength.
  • the subject of US201727544 is aqueous dispersions that contain lysine as a crosslinker and crosslinkable copolymers of 1, 3-dicarbonyl monomers and other monomers.
  • US 6063865 A relates to a water-redispersible, crosslinkable powder composition containing a) 30 to 95 wt. -Parts of water-insoluble, film-forming polymers of ethylenically unsaturated monomers, with 0.5 to 10 wt.
  • -% of the monomers carry an aldehyde, keto, epoxide, isocyanate, carboxylic anhydride or aziridine group, b) 5 to 70 wt. -Parts of water-soluble, film-forming polymers and c) compounds with at least two functional groups present in salt form from the series of amines, hydrazides, hydroxylamine esters, aryl and alkyl hydrazines or hydrazones.
  • US20220135784 and US20100197831 relate to crosslinkable, water-redispersible polymer powder compositions containing vinyl ester polymers and epoxy Compounds and optionally crosslinking hardeners containing two or more amino groups.
  • the invention relates to water-redispersible dispersion powder compositions (dispersion powder compositions) based on copolymers of a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more further ethylenically unsaturated monomers, characterized in that one or more Amino compounds (nitrogen compounds) selected from the group comprising polyoxyalkyleneamines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H are included, where in the formula R-NR'H the radical R is a linear or branched, optionally substituted is a hydrocarbon radical with 1 to 20 carbon atoms and R 'is a hydrogen atom, an NH2 group or a carbonyl radical, with the proviso that the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids; ethylenically unsaturated carboxylic
  • the nitrogen compounds preferably contain one or more amino groups, more preferably 1 to 50 amino groups, even more preferably 1 to 10 amino groups, particularly preferred 1 to 5 amino groups, most preferably 1 to 3 amino groups and most preferably two amino groups.
  • the radical R of the compounds of the formula R-NR'H is preferably a linear or branched, optionally substituted hydrocarbon radical with 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms and particularly preferably 1 to 5 carbon atoms.
  • Preferred substituents of the radicals R are acid, amide, amine, alcohol, oxyalkylene, thiol or thioether groups, such as methylthioether radicals, or aromatic or heteroaromatic radicals, such as phenyl or imidazole radicals.
  • Preferred substituents of the radicals R are amine or acid groups, such as sulfonic acid or, preferably, carboxylic acid groups.
  • the radicals R preferably carry at least two substituents, in particular two substituents.
  • the radical R' is preferably a carbonyl radical and particularly preferably a hydrogen atom. Nitrogen compounds with a carbonyl radical as the radical R' are also referred to as amides. Carbonyl radicals preferably contain 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms and most preferably 1 to 5 carbon atoms.
  • Preferred compounds of the formula R-NR'H are aliphatic or aromatic amines and in particular amino acids.
  • aliphatic or aromatic amines examples include hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, tetraethylenepentamine, 1,2-diaminopropane, diproprenediamine, diethylaminopropylamine, phenylenediamine, isophoronediamine.
  • Natural amino acids in particular proteinogenic amino acids, are preferred.
  • the most preferred amino acids are glycine, aspartic acid, glutamic acid and especially lysine.
  • the nitrogen compounds of the formula R-NR'H have a molecular weight Mw of preferably ⁇ 500 g/mol, particularly preferably ⁇ 300 g/mol and most preferably ⁇ 200 g/mol.
  • the nitrogen compounds of the formula R-NR'H have a molecular weight Mw of preferably >50 g/mol and particularly preferably >75 g/mol.
  • Polyoxyalkylene amines are preferably polyoxyalkylenes which carry one or more amino groups, preferably 1 to three amino groups and particularly preferably two amino groups.
  • the polyoxyalkylene unit is preferably based on ethylene oxide (EO), propylene oxide (PO) and/or butylene oxide groups. Ethylene oxide (EO) and/or propylene oxide (PO) are more preferred.
  • Polyalkoxylene glycols preferably carry an amine group at one or particularly preferably at both chain ends.
  • Polyoxyalkylene amines are available, for example, under the trade name Jef famine R.
  • Polyethyleneimines are preferably polymers with the repeating structural unit -CH2-CH2-NH-. Such polyethyleneimines are commercially available, for example under the trade name Lupasol R from BASF SE.
  • Aliphatic polyamines are also generally known and are commercially available, for example, under the trade names Anquamine R or Epilink R or Epilox R hardener available.
  • the polyoxyalkyleneamines, polyethyleneimines and aliphatic polyamines have a molecular weight Mw of preferably ⁇ 1. 000 . 000 g/mol, more preferably ⁇ 500. 000 g/mol, even more preferably ⁇ 100. 000 g/mol, particularly preferably ⁇ 50. 000 g/mol and most preferably ⁇ 10. 000 g/mol.
  • the polyoxyalkyleneamines, polyethyleneimines and aliphatic polyamines have a molecular weight Mw of preferably >200 g/mol, particularly preferably >300 g/mol and most preferably >400 g/mol.
  • the nitrogen compounds can also be present in the form of salts, for example in the form of their ammonium salts, for example wise with acid groups, such as carboxylic acids, or halides as counterions.
  • Preferred nitrogen compounds are polyoxyalkyleneamines and compounds of the formula R-NR'H, especially amino acids.
  • the dispersion powder compositions preferably contain 0.1 to 30% by weight, more preferably 0.2 to 20% by weight, even more preferably 0.3 to 15% by weight, particularly preferably 0.3 to 12% by weight , most preferably 0.3 to 10% by weight, most preferably 0.3 to 3% by weight of nitrogen compounds, based on the total weight of the dispersion powder compositions.
  • the copolymers are based on a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more further ethylenically unsaturated monomers.
  • the dispersion powder compositions preferably contain 40 to 99% by weight, particularly preferably 50 to 95% by weight and most preferably 70 to 90% by weight of copolymers according to the invention, based on the total weight of the dispersion powder compositions.
  • the copolymers are based on vinyl acetate a), preferably 50 to ⁇ 100% by weight, particularly preferably 59.8 to 94% by weight and most preferably 68.5 to 90% by weight, based on the total weight of the copolymers.
  • the copolymers are based on preferably >0 to 50% by weight, particularly preferably 0.1 to 40% by weight and most preferably 1 to 30% by weight of ethylene b), based on the total weight of the copolymers.
  • the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid nitriles, preferably acrylonitrile; Acrylamide (CH2CHCONH2) ; ethylenically unsaturated sulfonic acids or their salts, preferably vinyl sulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid; ethylenically unsaturated silicon-functional monomers, such as acryloxypropyl tri (alkoxy) - and methacryloxypropyl tri (alkoxy) - silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, where the alkoxy groups can contain, for example, methoxy, ethoxy and ethoxypropylene glycol ether residues; and hydroxye
  • auxiliary monomers c) are ethylenically unsaturated acids, such as acrylic acid, methacrylic acid and vinyl sulfonic acid.
  • the auxiliary monomers c) are generally different from vinyl acetate a), ethylene b) and the optional further ethylenically unsaturated monomers d).
  • the copolymers are based on preferably 0 to 20% by weight, particularly preferably 0.1 to 10% by weight and most preferably 0.5 to 5% by weight of auxiliary monomers c), based on the total weight of the copolymers.
  • the other ethylene unsaturated monomers d) are selected from the group comprehensively methylacrylate, methyl-methacrylate, ethylacrylate, ethyl methacrylate, propylacrylate, propyl methacrate, n-butylacrylate, n-butyl methacrylate, 2- ethylhexylacrylate, norbornylate Ylaromats, especially styrene and vinyltoluole, and vinyl halides , like vinyl chloride.
  • Vinyl chloride, methyl methacrylate, n-butyl acrylate and styrene are particularly preferred. Vinyl chloride is most preferred.
  • the other ethylenically unsaturated monomers d) are generally different from vinyl acetate a), ethylene b) and the optional auxiliary monomers c).
  • the copolymers are based on preferably 0 to ⁇ 50% by weight, particularly preferably 0.1 to 40% by weight and most preferably 1 to 30% by weight of further ethylenically unsaturated monomers d), based on the total weight of the copolymers .
  • the copolymers preferably consist of units of vinyl acetate a), ethylene b), optionally auxiliary monomers c) and optionally further ethylenically unsaturated monomers d).
  • the copolymers particularly preferably consist of units of vinyl acetate a), ethylene b) and optionally further ethylenically unsaturated monomers d).
  • the monomer selection or the selection of the weight proportions of the comonomers is carried out in such a way that a glass transition temperature Tg of -50°C to +40°C, preferably -30°C to +35°C, generally results.
  • the glass transition temperature Tg of the polymers can be determined in a known manner using differential scanning calorimetry (DSC).
  • Tgn glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
  • the copolymers are preferably produced using the emulsion polymerization process.
  • Emulsion polymerization usually takes place in an aqueous medium.
  • the polymerization temperature is generally 40°C to 110°C, preferably 60°C to 95°C.
  • the copolymerization of gaseous comonomers such as ethylene, 1,3-butadiene or vinyl chloride can also be carried out under pressure, generally between 5 bar and 100 bar.
  • the polymerization can generally be initiated using the redox initiator combinations commonly used for emulsion polymerization.
  • the monomer turnover can be carried out as usual the initiator dosage can be controlled.
  • the initiators are generally added in total in such a way that continuous polymerization is ensured.
  • suitable oxidation initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, t-butyl hydroperoxide, potassium peroxodiphosphate, tert. -Butyl peroxopivalate, cumene hydroperoxide, azobisiso-butyronitrile.
  • the sodium, potassium and ammonium salts of peroxodisulfuric acid and hydrogen peroxide are preferred.
  • the initiators mentioned are generally used in an amount of 0.01 to 2.0% by weight, based on the total weight of the monomers.
  • Suitable reducing agents are, for example, the sulfites and bisulfites of alkali metals and ammonium, such as sodium sulfite, the derivatives of sulfoxylic acid such as zinc or alkali formaldehyde sulfoxylates, for example sodium hydroxymethane sulfinate (Brüggolite), and (iso-)ascorbic acid. Sodium hydroxymethanesulfinate and (iso-)ascorbic acid are preferred.
  • the amount of reducing agent is preferably 0.015 to 3% by weight, based on the total weight of the monomers.
  • oxidizing agents mentioned in particular the salts of peroxodisulphuric acid and hydrogen peroxide, can also be used solely as thermal initiators.
  • regulating substances can be used during the emulsion polymerization processes. If regulators are used, they are usually used in amounts between 0.001 and 5.0% by weight, based on the monomers to be polymerized, and metered separately or premixed with reaction components. Examples of such substances are n-dodecyl mercaptan, tert. -Dodecylmer-captan, mercaptopropionic acids or their alkali metal salts, methyl mercaptopropionate, isopropanol, phosphonic acid or their derivatives, phosphinic acid or their derivatives and acetaldehyde.
  • 2-Mercaptopropionic acid or tert-dodecyl mercaptan is preferably used.
  • Protective colloids optionally in combination with emulsifiers, can be used for stabilization. In the emulsion polymerization process, polymerization can also take place in the presence of emulsifiers. Preferred amounts of emulsifiers are 1 to 7 wt. -%, based on the total weight of the monomers.
  • emulsifiers are anionic, cationic or nonionic emulsifiers, such as anionic surfactants, in particular alkyl sulfates with a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic residue and up to 40 ethylene sulfates.
  • anionic surfactants in particular alkyl sulfates with a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic residue and up to 40 ethylene sulfates.
  • alkyl or alkylaryl sulfonates with 8 to 18 carbon atoms esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers with 8 to 40 ethylene oxide units.
  • Polymerization is particularly preferred in the absence of emulsifiers.
  • the aqueous dispersions and/or the polymer powders preferably do not contain any emulsifiers.
  • residual monomer can be removed using known methods, for example by post-polymerization initiated with a redox catalyst. Volatile residual monomers can also be removed by distillation, preferably under reduced pressure, and optionally with the passage or passage of inert carrier gases such as air, nitrogen or water vapor.
  • inert carrier gases such as air, nitrogen or water vapor.
  • copolymers obtainable in this way are preferably in the form of protective colloid-stabilized, aqueous dispersions.
  • the copolymers according to the invention are preferably protective colloid stabilized.
  • protective colloids are polyvinyl alcohols; polyvinyl acetals; polyvinylpyrrolidones; Polysaccharides in water-soluble form such as starches (amylose and amylopectin), Celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives, dextrins and cyclodextrins; Proteins such as casein or caseinate, soy protein, gelatin; lignin sulfonates; synthetic polymers such as poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxyl-functional comonomer units, poly(meth)acrylamide, polyvinylsulfonic acids and their water-soluble copolymers; Melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene maleic acid and vinyl ether maleic acid copolymers.
  • Partially saponified or fully saponified polyvinyl alcohols with a degree of hydrolysis of preferably 80 to 100 mol% are preferred. Particularly preferred are partially saponified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol%, in particular with a Höppler viscosity, in 4% aqueous solution of 1 to 30 mPas (Höppler method at 20 ° C, DIN 53015). Most preferred are polyvinyl alcohols with a degree of hydrolysis of 85 to 94 mol%, in particular with a Höppler viscosity, in 4% aqueous solution of 3 to 15 mPas (Höppler method at 20 ° C, DIN 53015).
  • the protective colloids mentioned are accessible using methods known to those skilled in the art. Protective colloids are contained in an amount of preferably 1 to 30% by weight, particularly preferably 3 to 20% by weight, based on the total weight of the copolymers.
  • the aqueous dispersions have a solids content of preferably 30 to 75% by weight, particularly preferably 45 to 70% by weight.
  • aqueous dispersions of the copolymers can be converted in a conventional manner into copolymers in the form of water-redispersible powders, analogous to, for example, described further below for drying to produce the dispersion powder compositions.
  • the water-redispersible dispersion powder compositions do not contain any compounds bearing epoxy groups. gen (epoxy compound). Epoxy compounds are harmful for solving the problem according to the invention.
  • epoxy compounds are epoxy resins.
  • An example of this are epoxy compounds of the bisphenol A type, that is, condensation products of bisphenol A and epichlorohydrin or methylepichlorohydrin.
  • Further examples are epoxy resins based on bisphenol-F, which generally contain a mixture of bisglycidyloxyphenylmethanes.
  • aliphatic epoxy compounds such as glycidyl ethers of aliphatic polyols, in particular butyl diglycidyl ether; cycloaliphatic epoxy resins such as vinylcyclohexane dioxide, dicyclopentadiene dioxide and 3, 4-epoxy-6-methyl-cyclohexyl-methyl; and heterocyclic epoxy compounds such as triglycidyl-isocyanurate.
  • epoxy resins are commercially available, for example the bisphenol A and bisphenol F types as Epilox R resins. It is particularly preferred not to contain epoxy resins of the bisphenol A type and bisphenol F type.
  • epoxide compounds are bisglycidyloxyphenylmethane, butyl diglycidyl ether, vinylcyclohexane dioxide, dicyclopentadiene dioxide, 3,4-epoxy-6-methyl-cyclohexyl-methyl and triglycidyl-isocyanurate.
  • Epoxy compounds also include free-radically polymerizable epoxy compounds with at least two epoxide groups per molecule.
  • the epoxy compounds can be aliphatic, aliphatic or aromatic in nature.
  • Another subject of the invention are processes for producing the water-redispersible dispersion powder compositions (dispersion powder compositions), characterized in that copolymers based on a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more others ethylenically unsaturated monomers and one or more amino compounds (nitrogen compounds) selected from the group comprising polyoxyalkyleneamines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H, where in the formula R-NR'H the radical R represents a linear or branched, optionally substituted hydrocarbon radical with 1 to 20 carbon atoms and R 'is a hydrogen atom, an NH2 group or a carbonyl radical, with the proviso that the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids; ethylenically unsaturated carboxylic acid n
  • the nitrogen compounds are generally mixed after the copolymers have been produced by polymerization.
  • the copolymers can be mixed with the nitrogen compounds, for example, before, during or after drying the aqueous dispersions of the copolymers (polymer dispersion).
  • the nitrogen compounds are preferably added before the aqueous polymer dispersion is dried.
  • one or more nitrogen compounds are preferably added to the aqueous polymer dispersions and the resulting mixtures are then dried.
  • one or more copolymers can also be used in the form of redispersed in water Barable powders can be mixed with one or more nitrogen compounds.
  • Drying aids are generally added to the aqueous dispersions.
  • the drying aid is used in a total amount of 0.5 to 30% by weight, in particular 5 to 20% by weight, based on the solids content of the aqueous dispersion.
  • the total amount of drying aid and protective colloid before the drying process is preferably 1 to 30% by weight, based on the solids content of the aqueous dispersion.
  • the aqueous dispersions can be dried, for example, by means of fluidized bed drying, freeze drying or spray drying.
  • the dispersions are preferably spray-dried.
  • Spray drying is carried out in conventional spray drying systems, whereby atomization can be carried out using single, dual or multi-substance nozzles or with a rotating disc.
  • the outlet temperature is generally selected in the range from 45°C to 120°C, preferably 60°C to 90°C, depending on the system, Tg of the resin and the desired degree of drying.
  • the viscosity of the food to be atomized is adjusted via the solids content so that a value of ⁇ 500 mPas (Brookfield viscosity at 20 revolutions and 23 ° C), preferably ⁇ 250 mPas, is obtained.
  • the solids content of the dispersion to be sprayed is preferably 30 to 75% by weight and particularly preferably 45 to 70% by weight.
  • Antifoam is preferably added during drying.
  • the polymer powder obtained can, for example, be equipped with one or more anti-blocking agents (anti-caking agents).
  • antiblocking agents are preferably added during or after drying, in particular during drying in the spray drying system.
  • Preferred polymer powders contain antiblocking agents, in particular 1 to 40% by weight. -%, based on the total weight of polymer components.
  • antiblocking agents are Ca or Mg carbonate, talc, gypsum, silica, kaolins such as metakaolin, silicates, preferably with particle sizes in the range from 10 nm to 10 pm.
  • additives can be added, for example during drying.
  • Other components of dispersion powder compositions contained in preferred embodiments are, for example, pigments, fillers, foam stabilizers, water repellents or cement plasticizers.
  • the dispersion powder compositions in particular the copolymers based on the monomers a), b), optionally c) and optionally d) according to the invention, preferably do not contain any reactive group which can react with the nitrogen compounds according to the invention, in particular their amino groups, for example in a pH value of 3 to 10 and/or temperatures up to 150 ° C or, for example, during spray drying. This is also helpful for a better solution to the problem according to the invention.
  • the copolymers according to the invention based on the monomers a), b), optionally c) and optionally d) preferably do not contain any monomer unit which is substituted with an aldehyde, keto, epoxide, isocyanate, carboxylic anhydride or aziridine group is, in particular not a monomer unit substituted with an epoxide group.
  • monomers containing aldehyde and keto groups are acrolein, vinyl methyl ketone, allyl acetoacetate, vinyl acetoacetate, vinyl or allyl bisacetoacetate and acetoacetylated hydroxyalkyl (meth)acrylates.
  • Examples of monomers containing epoxy groups are glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether and glycidyl allyl ether.
  • I were socyanate Examples include meta- and para-isopropenyl-alpha, alpha-dimethyl-benzyl isocyanate (TMI), 2-methyl-2-isocyanatopropyl methacrylate, whereby the isocyanate groups of the monomers mentioned can optionally also be blocked, for example with phenol, salicylic acid ester, ketoxime, Caprolactam, dialkyl malonic acid, alkyl acetoacetate, 2, 2-dimethyl-1, 3-dioxane-4, 6-dione.
  • anhydride comonomers are allyl succinic anhydride and maleic anhydride.
  • the copolymers particularly preferably contain no unit of monomers from the group comprising glycidyl (meth) acrylate, meta- and para-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate (TMI), allyl acetoacetate, acetoacetylated hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.
  • TMI alpha-dimethylbenzyl isocyanate
  • allyl acetoacetate acetoacetylated hydroxyethyl (meth) acrylate
  • hydroxypropyl (meth) acrylate Most preferably, the copolymers do not contain any glycidyl (meth)acrylate unit.
  • the dispersion powder compositions are particularly suitable for use in construction chemical products. They can be used alone or in combination with conventional polymer dispersions or dispersion powders.
  • Another subject of the invention are dry building material formulations based on one or more hydraulically setting binders, such as cement (Portland, aluminate, trass, metallurgical, magnesia, phosphate cement), gypsum and water glass; one or more dispersion powder compositions according to the invention; optionally one or more fillers, for example quartz sand, quartz powder, limestone powder, calcium carbonate, calcium magnesium carbonate (dolomite), chalk or white lime hydrate; and optionally one or more additives, such as crosslinkers, preservatives, film-forming aids, dispersants, foam stabilizers, plasticizers, flow agents, flame retardants, dyes or biocides.
  • binders such as cement (Portland, aluminate, trass, metallurgical, magnesia, phosphate cement), gypsum and water glass
  • one or more dispersion powder compositions according to the invention optionally one or more fillers, for example quartz sand, quartz powder, limestone
  • the dry building material formulations preferably contain 0.1 to 40% by weight, particularly preferably 0.3 to 25.0% by weight and most preferably 0.5 to 15% by weight of dissolutions according to the invention. persion powder compositions, each based on the total weight of the dry building material formulations.
  • the dry building material formulations contain, for example, >0 to 2.0% by weight, preferably >0 to 1.0% by weight, more preferably >0 to 0.5% by weight, even more preferably >0 to 0.3% by weight .-% and particularly preferably > 0 to 0.2% by weight of nitrogen compounds, based on the total weight of the dry building material formulations.
  • the dry building material formulations preferably contain 1 to 90% by weight, particularly preferably 5 to 45% by weight and most preferably 10 to 35% by weight of hydraulically setting binders, based on the total weight of the dry building material formulations.
  • the dry building material formulations preferably contain 10 to 99% by weight, particularly preferably 30 to 90% by weight and most preferably 50 to 85% by weight of fillers, based on the total weight of the dry building material formulations.
  • the building material formulations preferably contain 0.001 to 30% by weight, particularly preferably 0.01 to 8% by weight and most preferably 0.03 to 4% by weight of additives, based on the dry weight of the building material formulations.
  • Aldehydes or ketones which can be contained in the dry building material formulations, preferably contain 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms and most preferably 1 to 3 carbon atoms.
  • aldehydes examples include hexanal, propionaldehyde and especially formaldehyde and acetaldehyde.
  • An example of a ketone is acetone.
  • the building material dry formulations containing aldehydes and ketones preferably contain a total of ⁇ 1% by weight, or more preferably ⁇ 0.5% by weight, particularly preferably ⁇ 0.1% by weight, most preferably ⁇ 0.03% by weight and most preferably ⁇ 0.01% by weight of aldehydes and ketones on the total weight of the dry building material formulations.
  • the dry building material formulations can be produced in a conventional manner in conventional devices.
  • the amount of water required to process the dry building material formulations is usually added with mixing immediately before application.
  • the dry building material formulations are suitable, for example, for the production of reinforcing compounds for thermal insulation composite systems, or for the production of adhesives or coating materials.
  • adhesives are adhesives for thermal insulation panels and sound insulation panels, tile adhesives, grout and adhesives for bonding wood and wood-based materials.
  • coating materials are mortar, leveling and sealing compounds, screeds, plasters.
  • the aldehyde or ketone concentration in building material formulations can be reduced using the dispersion powder compositions according to the invention.
  • the polyvinyl alcohol had a degree of hydrolysis of 88 mol% and a Höppler viscosity of 4 mPas (in 4% aqueous solution).
  • Table 1 Composition of the dispersion powder compositions: a) based on the polymer content of the dispersion (solid/solid).
  • the building material formulations correspond to a tile adhesive of class C2S1 with 8% polymer binder and are structured as follows: Table 2: Composition of the building material formulations:
  • Aldehyde emissions were measured based on ISO 16000-3.
  • the mortar sample was placed in a laboratory mixer with 28 wt. -% water freshly mixed and spread evenly on a glass plate over an area of 0.096 m 2 using a smoothing spatula.
  • the target layer thickness was 3 mm.
  • the chamber was set to a temperature of 23 ⁇ 1 ° C and a humidity of 50 ⁇ 5% at an air exchange rate of 2L/min.
  • the aldehyde emissions were collected via a DNPH column and quantitatively determined using gas chromatography.

Abstract

The invention relates to water-redispersible dispersion powder compositions (dispersion powder compositions) based on copolymers of a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers, and d) optionally one or more additional ethylenically unsaturated monomers. The invention is characterized in that one or more amino compounds (nitrogen compounds) selected from the group comprising polyoxyalkylene amines, polyethylene imines, aliphatic polyamines, and compounds of the formula R-NR'H are contained, wherein in the formula R-NR'H, the group R represents a linear or branched and optionally substituted hydrocarbon group with 1 to 20 carbon atoms and R' is a hydrogen atom, an NH2 group, or a carbonyl group, with the proviso that the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids, ethylenically unsaturated carboxylic acid nitriles, acrylamide (CH2CHCONH2), ethylenically unsaturated sulfonic acids, ethylenically unsaturated silicon-functional monomers, and hydroxyethyl, hydroxypropyl, or hydroxybutyl acrylate or methacrylate; the additional ethylenically unsaturated monomers d) are selected from the group comprising methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatics, and vinyl halides; and the water-redispersible dispersion powder compositions do not contain epoxide group-containing compounds (epoxide compounds).

Description

Aminoverbindungen enthaltende Dispersionspulverzusammensetzungen Dispersion powder compositions containing amino compounds
Die Erfindung betri f ft in Wasser redispergierbare Dispersionspulverzusammensetzungen enthaltend Aminoverbindungen, Verfahren zu deren Herstellung sowie deren Verwendung insbesondere in Beschichtungs- oder Klebemitteln, beispielsweise für den Baubereich . The invention relates to water-redispersible dispersion powder compositions containing amino compounds, processes for their production and their use, in particular in coatings or adhesives, for example for the construction sector.
In Wasser redispergierbare Polymerpulver ( Dispersionspulver ) werden im Allgemeinen durch Trocknen wässriger Polymerdispersionen erhalten . Das Trocknen erfolgt häufig in Gegenwart von Trocknungshil fsmittel , wodurch sich eine Hülle aus Trocknungshil fsmittel um die Polymerteilchen ausbilden kann . Beim Trocknungsvorgang können Trocknungshil fsmittel verhindern, dass die Polymerteilchen im Laufe von Herstellung, Lagerung, Transport und Einsatz in Trockenformulierungen irreversibel verkleben . Beim Dispergieren von Dispersionspulvern in Wasser löst sich die Trocknungshil fsmittel-Matrix wieder auf , so dass in der wässrigen Dispersion die Polymerpartikel wieder freigesetzt werden und darin mit der Partikelgrößenverteilung der Ausgangsdispersion vorliegen . Water-redispersible polymer powders (dispersion powders) are generally obtained by drying aqueous polymer dispersions. Drying often takes place in the presence of drying aids, whereby a coating of drying aids can form around the polymer particles. During the drying process, drying aids can prevent the polymer particles from sticking together irreversibly during production, storage, transport and use in dry formulations. When dispersion powders are dispersed in water, the drying aid matrix dissolves again, so that the polymer particles are released again in the aqueous dispersion and are present in it with the particle size distribution of the initial dispersion.
Derartige Dispersionspulver werden in vielerlei bauchemischen Produkten eingesetzt , beispielsweise in Beschichtungs- oder Klebemitteln, wie Fliesenklebern, Spachtelmassen, Verlaufsmassen, Wärmedämmverbundsystemen oder Fugenmörteln . Von Vorteil ist , dass Dispersionspulver in vorgefertigten, lagerfähigen Trockenmischungen, gegebenenfalls zusammen mit hydraulischen Bindemitteln, wie Zement , eingesetzt werden können, die erst unmittelbar vor ihrer Anwendung durch Wasserzugabe und Durchmischung in das gebrauchs fertige Produkt überführt werden . Such dispersion powders are used in many construction chemical products, for example in coatings or adhesives, such as tile adhesives, fillers, leveling compounds, thermal insulation composite systems or joint mortars. The advantage is that dispersion powders can be used in prefabricated, storable dry mixtures, if necessary together with hydraulic binders such as cement, which are only converted into the ready-to-use product immediately before use by adding water and mixing.
Zur Verbesserung der Verarbeitungs- und anwendungstechnischen Eigenschaften werden Baustof f formulierungen im Allgemeinen mit einer Reihe von Additiven vergütet , beispielsweise mit Polymerpulvern, Verdickern, Verflüssigern, Verzögerern, Abbinde- beschleunigern, Entschäumern, Luftporenbildnern oder vielen anderen mehr . Nachteiliger Weise kann es vorkommen, dass so modi fi zierte Baustof f formulierungen niedermolekulare , leicht flüchtige und andere Gefahrstof fe freisetzen, darunter Ketone oder Alkanale , umgangssprachlich Aldehyde , wie z . B . Formaldehyd, Acetaldehyd, Propionaldehyd oder höhere Homologe der Gruppe der Alkanale . Solche Carbonylverbindungen sind generell reaktiv und viel fach als cancerogen eingestuft , weswegen die Emission von Aldehyd- und Ketonverbindungen möglichst bereits formulierungsseitig zu vermeiden ist . Andernfalls können Aldehyde oder Ketone während der Verarbeitung oder Nutzung der Baustof fprodukte freigesetzt werden und die Gesundheit von Anwendern auf der Baustelle oder Konsumenten, insbesondere den Nutzern in Innenräumen im privaten und gewerblichen Umfeld, gefährden . To improve the processing and application properties, building material formulations are generally modified with a number of additives, for example polymer powders, thickeners, plasticizers, retarders, setting agents. accelerators, defoamers, air entraining agents or many others. Disadvantageously, it can happen that building material formulations modified in this way release low molecular weight, highly volatile and other hazardous substances, including ketones or alkanals, commonly known as aldehydes, such as: B. Formaldehyde, acetaldehyde, propionaldehyde or higher homologues of the group of alkanals. Such carbonyl compounds are generally reactive and are often classified as carcinogenic, which is why the emission of aldehyde and ketone compounds should be avoided in the formulation if possible. Otherwise, aldehydes or ketones can be released during the processing or use of the building material products and endanger the health of users on the construction site or consumers, especially indoor users in private and commercial environments.
Allgemein können gewerbliche Compoundierer von Baustof f formulierungen gar nicht feststellen, welches Additiv die Aldehydoder Keton-Freisetzung verursacht . Die Verfahren zur qualitativen und quantitativen Bestimmung der leicht- bis mittelflüchtigen und niedermolekularen Chemikalien ist aufwändig und keine Standardanalysemethode . Erschwerend kommt hinzu, dass Aldehyd- beziehungsweise Ketonverunreinigungen auch erst nach Herstellung der Baustof f formulierungen durch chemische Umsetzungen aus Additiven freigesetzt werden können, so dass Reinigungsschritte bei der Herstellung der Additive die Aldehyd- beziehungsweise Ketonfreisetzungsproblematik nicht vollständig zu lösen vermögen . Beispielsweise können Aldehyde in einem Frischmörtel mit hohem pH-Wert durch Hydrolyse von Vinylester-Restmonomeren langkettiger Carbonsäuren freigesetzt werden, welche in Folge ihrer geringen Flüchtigkeit nach herkömmlichen Verfahren, wie Strippen, nicht immer vollständig abgetrennt werden . Generell stellen Dispersionspulver per se aber keine nennenswerte Aldehyd- oder Ketonquelle dar, da etwaige , bei ihrer Herstellung mittels Emulsionspolymerisation gebildete oder eingebrachte Aldehyd- oder Ketonanteile , beispielsweise aus Initiatoren, wie Natriumformaldehydsul foxylat , spätestens bei der Trocknung der Polymerdispersionen der resultierenden Dispersionspulverzusammensetzung entzogen werden . In general, commercial compounders of building material formulations cannot determine which additive causes the aldehyde or ketone release. The process for the qualitative and quantitative determination of the highly volatile and medium-volatile and low-molecular chemicals is complex and not a standard analysis method. What makes matters worse is that aldehyde or ketone impurities can only be released from additives through chemical reactions after the building material formulations have been produced, so that cleaning steps in the production of the additives cannot completely solve the aldehyde or ketone release problem. For example, aldehydes can be released in a fresh mortar with a high pH value by hydrolysis of residual vinyl ester monomers of long-chain carboxylic acids, which, due to their low volatility, are not always completely separated using conventional processes such as stripping. In general, dispersion powders per se do not represent a significant source of aldehyde or ketone, since any aldehyde or ketone components formed or introduced during their production by means of emulsion polymerization, for example from initiators such as sodium formaldehyde sulfoxylate, at the latest when the polymer dispersions are dried resulting dispersion powder composition can be removed.
Vor diesem Hintergrund bestand die Aufgabe , Maßnahmen bereitzustellen, mit denen die Aldehyd- oder Ketonkonzentration von Baustof f formulierungen während oder nach der Applikation reduziert werden kann . Against this background, the task was to provide measures with which the aldehyde or ketone concentration of building material formulations can be reduced during or after application.
Überraschenderweise wurde die Aufgabe im Wesentlichen gelöst mit in Wasser redispergierbaren Dispersionspulverzusammensetzungen basierend auf Copolymeren von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls Hil fsmonomeren und d) gegebenenfalls weiteren ethylenisch ungesättigten Monomeren, dadurch gekennzeichnet , dass bestimmte Aminoverbindungen enthalten sind und die Hil fsmonomere c ) und auch die weiteren ethylenisch ungesättigten Monomere d) j e aus bestimmten Gruppen ausgewählt sind . Surprisingly, the problem was essentially solved with water-redispersible dispersion powder compositions based on copolymers of a) vinyl acetate, b) ethylene, c) optionally auxiliary monomers and d) optionally further ethylenically unsaturated monomers, characterized in that certain amino compounds are contained and the auxiliary monomers c) and also the other ethylenically unsaturated monomers d) are each selected from specific groups.
Die US 6080806 empfiehlt Dispersionspulverzusammensetzungen von Styrol-Butadien-Copolymerisaten und Aminosäuren zur Verbesserung von mechanischen Eigenschaften, wie Schlagfestigkeit , Flexibilität oder Haf t Zugfestigkeit . Die US201727544 hat wässrige Dispersionen zum Gegenstand, die Lysin als Vernetzer sowie vernetzbare Copolymere von 1 , 3-Dicarbonylmonomeren und weiteren Monomeren enthalten . Die US 6063865 A betri f ft in Wasser redispergierbare , vernetzbare Pulverzusammenset zung enthaltend a ) 30 bis 95 Gew . -Teile wasserunlösliche , filmbildende Polymerisate von ethylenisch ungesättigten Monomeren, wobei 0 , 5 bis 10 Gew . -% der Monomere eine Aldehyd- , Keto- , Epoxid- , I socyanat- , Carbonsäureanhydrid- oder Aziridin-Gruppe tragen, b ) 5 bis 70 Gew . -Teile wasserlösliche , filmbildende Polymere sowie c ) Verbindungen mit mindestens zwei in Sal z form vorliegenden funktionellen Gruppen aus der Reihe der Amine , der Hydrazide , der Hydroxylaminester, der Aryl- und Alkyl- hydrazine oder -hydrazone . Die US20220135784 und US20100197831 betref fen vernetzbare , in Wasser redispergierbare Polymerpulver-Zusammensetzungen, die Vinylesterpolymere sowie Epoxid- Verbindungen und gegebenenfalls vernetzende Härter mit zwei oder mehr Aminogruppen enthalten . US 6080806 recommends dispersion powder compositions of styrene-butadiene copolymers and amino acids to improve mechanical properties such as impact strength, flexibility or adhesive tensile strength. The subject of US201727544 is aqueous dispersions that contain lysine as a crosslinker and crosslinkable copolymers of 1, 3-dicarbonyl monomers and other monomers. US 6063865 A relates to a water-redispersible, crosslinkable powder composition containing a) 30 to 95 wt. -Parts of water-insoluble, film-forming polymers of ethylenically unsaturated monomers, with 0.5 to 10 wt. -% of the monomers carry an aldehyde, keto, epoxide, isocyanate, carboxylic anhydride or aziridine group, b) 5 to 70 wt. -Parts of water-soluble, film-forming polymers and c) compounds with at least two functional groups present in salt form from the series of amines, hydrazides, hydroxylamine esters, aryl and alkyl hydrazines or hydrazones. US20220135784 and US20100197831 relate to crosslinkable, water-redispersible polymer powder compositions containing vinyl ester polymers and epoxy Compounds and optionally crosslinking hardeners containing two or more amino groups.
Gegenstand der Erfindung sind in Wasser redispergierbare Dispersionspulverzusammensetzungen ( Dispersionspulverzusammensetzungen) basierend auf Copolymeren von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls einem oder mehreren Hil fsmonomeren und d) gegebenenfalls einem oder mehreren weiteren ethylenisch ungesättigten Monomeren, dadurch gekennzeichnet , dass ein oder mehrere Amino-Verbindungen ( Stickstof fverbindungen) ausgewählt aus der Gruppe umfassend Polyoxyalkylenamine , Polyethylenimine , aliphatische Polyamine und Verbindungen der Formel R-NR 'H enthalten sind, wobei in der Formel R-NR 'H der Rest R für einen linearen oder verzweigten, gegebenenfalls substituierten Kohlenwasserstof frest mit 1 bis 20 Kohlenstof f atomen steht und R ' ein Wasserstof fatom, eine NH2-Gruppe oder ein Carbonylrest ist , mit der Maßgabe , dass die Hil fsmonomere c ) ausgewählt werden aus der Gruppe umfassend ethylenisch ungesättigte Mono- und Dicarbonsäuren; ethylenisch ungesättigte Carbonsäurenitrile ; Acrylamid ( CH2CHCONH2 ) ; ethylenisch ungesättigte Sul fonsäuren; ethylenisch ungesättigte siliciumfunktionelle Monomere ; und Hydroxyethyl- , Hydroxypropyl- oder Hydroxybutyl-Acrylat oder - methacrylat und die weiteren ethylenisch ungesättigten Monomere d) ausgewählt werden aus der Gruppe umfassend Methylacrylat , Methylmethac- rylat , Ethylacrylat , Ethylmethacrylat , Propylacrylat , Propyl- methacrylat , n-Butylacrylat , n-Butylmethacrylat , 2-Ethylhexyl- acrylat , Norbornylacrylat , Vinylaromaten und Vinylhalogenide und die in Wasser redispergierbaren Dispersionspulverzusammensetzungen keine Epoxid-Gruppen tragenden Verbindungen (Epoxid- Verbindungen) enthalten . The invention relates to water-redispersible dispersion powder compositions (dispersion powder compositions) based on copolymers of a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more further ethylenically unsaturated monomers, characterized in that one or more Amino compounds (nitrogen compounds) selected from the group comprising polyoxyalkyleneamines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H are included, where in the formula R-NR'H the radical R is a linear or branched, optionally substituted is a hydrocarbon radical with 1 to 20 carbon atoms and R 'is a hydrogen atom, an NH2 group or a carbonyl radical, with the proviso that the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; Acrylamide (CH2CHCONH2); ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate and the further ethylenically unsaturated monomers d) are selected from the group comprising methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate , 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatics and vinyl halides and the water-redispersible dispersion powder compositions do not contain any compounds bearing epoxy groups (epoxy compounds).
Die Stickstof fverbindungen enthalten vorzugsweise ein oder mehrere Aminogruppen, mehr bevorzugt 1 bis 50 Aminogruppen, noch mehr bevorzugt 1 bis 10 Aminogruppen, besonders bevorzugt 1 bis 5 Aminogruppen, am meisten bevorzugt 1 bis 3 Aminogruppen und am allermeisten bevorzugt zwei Aminogruppen . The nitrogen compounds preferably contain one or more amino groups, more preferably 1 to 50 amino groups, even more preferably 1 to 10 amino groups, particularly preferred 1 to 5 amino groups, most preferably 1 to 3 amino groups and most preferably two amino groups.
Der Rest R der Verbindungen der Formel R-NR 'H ist vorzugsweise ein linearer oder verzweigter, gegebenenfalls substituierter Kohlenwasserstof f rest mit 1 bis 15 Kohlenstof f atomen, vorzugsweise 1 bis 10 Kohlenstof f atomen und besonders bevorzugt 1 bis 5 Kohlenstof f atomen . The radical R of the compounds of the formula R-NR'H is preferably a linear or branched, optionally substituted hydrocarbon radical with 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms and particularly preferably 1 to 5 carbon atoms.
Bevorzugte Substituenten der Reste R sind Säure- , Amid- , Amin- , Alkohol- , Oxyalkylen- , Thiol- oder Thioether-Gruppen, wie Methylthioether-Reste , oder aromatische oder heteroaromatische Reste , wie Phenyl- oder Imidazol-Reste . Bevorzugte Substituenten der Reste R sind Amin- oder Säure-Gruppen, wie Sul fonsäure- oder vorzugsweise Carbonsäure-Gruppen . Vorzugsweise tragen die Reste R mindestens zwei Substituenten, insbesondere zwei Substituenten . Preferred substituents of the radicals R are acid, amide, amine, alcohol, oxyalkylene, thiol or thioether groups, such as methylthioether radicals, or aromatic or heteroaromatic radicals, such as phenyl or imidazole radicals. Preferred substituents of the radicals R are amine or acid groups, such as sulfonic acid or, preferably, carboxylic acid groups. The radicals R preferably carry at least two substituents, in particular two substituents.
Der Rest R ' steht vorzugsweise für einen Carbonylrest und besonders bevorzugt für ein Wasserstof f atom . Stickstof fverbindungen mit einem Carbonylrest als Rest R ' werden auch als Amide bezeichnet . Carbonylreste enthalten vorzugsweise 1 bis 20 Kohlenstof f atome , besonders bevorzugt 1 bis 10 Kohlenstof fatome und am meisten bevorzugt 1 bis 5 Kohlenstof f atome . The radical R' is preferably a carbonyl radical and particularly preferably a hydrogen atom. Nitrogen compounds with a carbonyl radical as the radical R' are also referred to as amides. Carbonyl radicals preferably contain 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms and most preferably 1 to 5 carbon atoms.
Bevorzugte Verbindungen der Formel R-NR 'H sind aliphatische oder aromatische Amine und insbesondere Aminosäuren . Preferred compounds of the formula R-NR'H are aliphatic or aromatic amines and in particular amino acids.
Beispiele für aliphatische oder aromatische Amine sind Hexamethylendiamin, Diethylentriamin, Tetraethylenpentamin, Tetraethylenpentamine , 1 , 2-Diaminopropan, Diproprendiamin, Diethyl- aminopropylamine , Phenylendiamin, I sophorondiamin . Examples of aliphatic or aromatic amines are hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, tetraethylenepentamine, 1,2-diaminopropane, diproprenediamine, diethylaminopropylamine, phenylenediamine, isophoronediamine.
Bevorzugt sind natürliche Aminosäuren, insbesondere proteinogene Aminosäuren . Am meisten bevorzugte Aminosäure sind Glycin, Asparaginsäure , Glutaminsäure und insbesondere Lysin . Die Stickstof fverbindungen der Formel R-NR 'H haben ein Molekulargewicht Mw von vorzugsweise < 500 g/mol , besonders bevorzugt < 300 g/mol und am meisten bevorzugt < 200 g/mol . Die Stickstof fverbindungen der Formel R-NR 'H haben ein Molekulargewicht Mw von vorzugsweise > 50 g/mol und besonders bevorzugt > 75 g/mol . Natural amino acids, in particular proteinogenic amino acids, are preferred. The most preferred amino acids are glycine, aspartic acid, glutamic acid and especially lysine. The nitrogen compounds of the formula R-NR'H have a molecular weight Mw of preferably <500 g/mol, particularly preferably <300 g/mol and most preferably <200 g/mol. The nitrogen compounds of the formula R-NR'H have a molecular weight Mw of preferably >50 g/mol and particularly preferably >75 g/mol.
Polyoxyalkylenamine sind vorzugsweise Polyoxyalkylene , die ein oder mehrere Aminogruppen, vorzugsweise 1 bis drei Aminogruppen und besonders bevorzugt zwei Aminogruppen tragen . Die Polyoxyalkylen-Einheit basiert hierbei vorzugsweise auf Ethylenoxid- (EO) , Propylenoxid- ( PO) und/oder Butylenoxid-Gruppen . Ethylenoxid- (EO) und/oder Propylenoxid- ( PO) sind mehr bevorzugt . Polyalkoxylenglykole tragen vorzugsweise an einem oder besonders bevorzugt an beiden Kettenenden eine Amingruppe .Polyoxyalkylene amines are preferably polyoxyalkylenes which carry one or more amino groups, preferably 1 to three amino groups and particularly preferably two amino groups. The polyoxyalkylene unit is preferably based on ethylene oxide (EO), propylene oxide (PO) and/or butylene oxide groups. Ethylene oxide (EO) and/or propylene oxide (PO) are more preferred. Polyalkoxylene glycols preferably carry an amine group at one or particularly preferably at both chain ends.
Polyoxyalkylenamine sind beispielsweise unter dem Handelsnamen Jef famineR erhältlich . Polyoxyalkylene amines are available, for example, under the trade name Jef famine R.
Polyethylenimine sind bevorzugt Polymere mit der sich wiederholenden Struktureinheit -CH2-CH2-NH- . Solche Polyethylenimine sind im Handel erhältlich, beispielsweise unter dem Handelsnamen LupasolR von der Firma BASF SE . Polyethyleneimines are preferably polymers with the repeating structural unit -CH2-CH2-NH-. Such polyethyleneimines are commercially available, for example under the trade name Lupasol R from BASF SE.
Auch aliphatische Polyamine sind allgemein bekannt und im Handel beispielsweise unter den Handelsnamen AnquamineR bzw . EpilinkR oder EpiloxR-Härter erhältlich . Aliphatic polyamines are also generally known and are commercially available, for example, under the trade names Anquamine R or Epilink R or Epilox R hardener available.
Die Polyoxyalkylenamine , Polyethylenimine und aliphatischen Polyamine haben ein Molekulargewicht Mw von vorzugsweise < 1 . 000 . 000 g/mol , mehr bevorzugt < 500 . 000 g/mol , noch mehr bevorzugt < 100 . 000 g/mol , besonders bevorzugt < 50 . 000 g/mol und am meisten bevorzugt < 10 . 000 g/mol . Die Polyoxyalkylenamine , Polyethylenimine und aliphatischen Polyamine haben ein Molekulargewicht Mw von vorzugsweise > 200 g/mol , besonders bevorzugt > 300 g/mol und am meisten bevorzugt > 400 g/mol . The polyoxyalkyleneamines, polyethyleneimines and aliphatic polyamines have a molecular weight Mw of preferably <1. 000 . 000 g/mol, more preferably <500. 000 g/mol, even more preferably <100. 000 g/mol, particularly preferably <50. 000 g/mol and most preferably <10. 000 g/mol. The polyoxyalkyleneamines, polyethyleneimines and aliphatic polyamines have a molecular weight Mw of preferably >200 g/mol, particularly preferably >300 g/mol and most preferably >400 g/mol.
Die Stickstof fverbindungen können auch in Form von Sal zen vorliegen, beispielsweise in Form ihrer Ammoniumsal ze , beispiels- weise mit Säuregruppen, wie Carbonsäuren, oder Halogeniden als Gegenion . The nitrogen compounds can also be present in the form of salts, for example in the form of their ammonium salts, for example wise with acid groups, such as carboxylic acids, or halides as counterions.
Bevorzugte Stickstoffverbindungen sind Polyoxyalkylenamine und Verbindungen der Formel R-NR'H, insbesondere Aminosäuren. Preferred nitrogen compounds are polyoxyalkyleneamines and compounds of the formula R-NR'H, especially amino acids.
Die Dispersionspulverzusammensetzungen enthalten vorzugsweise 0,1 bis 30 Gew.-%, mehr bevorzugt 0,2 bis 20 Gew.-%, noch mehr bevorzugt 0,3 bis 15 Gew.-%, besonders bevorzugt 0,3 bis 12 Gew.-%, am meisten bevorzugt 0,3 bis 10 Gew.-% am allermeisten bevorzugt 0,3 bis 3 Gew.-% Stickstoffverbindungen, bezogen auf das Gesamtgewicht der Dispersionspulverzusammensetzungen. The dispersion powder compositions preferably contain 0.1 to 30% by weight, more preferably 0.2 to 20% by weight, even more preferably 0.3 to 15% by weight, particularly preferably 0.3 to 12% by weight , most preferably 0.3 to 10% by weight, most preferably 0.3 to 3% by weight of nitrogen compounds, based on the total weight of the dispersion powder compositions.
Die Copolymere basieren auf a) Vinylacetat, b) Ethylen, c) gegebenenfalls einem oder mehreren Hilfsmonomeren und d) gegebenenfalls einem oder mehreren weiteren ethylenisch ungesättigten Monomeren. The copolymers are based on a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more further ethylenically unsaturated monomers.
Die Dispersionspulverzusammensetzungen enthalten vorzugsweise 40 bis 99 Gew.-%, besonders bevorzugt 50 bis 95 Gew.-% und am meisten bevorzugt 70 bis 90 Gew.-% an erfindungsgemäßen Copolymeren, bezogen auf das Gesamtgewicht der Dispersionspulverzusammensetzungen . The dispersion powder compositions preferably contain 40 to 99% by weight, particularly preferably 50 to 95% by weight and most preferably 70 to 90% by weight of copolymers according to the invention, based on the total weight of the dispersion powder compositions.
Die Copolymere basieren zu vorzugsweise 50 bis < 100 Gew.-%, besonders bevorzugt 59,8 bis 94 Gew.-% und am meisten bevorzugt 68,5 bis 90 Gew.-% auf Vinylacetat a) , bezogen auf das Gesamtgewicht der Copolymere. The copolymers are based on vinyl acetate a), preferably 50 to <100% by weight, particularly preferably 59.8 to 94% by weight and most preferably 68.5 to 90% by weight, based on the total weight of the copolymers.
Die Copolymere basieren zu vorzugsweise > 0 bis 50 Gew.-%, besonders bevorzugt 0,1 bis 40 Gew.-% und am meisten bevorzugt 1 bis 30 Gew.-% auf Ethylen b) , bezogen auf das Gesamtgewicht der Copolymere. The copolymers are based on preferably >0 to 50% by weight, particularly preferably 0.1 to 40% by weight and most preferably 1 to 30% by weight of ethylene b), based on the total weight of the copolymers.
Die Hilfsmonomere c) werden ausgewählt aus der Gruppe umfassend ethylenisch ungesättigte Mono- und Dicarbonsäuren, vorzugsweise Acrylsäure, Methacrylsäure, Fumarsäure und Maleinsäure; ethylenisch ungesättigte Carbonsäurenitrile, vorzugsweise Acrylnitril; Acrylamid (CH2CHCONH2) ; ethylenisch ungesättigte Sulfonsäuren bzw. deren Salze, vorzugsweise Vinyl sulfonsäure, 2-Acrylamido-2-methyl-propansulf onsäure ; ethylenisch ungesättigte siliciumfunktionelle Monomere, wie Acryloxypropyltri ( alkoxy ) - und Methacryloxypropyltri ( alkoxy ) - Silane, Vinyltrialkoxysilane und Vinylmethyldialkoxysilane, wobei als Alkoxygruppen beispielsweise Methoxy-, Ethoxy- und Ethoxypropylenglykolether-Reste enthalten sein können; und Hydroxyethyl- , Hydroxypropyl- oder Hydroxybutylacrylat oder - methacrylat . The auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated carboxylic acid nitriles, preferably acrylonitrile; Acrylamide (CH2CHCONH2) ; ethylenically unsaturated sulfonic acids or their salts, preferably vinyl sulfonic acid, 2-acrylamido-2-methyl-propanesulfonic acid; ethylenically unsaturated silicon-functional monomers, such as acryloxypropyl tri (alkoxy) - and methacryloxypropyl tri (alkoxy) - silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, where the alkoxy groups can contain, for example, methoxy, ethoxy and ethoxypropylene glycol ether residues; and hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate.
Besonders bevorzugte Hilfsmonomere c) sind ethylenisch ungesättigte Säuren, wie Acrylsäure, Methacrylsäure und Vinylsulfonsäure . Particularly preferred auxiliary monomers c) are ethylenically unsaturated acids, such as acrylic acid, methacrylic acid and vinyl sulfonic acid.
Die Hilfsmonomere c) sind generell von Vinylacetat a) , Ethylen b) und den optionalen weiteren ethylenisch ungesättigten Monomeren d) verschieden. The auxiliary monomers c) are generally different from vinyl acetate a), ethylene b) and the optional further ethylenically unsaturated monomers d).
Die Copolymere basieren zu vorzugsweise 0 bis 20 Gew.-%, besonders bevorzugt 0,1 bis 10 Gew.-% und am meisten bevorzugt 0,5 bis 5 Gew.-% auf Hilfsmonomeren c) , bezogen auf das Gesamtgewicht der Copolymere. The copolymers are based on preferably 0 to 20% by weight, particularly preferably 0.1 to 10% by weight and most preferably 0.5 to 5% by weight of auxiliary monomers c), based on the total weight of the copolymers.
Die weiteren ethylenisch ungesättigten Monomeren d) werden ausgewählt aus der Gruppe umfassend Methylacrylat , Methyl- methacrylat, Ethylacrylat , Ethylmethacrylat , Propylacrylat , Propylmethacrylat , n-Butylacrylat , n-Butylmethacrylat , 2- Ethylhexylacrylat , Norbornylacrylat , Vinylaromaten, insbesondere Styrol und Vinyltoluol, und Vinylhalogenide, wie Vinylchlorid. Besonders bevorzugt sind Vinylchlorid, Methyl- methacrylat, n-Butylacrylat und Styrol. Am meisten bevorzugt ist Vinylchlorid. The other ethylene unsaturated monomers d) are selected from the group comprehensively methylacrylate, methyl-methacrylate, ethylacrylate, ethyl methacrylate, propylacrylate, propyl methacrate, n-butylacrylate, n-butyl methacrylate, 2- ethylhexylacrylate, norbornylate Ylaromats, especially styrene and vinyltoluole, and vinyl halides , like vinyl chloride. Vinyl chloride, methyl methacrylate, n-butyl acrylate and styrene are particularly preferred. Vinyl chloride is most preferred.
Die weiteren ethylenisch ungesättigten Monomeren d) sind generell von Vinylacetat a) , Ethylen b) und den optionalen Hilfsmonomere c) verschieden. Die Copolymere basieren zu vorzugsweise 0 bis < 50 Gew.-%, besonders bevorzugt 0,1 bis 40 Gew.-% und am meisten bevorzugt 1 bis 30 Gew.-% auf weiteren ethylenisch ungesättigten Monomeren d) , bezogen auf das Gesamtgewicht der Copolymere. The other ethylenically unsaturated monomers d) are generally different from vinyl acetate a), ethylene b) and the optional auxiliary monomers c). The copolymers are based on preferably 0 to <50% by weight, particularly preferably 0.1 to 40% by weight and most preferably 1 to 30% by weight of further ethylenically unsaturated monomers d), based on the total weight of the copolymers .
Die Copolymere bestehen vorzugsweise aus Einheiten von Vinylacetat a) , Ethylen b) , gegebenenfalls Hilfsmonomeren c) und gegebenenfalls weiteren ethylenisch ungesättigten Monomeren d) . Besonders bevorzugt bestehen die Copolymere auf Einheiten von Vinylacetat a) , Ethylen b) und gegebenenfalls weiteren ethylenisch ungesättigten Monomeren d) . The copolymers preferably consist of units of vinyl acetate a), ethylene b), optionally auxiliary monomers c) and optionally further ethylenically unsaturated monomers d). The copolymers particularly preferably consist of units of vinyl acetate a), ethylene b) and optionally further ethylenically unsaturated monomers d).
Die Monomerauswahl bzw. die Auswahl der Gewichtsanteile der Comonomere erfolgt dabei so, dass im Allgemeinen eine Glasübergangstemperatur Tg von -50°C bis +40°C, vorzugsweise -30°C bis +35°C resultiert. Die Glasübergangstemperatur Tg der Polymerisate kann in bekannter Weise mittels Differential Scanning Calorimetry (DSC) ermittelt werden. Die Tg kann auch mittels der Fox-Gleichung näherungsweise vorausberechnet werden. Nach Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) gilt: 1/Tg = xl/Tgl + x2/Tg2 + . . . + xn/Tgn, wobei xn für den Massebruch (Gew.-%/100) des Monomeren n steht, und Tgn die Glasübergangstemperatur in Kelvin des Homopolymeren des Monomeren n ist. Tg-Werte für Homopolymerisate sind in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) aufgeführt. The monomer selection or the selection of the weight proportions of the comonomers is carried out in such a way that a glass transition temperature Tg of -50°C to +40°C, preferably -30°C to +35°C, generally results. The glass transition temperature Tg of the polymers can be determined in a known manner using differential scanning calorimetry (DSC). The Tg can also be approximately calculated using the Fox equation. After Fox T. G., Bull. Am. Physics Soc. 1, 3, page 123 (1956) applies: 1/Tg = xl/Tgl + x2/Tg2 + . . . + xn/Tgn, where xn is the mass fraction (% by weight/100) of the monomer n, and Tgn is the glass transition temperature in Kelvin of the homopolymer of the monomer n. Tg values for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).
Die Herstellung der Copolymere erfolgt vorzugsweise nach dem Emulsionspolymerisationsverfahren. Die Emulsionspolymerisation erfolgt üblicherweise in wässrigem Medium. Die Polymerisationstemperatur beträgt im Allgemeinen 40°C bis 110°C, vorzugsweise 60°C bis 95°C. Bei der Copolymerisation von gasförmigen Comonomeren wie Ethylen, 1,3-Butadien oder Vinylchlorid kann auch unter Druck, im Allgemeinen zwischen 5 bar und 100 bar, gearbeitet werden. The copolymers are preferably produced using the emulsion polymerization process. Emulsion polymerization usually takes place in an aqueous medium. The polymerization temperature is generally 40°C to 110°C, preferably 60°C to 95°C. The copolymerization of gaseous comonomers such as ethylene, 1,3-butadiene or vinyl chloride can also be carried out under pressure, generally between 5 bar and 100 bar.
Die Initiierung der Polymerisation kann generell mit den für die Emulsionspolymerisation gebräuchlichen Redox-Initiator- Kombinationen erfolgen. Der Monomerumsatz kann wie üblich mit der Initiatordosierung gesteuert werden. Die Initiatoren werden im Allgemeinen insgesamt so zudosiert, dass eine kontinuierliche Polymerisation gewährleistet ist. Beispiele für geeignete Oxidationsinitiatoren sind die Natrium-, Kalium- und Ammoniumsalze der Peroxodischwef elsäure, Wasserstoffperoxid, t-Butylperoxid, t-Butylhydroperoxid, Kaliumperoxodiphos- phat, tert . -Butylperoxopivalat , Cumolhydroperoxid, Azobisiso- butyronitril . Bevorzugt werden die Natrium-, Kalium- und Ammoniumsalze der Peroxodischwef elsäure und Wasserstoffperoxid.The polymerization can generally be initiated using the redox initiator combinations commonly used for emulsion polymerization. The monomer turnover can be carried out as usual the initiator dosage can be controlled. The initiators are generally added in total in such a way that continuous polymerization is ensured. Examples of suitable oxidation initiators are the sodium, potassium and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, t-butyl hydroperoxide, potassium peroxodiphosphate, tert. -Butyl peroxopivalate, cumene hydroperoxide, azobisiso-butyronitrile. The sodium, potassium and ammonium salts of peroxodisulfuric acid and hydrogen peroxide are preferred.
Die genannten Initiatoren werden im Allgemeinen in einer Menge von 0,01 bis 2,0 Gew.-%, bezogen auf das Gesamtgewicht der Monomere, eingesetzt. The initiators mentioned are generally used in an amount of 0.01 to 2.0% by weight, based on the total weight of the monomers.
Geeignete Reduktionsmittel sind beispielsweise die Sulfite und Bisulfite der Alkalimetalle und von Ammonium, wie Natriumsulfit, die Derivate der Sulfoxylsäure wie Zink- oder Alkaliform- aldehydsulfoxylate, beispielsweise Natriumhydroxymethansulf i- nat (Brüggolit) , und ( Iso- ) Ascorbinsäure . Bevorzugt werden Natriumhydroxymethansulf inat, und ( Iso- ) Ascorbinsäure . Die Reduktionsmittelmenge beträgt vorzugsweise 0,015 bis 3 Gew.-%, bezogen auf das Gesamtgewicht der Monomere. Suitable reducing agents are, for example, the sulfites and bisulfites of alkali metals and ammonium, such as sodium sulfite, the derivatives of sulfoxylic acid such as zinc or alkali formaldehyde sulfoxylates, for example sodium hydroxymethane sulfinate (Brüggolite), and (iso-)ascorbic acid. Sodium hydroxymethanesulfinate and (iso-)ascorbic acid are preferred. The amount of reducing agent is preferably 0.015 to 3% by weight, based on the total weight of the monomers.
Die genannten Oxidationsmittel, insbesondere die Salze der Peroxodischwef elsäure sowie Wasserstoffperoxid, können auch alleinig als thermische Initiatoren eingesetzt werden. The oxidizing agents mentioned, in particular the salts of peroxodisulphuric acid and hydrogen peroxide, can also be used solely as thermal initiators.
Zur Steuerung des Molekulargewichts können während der Emulsionspolymerisationsverfahren regelnde Substanzen eingesetzt werden. Falls Regler eingesetzt werden, werden diese üblicherweise in Mengen zwischen 0,001 bis 5,0 Gew.-%, bezogen auf die zu polymerisierenden Monomeren, eingesetzt und separat oder auch vorgemischt mit Reaktionskomponenten dosiert. Beispiele solcher Substanzen sind n-Dodecylmercaptan, tert . -Dodecylmer- captan, Mercaptopropionsäuren oder deren Alkalisalze, Mercaptopropionsäuremethylester, Isopropanol, Phosphonsäure oder deren Derivate, Phosphinsäure oder deren Derivate und Acetaldehyd. Vorzugsweise wird 2-Mercaptopropionsäure oder tert.- Dodecylmercaptan verwendet. Zur Stabilisierung können Schutzkolloide , gegebenenfalls in Kombination mit Emulgatoren, eingesetzt werden . Im Emulsionspolymerisationsverfahren kann auch in Gegenwart von Emulgatoren polymerisiert werden . Bevorzugte Mengen an Emulgatoren sind 1 bis 7 Gew . -% , bezogen auf das Gesamtgewicht der Monomere . Beispiele für Emulgatoren sind anionische , kationische oder nichtionische Emulgatoren, wie anionische Tenside , insbesondere Alkylsul fate mit einer Kettenlänge von 8 bis 18 C- Atomen, Alkyl- oder Alkylarylethersul fate mit 8 bis 18 C- Atomen im hydrophoben Rest und bis zu 40 Ethylen- oder Propylenoxideinheiten, Alkyl- oder Alkylarylsul fonate mit 8 bis 18 C-Atomen, Ester und Halbester der Sul fobernsteinsäure mit einwertigen Alkoholen oder Alkylphenolen, oder nichtionische Tenside wie Alkylpolyglykolether oder Alkylarylpolyglykolether mit 8 bis 40 Ethylenoxid-Einheiten . To control the molecular weight, regulating substances can be used during the emulsion polymerization processes. If regulators are used, they are usually used in amounts between 0.001 and 5.0% by weight, based on the monomers to be polymerized, and metered separately or premixed with reaction components. Examples of such substances are n-dodecyl mercaptan, tert. -Dodecylmer-captan, mercaptopropionic acids or their alkali metal salts, methyl mercaptopropionate, isopropanol, phosphonic acid or their derivatives, phosphinic acid or their derivatives and acetaldehyde. 2-Mercaptopropionic acid or tert-dodecyl mercaptan is preferably used. Protective colloids, optionally in combination with emulsifiers, can be used for stabilization. In the emulsion polymerization process, polymerization can also take place in the presence of emulsifiers. Preferred amounts of emulsifiers are 1 to 7 wt. -%, based on the total weight of the monomers. Examples of emulsifiers are anionic, cationic or nonionic emulsifiers, such as anionic surfactants, in particular alkyl sulfates with a chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic residue and up to 40 ethylene sulfates. or propylene oxide units, alkyl or alkylaryl sulfonates with 8 to 18 carbon atoms, esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers with 8 to 40 ethylene oxide units.
Besonders bevorzugt wird in Abwesenheit von Emulgatoren polymerisiert . Die wässrigen Dispersionen und/oder die Polymerpulver enthalten vorzugsweise keine Emulgatoren . Polymerization is particularly preferred in the absence of emulsifiers. The aqueous dispersions and/or the polymer powders preferably do not contain any emulsifiers.
Nach Abschluss der Polymerisation kann zur Restmonomerentfernung in Anwendung bekannter Methoden nachpolymerisiert werden, beispielsweise durch mit Redoxkatalysator initiierter Nachpolymerisation . Flüchtige Restmonomere können auch mittels Destillation, vorzugsweise unter reduziertem Druck, und gegebenenfalls unter Durchleiten oder Überleiten von inerten Schleppgasen wie Luft , Stickstof f oder Wasserdampf entfernt werden . After completion of the polymerization, residual monomer can be removed using known methods, for example by post-polymerization initiated with a redox catalyst. Volatile residual monomers can also be removed by distillation, preferably under reduced pressure, and optionally with the passage or passage of inert carrier gases such as air, nitrogen or water vapor.
Die so erhältlichen Copolymere liegen vorzugsweise in Form von Schutzkolloid stabilisierten, wässrigen Dispersionen vor . Die erfindungsgemäßen Copolymere sind vorzugsweise Schutzkolloid stabilisiert . The copolymers obtainable in this way are preferably in the form of protective colloid-stabilized, aqueous dispersions. The copolymers according to the invention are preferably protective colloid stabilized.
Beispiele für Schutzkolloide sind Polyvinylalkohole ; Polyvinylacetale ; Polyvinylpyrrolidone ; Polysaccharide in wasserlöslicher Form wie Stärken (Amylose und Amylopectin) , Cellulosen und deren Carboxymethyl-, Methyl-, Hydroxyethyl- , Hydroxypropyl-Derivate, Dextrine und Cyclodextrine; Proteine wie Kasein oder Kaseinat, Sojaprotein, Gelatine; Ligninsul- fonate; synthetische Polymere wie Poly (meth) acrylsäure, Copo- lymerisate von (Meth) acrylaten mit carboxylfunktionellen Comonomereinheiten, Poly (meth) acrylamid, Polyvinylsulfonsäuren und deren wasserlöslichen Copolymere; Melaminformaldehydsulfo- nate, Naphthalinformaldehydsulfonate, Styrolmaleinsäure- und Vinylethermaleinsäure-Copolymere . Examples of protective colloids are polyvinyl alcohols; polyvinyl acetals; polyvinylpyrrolidones; Polysaccharides in water-soluble form such as starches (amylose and amylopectin), Celluloses and their carboxymethyl, methyl, hydroxyethyl, hydroxypropyl derivatives, dextrins and cyclodextrins; Proteins such as casein or caseinate, soy protein, gelatin; lignin sulfonates; synthetic polymers such as poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxyl-functional comonomer units, poly(meth)acrylamide, polyvinylsulfonic acids and their water-soluble copolymers; Melamine formaldehyde sulfonates, naphthalene formaldehyde sulfonates, styrene maleic acid and vinyl ether maleic acid copolymers.
Bevorzugt sind teilverseifte oder vollverseifte Polyvinylalkohole mit einem Hydrolysegrad von vorzugsweise 80 bis 100 Mol-%. Besonders bevorzugt sind teilverseifte Polyvinylalkohole mit einem Hydrolysegrad von 80 bis 95 Mol-%, insbesondere mit einer Höpplerviskosität, in 4 %-iger wässriger Lösung von 1 bis 30 mPas (Methode nach Höppler bei 20°C, DIN 53015) . Am meisten bevorzugt werden Polyvinylalkohole mit einem Hydrolysegrad von 85 bis 94 Mol-%, insbesondere mit einer Höpplerviskosität, in 4 %-iger wässriger Lösung von 3 bis 15 mPas (Methode nach Höppler bei 20°C, DIN 53015) . Die genannten Schutzkolloide sind mittels des Fachmanns bekannter Verfahren zugänglich. Schutzkolloide sind in einer Menge von vorzugsweise 1 bis 30 Gew.-%, besonders bevorzugt 3 bis 20 Gew.-%, bezogen auf das Gesamtgewicht der Copolymerisate enthalten. Partially saponified or fully saponified polyvinyl alcohols with a degree of hydrolysis of preferably 80 to 100 mol% are preferred. Particularly preferred are partially saponified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol%, in particular with a Höppler viscosity, in 4% aqueous solution of 1 to 30 mPas (Höppler method at 20 ° C, DIN 53015). Most preferred are polyvinyl alcohols with a degree of hydrolysis of 85 to 94 mol%, in particular with a Höppler viscosity, in 4% aqueous solution of 3 to 15 mPas (Höppler method at 20 ° C, DIN 53015). The protective colloids mentioned are accessible using methods known to those skilled in the art. Protective colloids are contained in an amount of preferably 1 to 30% by weight, particularly preferably 3 to 20% by weight, based on the total weight of the copolymers.
Die wässrigen Dispersionen haben einen Feststoff gehalt von vorzugsweise 30 bis 75 Gew.-%, besonders bevorzugt von 45 bis 70 Gew.-%. The aqueous dispersions have a solids content of preferably 30 to 75% by weight, particularly preferably 45 to 70% by weight.
Die wässrigen Dispersionen der Copolymere können auf an sich herkömmliche Weise in Copolymere in Form von in Wasser redis- pergierbaren Pulvern überführt werden, analog wie beispielsweise weiter unten für die Trocknung zur Herstellung der Dispersionspulverzusammensetzungen beschrieben . The aqueous dispersions of the copolymers can be converted in a conventional manner into copolymers in the form of water-redispersible powders, analogous to, for example, described further below for drying to produce the dispersion powder compositions.
Die in Wasser redispergierbaren Dispersionspulverzusammensetzungen enthalten keine Epoxid-Gruppen tragenden Verbindun- gen (Epoxid-Verbindung) . Epoxid-Verbindungen sind zum Lösen der erfindungsgemäßen Aufgabe schädlich . The water-redispersible dispersion powder compositions do not contain any compounds bearing epoxy groups. gen (epoxy compound). Epoxy compounds are harmful for solving the problem according to the invention.
Beispiele für Epoxid-Verbindungen sind Epoxidharze . Ein Beispiel hierfür sind Epoxid-Verbindungen vom Bisphenol-A-Typ, das heißt Kondensationsprodukte von Bisphenol-A und Epichlorhydrin oder Methylepichlorhydrin . Weitere Beispiele sind Epoxidharze auf Basis von Bisphenol-F, welche im Allgemeinen eine Mischung von Bisglycidyloxyphenylmethanen enthalten . Weitere Beispiele sind aliphatische Epoxidverbindungen wie Glycidyl- ether von aliphatischen Polyolen, insbesondere der Butyldigly- cidylether ; cycloaliphatische Epoxidharze wie Vinylcyclohexandioxid, Dicyclopentadiendioxid und 3 , 4-Epoxy- 6-methyl-cyclohe- xyl-methyl ; und heterocyclische Epoxidverbindungen wie Trigly- cidyl- I socyanurat . Derartige Epoxidharze sind im Handel erhältlich, beispielsweise die Bisphenol-A- und Bisphenol-F- Typen als EpiloxR-Harze . Besonders bevorzugt sind keine Epoxidharze vom Bisphenol-A-Typ und Bisphenol-F-Typ enthalten . Examples of epoxy compounds are epoxy resins. An example of this are epoxy compounds of the bisphenol A type, that is, condensation products of bisphenol A and epichlorohydrin or methylepichlorohydrin. Further examples are epoxy resins based on bisphenol-F, which generally contain a mixture of bisglycidyloxyphenylmethanes. Further examples are aliphatic epoxy compounds such as glycidyl ethers of aliphatic polyols, in particular butyl diglycidyl ether; cycloaliphatic epoxy resins such as vinylcyclohexane dioxide, dicyclopentadiene dioxide and 3, 4-epoxy-6-methyl-cyclohexyl-methyl; and heterocyclic epoxy compounds such as triglycidyl-isocyanurate. Such epoxy resins are commercially available, for example the bisphenol A and bisphenol F types as Epilox R resins. It is particularly preferred not to contain epoxy resins of the bisphenol A type and bisphenol F type.
Weitere Beispiele für Epoxid-Verbindungen sind Bisglycidyloxy- phenylmethan, Butyldiglycidylether , Vinylcyclohexandioxid, Dicyclopentadiendioxid, 3 , 4-Epoxy- 6-methyl-cyclohexyl-methyl und Triglycidyl- I socyanurat . Further examples of epoxide compounds are bisglycidyloxyphenylmethane, butyl diglycidyl ether, vinylcyclohexane dioxide, dicyclopentadiene dioxide, 3,4-epoxy-6-methyl-cyclohexyl-methyl and triglycidyl-isocyanurate.
Epoxid-Verbindungen umfassen auch radikalisch polymerisierbare Epoxidverbindungen mit mindestens zwei Epoxidgruppen pro Molekül . Die Epoxid-Verbindungen können aliphatischer, aliphatischer oder aromatischer Natur sein . Epoxy compounds also include free-radically polymerizable epoxy compounds with at least two epoxide groups per molecule. The epoxy compounds can be aliphatic, aliphatic or aromatic in nature.
Ein weiterer Gegenstand der Erfindung sind Verfahren zur Herstellung der in Wasser redispergierbaren Dispersionspulverzusammensetzungen ( Dispersionspulverzusammensetzungen) , dadurch gekennzeichnet , dass Copolymere auf Basis von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls einem oder mehreren Hil fsmonomeren und d) gegebenenfalls einem oder mehreren weiteren ethylenisch ungesättigten Monomeren und ein oder mehrere Amino-Verbindungen ( Stickstof fverbindungen) ausgewählt aus der Gruppe umfassend Polyoxyalkylenamine , Polyethylenimine , aliphatische Polyamine und Verbindungen der Formel R-NR 'H gemischt werden, wobei in der Formel R-NR 'H der Rest R für einen linearen oder verzweigten, gegebenenfalls substituierten Kohlenwasserstof f rest mit 1 bis 20 Kohlenstof f atomen steht und R ' ein Wasserstof f atom, eine NH2-Gruppe oder ein Carbonylrest ist , mit der Maßgabe , dass die Hil fsmonomere c ) ausgewählt werden aus der Gruppe umfassend ethylenisch ungesättigte Mono- und Dicarbonsäuren; ethylenisch ungesättigte Carbonsäurenitrile ; Acrylamid ( CH2CHCONH2 ) ; ethylenisch ungesättigte Sul fonsäuren; ethylenisch ungesättigte siliciumfunktionelle Monomere ; und Hydroxyethyl- , Hydroxypropyl- oder Hydroxybutylacrylat oder - methacrylat und die weiteren ethylenisch ungesättigten Monomere d) ausgewählt werden aus der Gruppe umfassend Methylacrylat , Methylmethac- rylat , Ethylacrylat , Ethylmethacrylat , Propylacrylat , Propyl- methacrylat , n-Butylacrylat , n-Butylmethacrylat , 2-Ethylhexyl- acrylat , Norbornylacrylat , Vinylaromaten und Vinylhalogenide und in die in Wasser redispergierbaren Dispersionspulverzusammensetzungen keine Epoxid-Gruppen tragenden Verbindungen (Epoxid- Verbindung) eingebracht werden . Another subject of the invention are processes for producing the water-redispersible dispersion powder compositions (dispersion powder compositions), characterized in that copolymers based on a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more others ethylenically unsaturated monomers and one or more amino compounds (nitrogen compounds) selected from the group comprising polyoxyalkyleneamines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H, where in the formula R-NR'H the radical R represents a linear or branched, optionally substituted hydrocarbon radical with 1 to 20 carbon atoms and R 'is a hydrogen atom, an NH2 group or a carbonyl radical, with the proviso that the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; Acrylamide (CH2CHCONH2); ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate and the further ethylenically unsaturated monomers d) are selected from the group comprising methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2 -Ethylhexyl acrylate, norbornyl acrylate, vinyl aromatics and vinyl halides and no compounds bearing epoxy groups (epoxy compound) are introduced into the water-redispersible dispersion powder compositions.
Das Mischen der Stickstof fverbindungen erfolgt allgemein nach der Herstellung der Copolymere mittels Polymerisation . The nitrogen compounds are generally mixed after the copolymers have been produced by polymerization.
Das Mischen der Copolymere mit den Stickstof fverbindungen kann beispielsweise vor, während oder nach dem Trocknen der wässrigen Dispersionen der Copolymere ( Polymerdispersion) erfolgen . Bevorzugt erfolgt die Zugabe der Stickstof fverbindungen vor der Trocknung der wässrigen Polymerdispersion . Dazu werden vorzugsweise ein oder mehrere Stickstof fverbindungen den wässrigen Polymerdispersionen zugegeben und anschließend die so erhaltenen Mischungen getrocknet . Alternativ können auch ein oder mehrere Copolymere in Form von in Wasser redispergier- baren Pulvern mit einer oder mehreren Stickstoffverbindungen gemischt werden. The copolymers can be mixed with the nitrogen compounds, for example, before, during or after drying the aqueous dispersions of the copolymers (polymer dispersion). The nitrogen compounds are preferably added before the aqueous polymer dispersion is dried. For this purpose, one or more nitrogen compounds are preferably added to the aqueous polymer dispersions and the resulting mixtures are then dried. Alternatively, one or more copolymers can also be used in the form of redispersed in water Barable powders can be mixed with one or more nitrogen compounds.
Den wässrigen Dispersionen wird im Allgemeinen Trocknungshilfsmittel zugesetzt. In der Regel wird das Trocknungshilfsmittel in einer Gesamtmenge von 0,5 bis 30 Gew.-%, insbesondere 5 bis 20 Gew.-%, bezogen auf den Feststoff gehalt der wässrigen Dispersion, eingesetzt. Die Gesamtmenge an Trocknungshilfsmittel und Schutzkolloid vor dem Trocknungsvorgang beträgt vorzugsweise 1 bis 30 Gew.-%, bezogen auf den Feststoffgehalt der wässrigen Dispersion. Drying aids are generally added to the aqueous dispersions. As a rule, the drying aid is used in a total amount of 0.5 to 30% by weight, in particular 5 to 20% by weight, based on the solids content of the aqueous dispersion. The total amount of drying aid and protective colloid before the drying process is preferably 1 to 30% by weight, based on the solids content of the aqueous dispersion.
Das Trocknen der wässrigen Dispersionen kann beispielsweise mittels Wirbelschichttrocknung, Gefriertrocknung oder Sprühtrocknung erfolgen. Vorzugsweise werden die Dispersionen sprühgetrocknet. Die Sprühtrocknung erfolgt dabei in üblichen Sprühtrocknungsanlagen, wobei die Zerstäubung mittels Ein-, Zwei- oder Mehrstoffdüsen oder mit einer rotierenden Scheibe erfolgen kann. Die Austrittstemperatur wird im Allgemeinen im Bereich von 45°C bis 120°C, bevorzugt 60°C bis 90°C, je nach Anlage, Tg des Harzes und gewünschtem Trocknungsgrad, gewählt. Die Viskosität der zu verdüsenden Speise wird über den Feststoffgehalt so eingestellt, dass ein Wert von < 500 mPas (Brookf ield-Viskosität bei 20 Umdrehungen und 23°C) , bevorzugt < 250 mPas, erhalten wird. Der Feststoff gehalt der zu verdüsenden Dispersion beträgt vorzugsweise 30 bis 75 Gew.-% und besonders bevorzugt 45 bis 70 Gew.-%. The aqueous dispersions can be dried, for example, by means of fluidized bed drying, freeze drying or spray drying. The dispersions are preferably spray-dried. Spray drying is carried out in conventional spray drying systems, whereby atomization can be carried out using single, dual or multi-substance nozzles or with a rotating disc. The outlet temperature is generally selected in the range from 45°C to 120°C, preferably 60°C to 90°C, depending on the system, Tg of the resin and the desired degree of drying. The viscosity of the food to be atomized is adjusted via the solids content so that a value of <500 mPas (Brookfield viscosity at 20 revolutions and 23 ° C), preferably <250 mPas, is obtained. The solids content of the dispersion to be sprayed is preferably 30 to 75% by weight and particularly preferably 45 to 70% by weight.
Vielfach hat sich ein Gehalt von bis zu 1,5 Gew.-% Antischaummittel, bezogen auf das Copolymerisat , als günstig erwiesen. Antischaummittel wird vorzugsweise bei der Trocknung zugegeben . In many cases, a content of up to 1.5% by weight of antifoam, based on the copolymer, has proven to be beneficial. Antifoam is preferably added during drying.
Zur Erhöhung der Lagerf ähigkeit durch Verbesserung der Verblockungsstabilität, insbesondere bei Copolymeren mit niedriger Glasübergangstemperatur, kann das erhaltene Polymerpulver beispielsweise mit einem oder mehreren Antiblockmitteln (Antibackmittel) ausgerüstet werden. Die Antiblockmittel werden vorzugsweise während oder nach der Trocknung, insbesondere während der Trocknung in die Sprühtrocknungsanlage zugegeben . Bevorzugte Polymerpulver enthalten Antiblockmittel , insbesondere 1 bis 40 Gew . -% , bezogen auf das Gesamtgewicht polymerer Bestandteile . Beispiele für Antiblockmittel sind Ca- bzw . Mg- Carbonat , Talk, Gips , Kieselsäure , Kaoline wie Metakaolin, Silicate , vorzugsweise mit Teilchengrößen im Bereich von 10 nm bis 10 pm . In order to increase the storage stability by improving the blocking stability, especially in copolymers with a low glass transition temperature, the polymer powder obtained can, for example, be equipped with one or more anti-blocking agents (anti-caking agents). The antiblocking agents are preferably added during or after drying, in particular during drying in the spray drying system. Preferred polymer powders contain antiblocking agents, in particular 1 to 40% by weight. -%, based on the total weight of polymer components. Examples of antiblocking agents are Ca or Mg carbonate, talc, gypsum, silica, kaolins such as metakaolin, silicates, preferably with particle sizes in the range from 10 nm to 10 pm.
Zur Verbesserung der anwendungstechnischen Eigenschaften können weitere Zusätze zugegeben werden, beispielsweise bei der Trocknung . Weitere , in bevorzugten Aus führungs formen enthaltene Bestandteile von Dispersionspulverzusammensetzungen sind beispielsweise Pigmente , Füllstof fe , Schaumstabilisatoren, Hydrophobierungsmittel oder Zementverflüssiger . To improve the application properties, further additives can be added, for example during drying. Other components of dispersion powder compositions contained in preferred embodiments are, for example, pigments, fillers, foam stabilizers, water repellents or cement plasticizers.
Die Dispersionspulverzusammensetzungen, insbesondere die Copolymere auf Basis der erfindungsgemäßen Monomere a ) , b ) , gegebenenfalls c ) und gegebenenfalls d) , enthalten vorzugsweise keine reaktive Gruppe , die mit den erfindungsgemäßen Stickstof fverbindungen, insbesondere deren Amino-Gruppen, reagieren können, beispielsweise bei einem pH-Wert von 3 bis 10 und/oder Temperaturen bis 150 ° C oder beispielsweise während der Sprühtrocknung . Auch dies ist zur besseren Lösung der erfindungsgemäßen Aufgabe hil freich . The dispersion powder compositions, in particular the copolymers based on the monomers a), b), optionally c) and optionally d) according to the invention, preferably do not contain any reactive group which can react with the nitrogen compounds according to the invention, in particular their amino groups, for example in a pH value of 3 to 10 and/or temperatures up to 150 ° C or, for example, during spray drying. This is also helpful for a better solution to the problem according to the invention.
Die erfindungsgemäßen Copolymere auf Basis der Monomere a ) , b ) , gegebenenfalls c ) und gegebenenfalls d) enthalten vorzugsweise keine Monomer-Einheit , die mit einer Aldehyd- , Keto- , Epoxid- , I socyanat- , Carbonsäureanhydrid- oder Aziridin-Gruppe substituiert ist , insbesondere keine mit einer Epoxid-Gruppe substituierte Monomer-Einheit . Beispiele für Aldehyd- und Ketogruppen enthaltende Monomere sind Acrolein, Vinylmethylketon, Acetessigsäureallylester, Acetessigsäurevinylester, Vinyl- oder Allylbisacetoacetat und acetoacetylierte Hydroxyalkyl (meth) acrylate . Beispiele für epoxygruppenhaltige Monomere sind Glycidylacrylat , Glycidylmethacrylat , Glycidyl- vinylether und Glycidylallylether . Als I socyanate seien beispielhaft genannt meta- und para-Isopropenyl-alpha, alpha- dimethyl-benzylisocyanat (TMI) , 2-Methyl-2-isocyanatopropyl- methacrylat, wobei die Isocyanatgruppen der genannten Monomere gegebenenfalls auch blockiert sein können, beispielsweise mit Phenol, Salicylsäureester, Ketoxim, Caprolactam, Malonsäure- dialkylester , Acetessigsäurealkylester, 2 , 2-Dimethyl-l , 3- dioxan-4 , 6-dion . Beispiele für Anhydrid-Comonomere sind Allylbernsteinsäureanhydrid und Maleinsäureanhydrid. Besonders bevorzugt enthalten die Copolymere keine Einheit von Monomeren aus der Gruppe umfassend Glycidyl (meth) acrylat, meta- und para-Isopropenyl-alpha, alpha-dimethylbenzylisocyanat (TMI) , Allylacetoacetat, acetoacetyliertes Hydroxyethyl (meth) acrylat und Hydroxypropyl (meth) acrylat . Am meisten bevorzugt enthalten die Copolymere keine Glycidyl (meth) acrylat-Einheit . The copolymers according to the invention based on the monomers a), b), optionally c) and optionally d) preferably do not contain any monomer unit which is substituted with an aldehyde, keto, epoxide, isocyanate, carboxylic anhydride or aziridine group is, in particular not a monomer unit substituted with an epoxide group. Examples of monomers containing aldehyde and keto groups are acrolein, vinyl methyl ketone, allyl acetoacetate, vinyl acetoacetate, vinyl or allyl bisacetoacetate and acetoacetylated hydroxyalkyl (meth)acrylates. Examples of monomers containing epoxy groups are glycidyl acrylate, glycidyl methacrylate, glycidyl vinyl ether and glycidyl allyl ether. As I were socyanate Examples include meta- and para-isopropenyl-alpha, alpha-dimethyl-benzyl isocyanate (TMI), 2-methyl-2-isocyanatopropyl methacrylate, whereby the isocyanate groups of the monomers mentioned can optionally also be blocked, for example with phenol, salicylic acid ester, ketoxime, Caprolactam, dialkyl malonic acid, alkyl acetoacetate, 2, 2-dimethyl-1, 3-dioxane-4, 6-dione. Examples of anhydride comonomers are allyl succinic anhydride and maleic anhydride. The copolymers particularly preferably contain no unit of monomers from the group comprising glycidyl (meth) acrylate, meta- and para-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate (TMI), allyl acetoacetate, acetoacetylated hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate. Most preferably, the copolymers do not contain any glycidyl (meth)acrylate unit.
Die Dispersionspulverzusammensetzungen eignen sich insbesondere zum Einsatz in bauchemischen Produkten. Sie können alleine oder in Kombination mit herkömmlichen Polymerdispersionen oder Dispersionspulvern eingesetzt werden. The dispersion powder compositions are particularly suitable for use in construction chemical products. They can be used alone or in combination with conventional polymer dispersions or dispersion powders.
Ein weiterer Gegenstand der Erfindung sind Baustofftrockenformulierungen basierend auf einem oder mehreren hydraulisch abbindenden Bindemitteln, wie Zement (Portland-, Aluminat-, Trass-, Hütten-, Magnesia-, Phosphatzement) , Gips und Wasserglas-; einer oder mehreren erfindungsgemäßen Dispersionspulverzusammensetzungen; gegebenenfalls einem oder mehreren Füllstoffen, beispielsweise Quarzsand, Quarzmehl, Kalksteinmehl, Calciumcarbonat, Calciummagnesiumcarbonat (Dolomit) , Kreide oder Weißkalkhydrat; und gegebenenfalls einem oder mehreren Zusatzmitteln, wie Vernetzer, Konservierungsmittel, Filmbildehilfsmittel, Dispergiermittel, Schaumstabilisatoren, Verflüssiger, Fließmittel, Flammschutzmittel, Farbstoffe oder Biozide. Another subject of the invention are dry building material formulations based on one or more hydraulically setting binders, such as cement (Portland, aluminate, trass, metallurgical, magnesia, phosphate cement), gypsum and water glass; one or more dispersion powder compositions according to the invention; optionally one or more fillers, for example quartz sand, quartz powder, limestone powder, calcium carbonate, calcium magnesium carbonate (dolomite), chalk or white lime hydrate; and optionally one or more additives, such as crosslinkers, preservatives, film-forming aids, dispersants, foam stabilizers, plasticizers, flow agents, flame retardants, dyes or biocides.
Die Baustofftrockenformulierungen enthalten vorzugsweise 0,1 bis 40 Gew.-%, besonders bevorzugt 0,3 bis 25,0 Gew.-% und am meisten bevorzugt 0,5 bis 15 Gew.-% an erfindungsgemäßen Dis- persionspulverzusammenset zungen, jeweils bezogen auf das Gesamtgewicht der Baustofftrockenformulierungen. The dry building material formulations preferably contain 0.1 to 40% by weight, particularly preferably 0.3 to 25.0% by weight and most preferably 0.5 to 15% by weight of dissolutions according to the invention. persion powder compositions, each based on the total weight of the dry building material formulations.
Die Baustofftrockenformulierungen enthalten beispielsweise > 0 bis 2,0 Gew.-%, bevorzugt > 0 bis 1,0 Gew.-%, mehr bevorzugt > 0 bis 0,5 Gew.-%, noch mehr bevorzugt > 0 bis 0,3 Gew.-% und besonders bevorzugt > 0 bis 0,2 Gew.-% Stickstoffverbindungen, bezogen auf das Gesamtgewicht der Baustofftrockenformulierungen . The dry building material formulations contain, for example, >0 to 2.0% by weight, preferably >0 to 1.0% by weight, more preferably >0 to 0.5% by weight, even more preferably >0 to 0.3% by weight .-% and particularly preferably > 0 to 0.2% by weight of nitrogen compounds, based on the total weight of the dry building material formulations.
Die Baustofftrockenformulierungen enthalten vorzugsweise 1 bis 90 Gew.-%, besonders bevorzugt 5 bis 45 Gew.-% und am meisten bevorzugt 10 bis 35 Gew.-% an hydraulisch abbindenden Bindemitteln, bezogen auf das Gesamtgewicht der Baustofftrockenformulierungen . The dry building material formulations preferably contain 1 to 90% by weight, particularly preferably 5 to 45% by weight and most preferably 10 to 35% by weight of hydraulically setting binders, based on the total weight of the dry building material formulations.
Die Baustofftrockenformulierungen enthalten vorzugsweise 10 bis 99 Gew.-%, besonders bevorzugt 30 bis 90 Gew.-% und am meisten bevorzugt 50 bis 85 Gew.-% an Füllstoffen, bezogen auf das Gesamtgewicht der Baustofftrockenformulierungen. The dry building material formulations preferably contain 10 to 99% by weight, particularly preferably 30 to 90% by weight and most preferably 50 to 85% by weight of fillers, based on the total weight of the dry building material formulations.
Die Baustoff formulierungen enthalten vorzugsweise 0,001 bis 30 Gew.-%, besonders bevorzugt 0,01 bis 8 Gew.-% und am meisten bevorzugt 0,03 bis 4 Gew.-% an Zusatzmitteln, bezogen auf das Trockengewicht der Baustoff formulierungen . The building material formulations preferably contain 0.001 to 30% by weight, particularly preferably 0.01 to 8% by weight and most preferably 0.03 to 4% by weight of additives, based on the dry weight of the building material formulations.
Aldehyde oder Ketone, die in den Baustofftrockenformulierungen enthalten sein können, enthalten vorzugsweise 1 bis 20 Kohlenstoffatome, mehr bevorzugt 1 bis 10 Kohlenstoff atome, besonders bevorzugt 1 bis 5 Kohlenstoff atome und am meisten bevorzugt 1 bis 3 Kohlenstoff atome . Aldehydes or ketones, which can be contained in the dry building material formulations, preferably contain 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 5 carbon atoms and most preferably 1 to 3 carbon atoms.
Beispiele für Aldehyde sind Hexanal, Propionaldehyd und insbesondere Formaldehyd und Acetaldehyd. Ein Beispiel für ein Keton ist Aceton. Examples of aldehydes are hexanal, propionaldehyde and especially formaldehyde and acetaldehyde. An example of a ketone is acetone.
Die Aldehyde und Ketone enthaltenden Baustoff trockenf ormulierungen enthalten insgesamt vorzugsweise < 1 Gew.-%, mehr bevorzugt < 0,5 Gew.-%, besonders bevorzugt < 0,1 Gew.-%, am meisten bevorzugt < 0,03 Gew.-% und am allermeisten bevorzugt < 0,01 Gew.-% an Aldehyden und Ketonen, bezogen auf das Gesamtgewicht der Baustofftrockenformulierungen. The building material dry formulations containing aldehydes and ketones preferably contain a total of <1% by weight, or more preferably <0.5% by weight, particularly preferably <0.1% by weight, most preferably <0.03% by weight and most preferably <0.01% by weight of aldehydes and ketones on the total weight of the dry building material formulations.
Das Herstellen der Baustofftrockenformulierungen kann in an sich herkömmlicher Weise in herkömmlichen Vorrichtungen erfolgen. Die zur Verarbeitung der Baustofftrockenformulierungen erforderliche Wassermenge wird üblicherweise unmittelbar vor der Applikation unter Mischen hinzugefügt. The dry building material formulations can be produced in a conventional manner in conventional devices. The amount of water required to process the dry building material formulations is usually added with mixing immediately before application.
Die Baustofftrockenformulierungen eignen sich beispielsweise zur Herstellung von Armierungsmassen für Wärmedämmverbundsysteme, oder zur Herstellung von Klebemitteln oder Beschichtungsmitteln. Beispiele für Klebemittel sind Klebemittel für Wärmedämmplatten und Schallschutzplatten, Fliesenkleber, Fugenmörtel und Klebemittel zur Verklebung von Holz und Holzwerkstoffen. Beispiele für Beschichtungsmittel sind Mörtel, Verlaufs- und Abdichtungsmassen, Estriche, Putze. The dry building material formulations are suitable, for example, for the production of reinforcing compounds for thermal insulation composite systems, or for the production of adhesives or coating materials. Examples of adhesives are adhesives for thermal insulation panels and sound insulation panels, tile adhesives, grout and adhesives for bonding wood and wood-based materials. Examples of coating materials are mortar, leveling and sealing compounds, screeds, plasters.
Überraschenderweise lassen sich mit den erfindungsgemäßen Dispersionspulverzusammensetzungen die Aldehyd- oder Ketonkonzentration in Baustoff formulierungen reduzieren. Surprisingly, the aldehyde or ketone concentration in building material formulations can be reduced using the dispersion powder compositions according to the invention.
Die nachfolgenden Beispiele dienen zur weiteren Erläuterung der Erfindung. The following examples serve to further explain the invention.
Copolymer-Dispersion : Copolymer dispersion:
Wässrige Dispersion eines Polyvinylalkohol-stabilisierten Vinylacetat-Ethylen-Vinylchlorid-Copolymers mit einer Glasübergangstemperatur von 13°C. Der Polyvinylalkohol hatte einen Hydrolysegrad von 88 Mol-% und eine Höpplerviskosität von 4 mPas (in 4%-iger wässriger Lösung) . Aqueous dispersion of a polyvinyl alcohol-stabilized vinyl acetate-ethylene-vinyl chloride copolymer with a glass transition temperature of 13°C. The polyvinyl alcohol had a degree of hydrolysis of 88 mol% and a Höppler viscosity of 4 mPas (in 4% aqueous solution).
Herstellung der Dispersionspulverzusammensetzungen (DPP) der (Vergleichs ) Beispiele 1~4: Die Copolymer-Dispersion wurde gegebenenfalls mit einer Stick- stof fverbindung versetzt, entsprechend der Angabe in Tabelle 1, und mittels Sprühtrocknung in an sich herkömmlicher Weise bei einer Eintrittstemperatur von 130°C und einer Austrittstemperatur von 80°C getrocknet, wodurch eine Dispersionspulverzusammensetzung erhalten wurde. Der Dispersionspulverzusammensetzung wurden 5 Gew.-% Kaolin und 10 Gew.-% Calciumcarbonat als Antibackmittel zugegeben. Preparation of the dispersion powder compositions (DPP) of (comparative) examples 1~4: The copolymer dispersion was optionally mixed with a nitrogen compound, as shown in Table 1, and dried by spray drying in a conventional manner at an inlet temperature of 130 ° C and an outlet temperature of 80 ° C, whereby a dispersion powder composition was obtained . 5% by weight of kaolin and 10% by weight of calcium carbonate were added to the dispersion powder composition as anti-caking agents.
Tabelle 1: Zusammensetzung der Dispersionspulverzusammensetzungen :
Figure imgf000022_0001
a) bezogen auf den Polymergehalt der Dispersion (fest/fest) . Table 1: Composition of the dispersion powder compositions:
Figure imgf000022_0001
a) based on the polymer content of the dispersion (solid/solid).
Herstellung der Baustoff formulierungen der Production of building material formulations
(Vergleichs ) Beispiele 5~8: (Comparative) Examples 5~8:
Zement, Füllstoff, Celluloseether und Calciumf ormiat und die jeweilige Dispersionspulverzusammensetzung entsprechend den Angaben in Tabelle 2 wurden gemischt. Cement, filler, cellulose ether and calcium formate and the respective dispersion powder composition according to the information in Table 2 were mixed.
Das Anmachen erfolgte mit 28 Gew.-% Wasser, bezogen auf das Gesamtgewicht der Feststoffe. Die resultierenden Baustoff for- mulierung wurde für insgesamt 10 min in einem Planetenmischer homogenisiert . Mixing was carried out with 28% by weight of water, based on the total weight of the solids. The resulting building material formulation was homogenized in a planetary mixer for a total of 10 minutes.
Die Baustoff formulierungen entsprechen einem Fliesenkleber der Klasse C2S1 mit 8% Anteil an polymerem Bindemittel und sind wie folgt auf gebaut: Tabelle 2 : Zusammensetzung der Baustof f formulierungen :
Figure imgf000023_0001
The building material formulations correspond to a tile adhesive of class C2S1 with 8% polymer binder and are structured as follows: Table 2: Composition of the building material formulations:
Figure imgf000023_0001
Austestung der Aldehyd-Emission : Testing the aldehyde emission:
Messung der Aldehyd-Emissionen erfolgte in Anlehnung an die ISO 16000-3 . Hierfür wurde die Mörtelprobe in einem Labormischer mit 28 Gew . -% Wasser frisch angerührt und mit einem Glättspachtel gleichmäßig auf einer Glasplatte über eine Fläche von 0 , 096 m2 verteilt . Die Zielschichtdicke lag bei 3 mm . Die j eweilige Probe wurde unmittelbar danach in die VOC Testkammer (Hersteller Vötsch, Volumen = 240 L ) überführt . Die Kammer wurde auf eine Temperatur von 23 ± 1 ° C und eine Luftfeuchtigkeit von 50 ± 5 % bei einer Luft-Austauschrate von 2L/min eingestellt . Über einen Zeitraum von insgesamt 3 Tagen wurden die Aldehyd-Emissionen über eine DNPH-Säule gesammelt und mittels Gaschromatographie quantitativ bestimmt . Aldehyde emissions were measured based on ISO 16000-3. For this purpose, the mortar sample was placed in a laboratory mixer with 28 wt. -% water freshly mixed and spread evenly on a glass plate over an area of 0.096 m 2 using a smoothing spatula. The target layer thickness was 3 mm. The respective sample was immediately transferred to the VOC test chamber (manufacturer Vötsch, volume = 240 L). The chamber was set to a temperature of 23 ± 1 ° C and a humidity of 50 ± 5% at an air exchange rate of 2L/min. Over a total period of 3 days, the aldehyde emissions were collected via a DNPH column and quantitatively determined using gas chromatography.
Die Ergebnisse der Austestung sind in Tabelle 3 zusammengefasst . The results of the testing are summarized in Table 3.
Mörtel mit den erfindungsmäßigen Pulvern der Beispiele 2 bis 4 wiesen deutlich reduzierte Aldehyd-Emissionen auf . Tabelle 3: Ergebnisse der Austestung der Aldehyd-Emission der Baustoff formulierungen :
Figure imgf000024_0001
Mortars with the powders according to the invention from Examples 2 to 4 had significantly reduced aldehyde emissions. Table 3: Results of testing the aldehyde emissions of the building material formulations:
Figure imgf000024_0001

Claims

Patentansprüche : Patent claims:
1 . In Wasser redispergierbare Dispersionspulverzusammensetzungen basierend auf Copolymeren von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls einem oder mehreren Hil fsmonomeren und d) gegebenenfalls einem oder mehreren weiteren ethylenisch ungesättigten Monomeren, dadurch gekennzeichnet , dass ein oder mehrere Amino-Verbindungen ausgewählt aus der Gruppe umfassend Polyoxyalkylenamine , Polyethylenimine , aliphatische Polyamine und Verbindungen der Formel R-NR 'H enthalten sind, wobei in der Formel R-NR 'H der Rest R für einen linearen oder verzweigten, gegebenenfalls substituierten Kohlenwasserstof frest mit 1 bis 20 Kohlenstof f atomen steht und R ' ein Wasserstof f atom, eine NH2-Gruppe oder ein Carbonylrest ist , mit der Maßgabe , dass die Hil fsmonomere c ) ausgewählt werden aus der Gruppe umfassend ethylenisch ungesättigte Mono- und Dicarbonsäuren; ethylenisch ungesättigte Carbonsäurenitrile ; Acrylamid; ethylenisch ungesättigte Sul fonsäuren; ethylenisch ungesättigte siliciumfunktionelle Monomere ; und Hydroxyethyl- , Hydroxypropyl- oder Hydroxy- butylacrylat oder -methacrylat und die weiteren ethylenisch ungesättigten Monomere d) ausgewählt werden aus der Gruppe umfassend Methylacrylat , Methylmethacrylat , Ethylacrylat , Ethylmethacrylat , Propyl- acrylat , Propylmethacrylat , n-Butylacrylat , n-Butylmeth- acrylat , 2-Ethylhexylacrylat , Norbornylacrylat , Vinylaromaten und Vinylhalogenide und die in Wasser redispergierbaren Dispersionspulverzusammensetzungen keine Epoxid-Gruppen tragenden Verbindungen enthalten . 1 . Water-redispersible dispersion powder compositions based on copolymers of a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more further ethylenically unsaturated monomers, characterized in that one or more amino compounds selected from the group comprising polyoxyalkyleneamines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H, where in the formula R-NR'H the radical R represents a linear or branched, optionally substituted hydrocarbon radical with 1 to 20 carbon atoms and R 'is a hydrogen atom, an NH2 group or a carbonyl radical, with the proviso that the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; acrylamide; ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate and the further ethylenically unsaturated monomers d) are selected from the group comprising methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate , 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatics and vinyl halides and the water-redispersible dispersion powder compositions do not contain any compounds bearing epoxide groups.
2 . In Wasser redispergierbare Dispersionspulverzusammensetzungen nach Anspruch 1 , dadurch gekennzeichnet , dass j ede Amino-Verbindung 1 bis 50 Aminogruppen enthält . In Wasser redispergierbare Dispersionspulverzusammensetzungen nach Anspruch 1 oder 2 , dadurch gekennzeichnet , dass die Reste R ein oder mehrere Substituenten tragen ausgewählt aus der Gruppe umfassend Säure- , Amid- , Amin- , Alkohol- , Oxyalkylen- , Thiol- und Thioether-Gruppen und aromatische oder heteroaromatische Reste . In Wasser redispergierbare Dispersionspulverzusammensetzungen nach Anspruch 1 bis 3 , dadurch gekennzeichnet , dass ein oder mehrere Amino-Verbindungen ausgewählt werden aus der Gruppe umfassend Hexamethylendiamin, Diethylentriamin, Tetraethylenpentamin, Tetraethylenepentamine , Diproprenediamine , Diethylaminopropylamine , Phenylendiamin, I sophorondiamin und Aminosäuren . In Wasser redispergierbare Dispersionspulverzusammensetzungen nach Anspruch 1 bis 4 , dadurch gekennzeichnet , dass die Polyoxyalkylenamine auf Ethylenoxid- (EO) , Propylenoxid- ( PO) und/oder Butylenoxid-Einheiten basieren und ein oder mehrere Aminogruppen tragen und Polyethylenimine auf Struktureinheiten -CH2-CH2-NH- basieren . In Wasser redispergierbare Dispersionspulverzusammensetzungen nach Anspruch 1 bis 5 , dadurch gekennzeichnet , dass die in Wasser redispergierbaren Dispersionspulverzusammensetzungen 0 , 1 bis 20 Gew . -% an Amino-Verbindungen enthalten, bezogen auf das Gesamtgewicht der in Wasser redispergierbaren Dispersionspulverzusammensetzungen . In Wasser redispergierbare Dispersionspulverzusammensetzungen nach Anspruch 1 bis 6 , dadurch gekennzeichnet , dass die in Wasser redispergierbaren Dispersionspulverzusammensetzungen 40 bis 99 Gew . -% an Copolymeren von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls Hil fsmonomeren und d) gegebenenfalls weiteren ethylenisch ungesättigten Monomeren enthalten, bezogen auf das Gesamtgewicht der in Wasser redispergierbaren Dispersionspulverzusammensetzungen . In Wasser redispergierbare Dispersionspulverzusammensetzungen nach Anspruch 1 bis 7 , dadurch gekennzeichnet , dass die in Wasser redispergierbaren Dispersionspulverzusammensetzungen keine Epoxid-Gruppen tragenden Verbindungen enthalten ausgewählt aus der Gruppe umfassend Epoxidharze , aliphatische Epoxidverbindungen, heterocyclische Epoxidverbindungen, Bisglycidyloxyphenylmethan, Butyldiglycidylether , Vinylcyclohexandioxid, Dicyclopenta- diendioxid, 3 , 4-Epoxy- 6-methyl-cyclohexyl-methyl , Trigly- cidyl- I socyanurat und radikalisch polymerisierbare Epoxidverbindungen mit mindestens zwei Epoxidgruppen pro Molekül . Verfahren zur Herstellung der in Wasser redispergierbaren Dispersionspulverzusammensetzungen, dadurch gekennzeichnet , dass Copolymere auf Basis von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls einem oder mehreren Hil fsmonomeren und d) gegebenenfalls einem oder mehreren weiteren ethylenisch ungesättigten Monomeren und ein oder mehrere Amino-Verbindungen ausgewählt aus der Gruppe umfassend Polyoxyalkylenamine , Polyethylenimine , aliphatische Polyamine und Verbindungen der Formel R-NR 'H gemischt werden, wobei in der Formel R-NR 'H der Rest R für einen linearen oder verzweigten, gegebenenfalls substituierten Kohlenwasserstof frest mit 1 bis 20 Kohlenstof f atomen steht und R ' ein Wasserstof f atom, eine NH2-Gruppe oder ein Carbonylrest ist , mit der Maßgabe , dass die Hil fsmonomere c ) ausgewählt werden aus der Gruppe umfassend ethylenisch ungesättigte Mono- und Dicarbonsäuren; ethylenisch ungesättigte Carbonsäurenitrile ; Acrylamid; ethylenisch ungesättigte Sul fonsäuren; ethylenisch ungesättigte siliciumfunktionelle Monomere ; und Hydroxyethyl- , Hydroxypropyl- oder Hydroxy- butylacrylat oder -methacrylat und die weiteren ethylenisch ungesättigten Monomere d) ausgewählt werden aus der Gruppe umfassend Methylacrylat , Methylmethacrylat , Ethylacrylat , Ethylmethacrylat , Propyl- acrylat , Propylmethacrylat , n-Butylacrylat , n- Butylmethacrylat , 2-Ethylhexylacrylat , Norbornylacrylat , Vinylaromaten und Vinylhalogenide und in die in Wasser redispergierbaren Dispersionspulverzusammensetzungen keine Epoxid-Gruppen tragenden Verbindungen eingebracht werden . Verfahren zur Herstellung der in Wasser redispergierbaren Dispersionspulverzusammensetzungen nach Anspruch 9 , dadurch gekennzeichnet , dass Copolymere auf Basis von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls Hil fsmonomeren und d) gegebenenfalls weiteren ethylenisch ungesättigten Monomeren in Form von wässrigen Dispersionen getrocknet werden und vor, während oder nach dem Trocknen Amino- Verbindungen zugemischt werden; oder 2. Water-redispersible dispersion powder compositions according to claim 1, characterized in that each amino compound contains 1 to 50 amino groups. Water-redispersible dispersion powder compositions according to claim 1 or 2, characterized in that the radicals R carry one or more substituents selected from the group comprising acid, amide, amine, alcohol, oxyalkylene, thiol and thioether groups and aromatic or heteroaromatic residues. Water-redispersible dispersion powder compositions according to claims 1 to 3, characterized in that one or more amino compounds are selected from the group comprising hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, tetraethylenepentamine, diproprenediamine, diethylaminopropylamine, phenylenediamine, isophoronediamine and amino acids. Water-redispersible dispersion powder compositions according to claims 1 to 4, characterized in that the polyoxyalkylene amines are based on ethylene oxide (EO), propylene oxide (PO) and/or butylene oxide units and carry one or more amino groups and polyethyleneimines are based on structural units -CH2-CH2- NH-based. Water-redispersible dispersion powder compositions according to claims 1 to 5, characterized in that the water-redispersible dispersion powder compositions contain 0.1 to 20 wt. -% of amino compounds contained, based on the total weight of the water-redispersible dispersion powder compositions. Water-redispersible dispersion powder compositions according to claims 1 to 6, characterized in that the water-redispersible dispersion powder compositions contain 40 to 99 wt. -% of copolymers of a) vinyl acetate, b) ethylene, c) optionally auxiliary monomers and d) optionally contain further ethylenically unsaturated monomers, based on the total weight of the water-redispersible dispersion powder compositions. Water-redispersible dispersion powder compositions according to claims 1 to 7, characterized in that the water-redispersible dispersion powder compositions do not contain any compounds bearing epoxy groups selected from the group comprising epoxy resins, aliphatic epoxy compounds, heterocyclic epoxy compounds, bisglycidyloxyphenylmethane, butyl diglycidyl ether, vinylcyclohexane dioxide, dicyclopentadiene dioxide, 3 , 4-epoxy-6-methyl-cyclohexyl-methyl, triglycidyl-isocyanurate and free-radically polymerizable epoxy compounds with at least two epoxide groups per molecule. Process for producing the water-redispersible dispersion powder compositions, characterized in that copolymers based on a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers and d) optionally one or more further ethylenically unsaturated monomers and one or more amino Compounds selected from the group comprising polyoxyalkyleneamines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H are mixed, where in the formula R-NR'H the radical R is a linear or branched, optionally substituted hydrocarbon with 1 to 20 carbon atoms and R 'is a hydrogen atom, an NH2 group or a carbonyl radical, with the proviso that the auxiliary monomers c) are selected from the group comprising ethylenically unsaturated mono- and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; acrylamide; ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate and the other ethylenically unsaturated monomers d) are selected from the group comprising methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatics and vinyl halides and no compounds bearing epoxide groups are introduced into the water-redispersible dispersion powder compositions. Process for producing the water-redispersible dispersion powder compositions according to claim 9, characterized in that copolymers based on a) vinyl acetate, b) ethylene, c) optionally auxiliary monomers and d) optionally further ethylenically unsaturated monomers are dried in the form of aqueous dispersions and before , amino compounds are mixed in during or after drying; or
Copolymere auf Basis von a ) Vinylacetat , b ) Ethylen, c ) gegebenenfalls Hil fsmonomeren und d) gegebenenfalls weiteren ethylenisch ungesättigten Monomeren in Form von in Wasser redispergierbaren Pulvern mit Amino-Verbindungen gemischt werden . Baustof ftrockenformulierungen basierend auf einem oder mehreren hydraulisch abbindenden Bindemitteln, einer oder mehreren in Wasser redispergierbaren Dispersionspulverzusammensetzungen aus Anspruch 1 bis 8 , gegebenenfalls einem oder mehreren Füllstof fen und gegebenenfalls einem oder mehreren Zusatzmitteln . Baustof ftrockenformulierungen nach Anspruch 11 , dadurch gekennzeichnet , dass > 0 bis 1 , 0 Gew . -% Amino-Verbindungen enthalten sind, bezogen auf das Gesamtgewicht der Baustof ftrockenformulierungen . Verwendung der Baustof ftrockenformulierungen aus Anspruch 11 oder 12 zur Herstellung von Armierungsmassen für Wärmedämmverbundsysteme oder zur Herstellung von Klebemitteln oder Beschichtungsmitteln . Copolymers based on a) vinyl acetate, b) ethylene, c) optionally auxiliary monomers and d) optionally further ethylenically unsaturated monomers in the form of water-redispersible powders are mixed with amino compounds. Building material dry formulations based on one or more hydraulically setting binders, one or more water-redispersible dispersion powder compositions from claims 1 to 8, optionally one or more fillers and optionally one or more additives. Building material dry formulations according to claim 11, characterized in that >0 to 1.0 wt. -% amino compounds are contained, based on the total weight of the building material dry formulations. Use of the building material dry formulations from claim 11 or 12 for the production of reinforcing compounds for thermal insulation composite systems or for the production of adhesives or coating materials.
PCT/EP2022/074769 2022-09-06 2022-09-06 Amino compound-containing dispersion powder compositions WO2024051931A1 (en)

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