Amino compound-containing dispersion powder compositions

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

[0001] Dispersion powder compositions containing amino compounds

[0002] The invention relates to water-redispersible dispersion powder compositions containing amino compounds, processes for their preparation and their use, in particular in coating or adhesive compositions, for example for the construction sector.

[0003] Water-redispersible polymer powders (dispersion powders) are generally obtained by drying aqueous polymer dispersions. Drying is often carried out in the presence of a drying aid, which can cause a shell of drying aid to form around the polymer particles. During the drying process, drying aids can prevent the polymer particles from irreversibly sticking together 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 there with the particle size distribution of the starting dispersion.

[0004] Such dispersion powders are used in a wide variety of construction chemical products, for example in coatings or adhesives, such as tile adhesives, fillers, leveling compounds, thermal insulation composite systems, or grouts. The advantage of dispersion powders is that they can be used in prefabricated, storable dry mixes, optionally together with hydraulic binders such as cement, which are converted into the ready-to-use product by adding water and mixing immediately before use.

[0005] To improve processing and application properties, building material formulations are generally modified with a range of additives, for example polymer powders, thickeners, plasticizers, retarders, setting accelerators, defoamers, air entraining agents and many others. Unfortunately, building material formulations modified in this way can release low molecular weight, highly volatile and other hazardous substances, including ketones or alkanals, colloquially known as aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde or higher homologues of the alkanal group. Such carbonyl compounds are generally reactive and often classified as carcinogenic, which is why the emission of aldehyde and ketone compounds should be avoided wherever possible during the formulation process.Otherwise, aldehydes or ketones may be released during processing or use of the building products and endanger the health of users on the construction site or consumers, especially those using the products indoors in private and commercial environments.

[0006] In general, commercial compounders of building material formulations have no way of determining which additive is causing the aldehyde or ketone release. The processes for the qualitative and quantitative determination of highly to moderately volatile and low molecular weight chemicals are complex and not a standard analytical method. To make matters worse, aldehyde or ketone impurities can be released from additives through chemical reactions after the building material formulations have been manufactured, meaning that cleaning steps during additive production cannot completely solve the aldehyde or ketone release problem. For example, aldehydes can be released in fresh mortar with a high pH value through the hydrolysis of vinyl ester residual monomers of long-chain carboxylic acids, which, due to their low volatility, cannot always be completely removed using conventional processes such as stripping.In general, however, dispersion powders per se do not represent a significant source of aldehydes or ketones, 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 sulphoxylate, are removed from the resulting dispersion powder composition at the latest when the polymer dispersions are dried.

[0007] 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.

[0008] Surprisingly, the object was essentially achieved 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 present and the auxiliary monomers c) and also the further ethylenically unsaturated monomers d) are each selected from certain groups.

[0009] US 6080806 recommends dispersion powder compositions of styrene-butadiene copolymers and amino acids for improving mechanical properties such as impact resistance, flexibility or adhesive tensile strength. US201727544 relates to aqueous dispersions which contain lysine as a crosslinker and crosslinkable copolymers of 1,3-dicarbonyl monomers and further monomers. US 6063865 A relates to a water-redispersible, crosslinkable powder composition comprising a) 30 to 95 parts by weight of water-insoluble, film-forming polymers of ethylenically unsaturated monomers, where 0.5 to 10 parts by weight of lysine are present. -% 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 having 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 having two or more amino groups.

[0010] 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 present, where in the formula R-NR 'H the radical R stands for a linear or branched, optionally substituted hydrocarbon radical having 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 carrying epoxy groups (epoxide compounds).;

[0011] 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 preferably 1 to 5 amino groups, most preferably 1 to 3 amino groups and most preferably two amino groups.

[0012] The radical R of the compounds of the formula R-NR 'H is preferably a linear or branched, optionally substituted hydrocarbon radical having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms and particularly preferably 1 to 5 carbon atoms.

[0013] Preferred substituents of the R radicals are acid, amide, amine, alcohol, oxyalkylene, thiol, or thioether groups, such as methyl thioether radicals, or aromatic or heteroaromatic radicals, such as phenyl or imidazole radicals. Preferred substituents of the R radicals are amine or acid groups, such as sulfonic acid or, preferably, carboxylic acid groups. The R radicals preferably carry at least two substituents, in particular two substituents.

[0014] The radical R ' preferably represents a carbonyl radical and particularly preferably a hydrogen atom. Nitrogen compounds having 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.

[0015] Preferred compounds of the formula R-NR 'H are aliphatic or aromatic amines and in particular amino acids.

[0016] Examples of aliphatic or aromatic amines are hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, tetraethylenepentamine, 1,2-diaminopropane, diproprenediamine, diethylaminopropylamine, phenylenediamine, isophoronediamine.

[0017] Preference is given to natural amino acids, in particular proteinogenic amino acids. The most preferred amino acids are glycine, aspartic acid, glutamic acid and in particular 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.

[0018] Polyoxyalkyleneamines 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.

[0019] Polyoxyalkylenamines are available, for example, under the trade name Jeffamine R available .

[0020] Polyethylenimines 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 .

[0021] Aliphatic polyamines are also well known and are commercially available, for example, under the trade names Anquamine R or Epilink R or Epilox R -Hardener available.

[0022] 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.

[0023] The nitrogen compounds can also be present in the form of salts, for example in the form of their ammonium salts, for example with acid groups, such as carboxylic acids, or halides as counter ion.

[0024] Preferred nitrogen compounds are polyoxyalkyleneamines and compounds of the formula R-NR'H, especially amino acids.

[0025] The dispersion powder compositions preferably contain 0.1 to 30 wt.%, more preferably 0.2 to 20 wt.%, even more preferably 0.3 to 15 wt.%, particularly preferably 0.3 to 12 wt.%, most preferably 0.3 to 10 wt.%, most preferably 0.3 to 3 wt.% of nitrogen compounds, based on the total weight of the dispersion powder compositions.

[0026] 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.

[0027] 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.

[0028] The copolymers are based preferably on vinyl acetate a) to an extent of 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.

[0029] The copolymers are based preferably on ethylene b) to an extent of > 0 to 50 wt.%, particularly preferably 0.1 to 40 wt.% and most preferably 1 to 30 wt.%, based on the total weight of the copolymers.

[0030] 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 carbonitriles, preferably acrylonitrile; acrylamide (CH2CHCONH2); ethylenically unsaturated sulfonic acids or their salts, preferably vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid; ethylenically unsaturated silicon-functional monomers, such as acryloxypropyltri(alkoxy)- and methacryloxypropyltri(alkoxy)-silanes, vinyltrialkoxysilanes and vinylmethyldialkoxysilanes, where methoxy, ethoxy and ethoxypropylene glycol ether radicals can be present as alkoxy groups, for example; and hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate.

[0031] Particularly preferred auxiliary monomers c) are ethylenically unsaturated acids, such as acrylic acid, methacrylic acid and vinylsulfonic acid.

[0032] The auxiliary monomers c) are generally different from vinyl acetate a), ethylene b) and the optional further ethylenically unsaturated monomers d).

[0033] The copolymers are based preferably on 0 to 20 wt.%, particularly preferably 0.1 to 10 wt.% and most preferably 0.5 to 5 wt.% of auxiliary monomers c), based on the total weight of the copolymers.

[0034] 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, especially styrene and vinyltoluene, and vinyl halides, such as vinyl chloride. Particular preference is given to vinyl chloride, methyl methacrylate, n-butyl acrylate, and styrene. Most preferred is vinyl chloride.

[0035] 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 further ethylenically unsaturated monomers d) to an extent of preferably 0 to <50 wt. %, particularly preferably 0.1 to 40 wt. %, and most preferably 1 to 30 wt. %, based on the total weight of the copolymers.

[0036] 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).

[0037] The monomer selection or the selection of the weight fractions 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 predicted using the Fox equation. According to Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956), the following applies: 1 / Tg = xl / Tgl + x2 / Tg2 + . . . + xn / Tgn, where xn is the mass fraction (wt. % / 100) of monomer n, and Tgn is the glass transition temperature in Kelvin of the homopolymer of monomer n. Tg values ​​for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).

[0038] The copolymers are preferably prepared by 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. When copolymerizing gaseous comonomers such as ethylene, 1,3-butadiene, or vinyl chloride, the process can also be carried out under pressure, generally between 5 bar and 100 bar.

[0039] Polymerization can generally be initiated using the redox initiator combinations commonly used for emulsion polymerization. The monomer conversion can be controlled, as usual, by initiator dosage. The initiators are generally added in such a way as to ensure continuous polymerization. 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, and azobisisobutyronitrile. The sodium, potassium, and ammonium salts of peroxodisulfuric acid and hydrogen peroxide are preferred.

[0040] The initiators mentioned are generally used in an amount of 0.01 to 2.0 wt.%, based on the total weight of the monomers.

[0041] Suitable reducing agents include, for example, the sulfites and bisulfites of alkali metals and ammonium, such as sodium sulfite, and the derivatives of sulfoxylic acid, such as zinc or alkali formaldehyde sulfoxylates, for example sodium hydroxymethanesulfinate (Brüggolit), 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.

[0042] The oxidizing agents mentioned, in particular the salts of peroxodisulfuric acid and hydrogen peroxide, can also be used alone as thermal initiators.

[0043] Regulators can be used during the emulsion polymerization process to control the molecular weight. If regulators are used, they are usually used in amounts between 0.001 and 5.0 wt. %, based on the monomers to be polymerized, and are metered separately or premixed with the reaction components. Examples of such substances are n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptopropionic acids or their alkali metal salts, methyl mercaptopropionate, isopropanol, phosphonic acid or its derivatives, phosphinic acid or its 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 non-ionic emulsifiers, such as anionic surfactants, in particular alkyl sulfates with a chain length of 8 to 18 C atoms, alkyl or alkylaryl ether sulfates with 8 to 18 C atoms in the hydrophobic radical and up to 40 ethylene or propylene oxide units, alkyl or alkylaryl sulfonates with 8 to 18 C atoms, esters and half-esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or non-ionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers with 8 to 40 ethylene oxide units.

[0044] Particularly preferably, polymerization is carried out in the absence of emulsifiers. The aqueous dispersions and / or the polymer powders preferably contain no emulsifiers.

[0045] After polymerization, residual monomers can be removed by post-polymerization using known methods, for example, post-polymerization initiated with a redox catalyst. Volatile residual monomers can also be removed by distillation, preferably under reduced pressure, and optionally by passing or over inert carrier gases such as air, nitrogen, or steam.

[0046] The copolymers thus obtainable are preferably in the form of protective colloid-stabilized, aqueous dispersions. The copolymers according to the invention are preferably protective colloid-stabilized.

[0047] 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.

[0048] Partially saponified or fully saponified polyvinyl alcohols with a degree of hydrolysis of preferably 80 to 100 mol% are preferred. Partially saponified polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol% are particularly preferred, 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 by methods known to those skilled in the art. Protective colloids are present in an amount of preferably 1 to 30 wt.%, particularly preferably 3 to 20 wt.%, based on the total weight of the copolymers.

[0049] The aqueous dispersions have a solids content of preferably 30 to 75 wt.%, particularly preferably 45 to 70 wt.%.

[0050] The aqueous dispersions of the copolymers can be converted into copolymers in the form of water-redispersible powders in a conventional manner, analogously to that described, for example, further below for the drying for the preparation of the dispersion powder compositions.

[0051] The water-redispersible dispersion powder compositions do not contain any compounds containing epoxy groups (epoxide compounds). Epoxy compounds are detrimental to achieving the object of the invention.

[0052] Examples of epoxy compounds are epoxy resins. One example of these are epoxy compounds of the bisphenol A type, i.e., 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-methylcyclohexylmethyl; 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. Particularly preferred are no epoxy resins of the bisphenol A type or bisphenol F type.

[0053] Further examples of epoxy compounds are bisglycidyloxyphenylmethane, butyl diglycidyl ether, vinylcyclohexane dioxide, dicyclopentadiene dioxide, 3,4-epoxy-6-methyl-cyclohexyl-methyl and triglycidyl isocyanurate.

[0054] Epoxy compounds also include radically polymerizable epoxy compounds with at least two epoxy groups per molecule. The epoxy compounds can be aliphatic, aliphatic, or aromatic in nature.

[0055] The invention further relates to processes for the preparation of 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 further 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 are mixed, where in the formula R-NR 'H the radical R stands for a linear or branched, optionally substituted hydrocarbon radical having 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 carbonitriles; 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 carrying epoxy groups (epoxide compound) are introduced into the water-redispersible dispersion powder compositions.

[0056] The mixing of the nitrogen compounds generally takes place after the preparation of the copolymers by polymerization.

[0057] 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 drying the aqueous polymer dispersion. 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 be mixed with one or more nitrogen compounds in the form of water-redispersible powders.

[0058] A drying aid is generally added to the aqueous dispersions. The drying aid is generally used in a total amount of 0.5 to 30 wt.%, in particular 5 to 20 wt.%, 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 wt.%, based on the solids content of the aqueous dispersion.

[0059] The aqueous dispersions can be dried, for example, by fluidized-bed drying, freeze-drying, or spray-drying. The dispersions are preferably spray-dried. Spray-drying is carried out in conventional spray-drying systems, with atomization being achieved using single-, dual-, or multi-component nozzles or with a rotating disk. 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, the Tg of the resin, and the desired degree of drying. The viscosity of the feed to be sprayed is adjusted via the solids content to achieve a value of < 500 mPas (Brookfield viscosity at 20 revolutions and 23°C), preferably < 250 mPas. The solids content of the dispersion to be atomized is preferably 30 to 75 wt.% and particularly preferably 45 to 70 wt.%.

[0060] In many cases, a content of up to 1.5% by weight of antifoam, based on the copolymer, has proven advantageous. Antifoam is preferably added during drying.

[0061] To increase the storage life by improving the blocking stability, especially in the case of copolymers with a low glass transition temperature, the resulting polymer powder can be provided, for example, with one or more antiblocking agents (anticaking agents). The antiblocking agents are preferably added during or after drying, especially during drying in the spray drying system. Preferred polymer powders contain antiblocking agents, in particular 1 to 40 wt . -% , based on the total weight of polymeric constituents . 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 .

[0062] To improve the performance properties, further additives may be added, for example during drying. Other components of dispersion powder compositions contained in preferred embodiments include, for example, pigments, fillers, foam stabilizers, water repellents, or cement plasticizers.

[0063] The dispersion powder compositions, in particular the copolymers based on the inventive monomers a), b), optionally c), and optionally d), preferably contain no reactive group that can react with the inventive nitrogen compounds, in particular their amino groups, for example at a pH of 3 to 10 and / or temperatures up to 150°C or, for example, during spray drying. This is also helpful for better achieving the inventive object.

[0064] 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 by an aldehyde, keto, epoxy, isocyanate, carboxylic anhydride or aziridine group, in particular no monomer unit substituted by an epoxy 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.Examples of isocyanates include meta- and para-isopropenyl-alpha, alpha-dimethylbenzyl isocyanate (TMI) and 2-methyl-2-isocyanatopropyl methacrylate. The isocyanate groups of the monomers mentioned may optionally also be blocked, for example with phenol, salicylic acid esters, ketoxime, caprolactam, dialkyl malonate, alkyl acetoacetate, and 2,2-dimethyl-1,3-dioxane-4,6-dione. Examples of anhydride comonomers are allylsuccinic anhydride and maleic anhydride. Particularly preferably, the copolymers do not contain any 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.

[0065] 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.

[0066] The invention further relates to dry building material formulations based on one or more hydraulically setting binders, such as cement (Portland, aluminate, trass, granulated blast furnace, 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 flour, limestone flour, calcium carbonate, calcium magnesium carbonate (dolomite), chalk or hydrated lime; and optionally one or more additives, such as crosslinking agents, preservatives, film-forming aids, dispersants, foam stabilizers, plasticizers, flow agents, flame retardants, dyes or biocides.

[0067] The building material dry 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 dispersion powder compositions according to the invention, in each case based on the total weight of the building material dry formulations.

[0068] The building material dry formulations contain, for example, > 0 to 2.0 wt.%, preferably > 0 to 1.0 wt.%, more preferably > 0 to 0.5 wt.%, even more preferably > 0 to 0.3 wt.% and particularly preferably > 0 to 0.2 wt.% nitrogen compounds, based on the total weight of the building material dry formulations.

[0069] The dry building material formulations preferably contain 1 to 90 wt.%, particularly preferably 5 to 45 wt.% and most preferably 10 to 35 wt.% of hydraulically setting binders, based on the total weight of the dry building material formulations.

[0070] The dry building material formulations preferably contain 10 to 99 wt.%, particularly preferably 30 to 90 wt.% and most preferably 50 to 85 wt.% of fillers, based on the total weight of the dry building material formulations.

[0071] The building material formulations preferably contain 0.001 to 30 wt.%, particularly preferably 0.01 to 8 wt.% and most preferably 0.03 to 4 wt.% of additives, based on the dry weight of the building material formulations.

[0072] Aldehydes or ketones which may be present in the building material dry 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.

[0073] Examples of aldehydes are hexanal, propionaldehyde, and especially formaldehyde and acetaldehyde. An example of a ketone is acetone.

[0074] The building material dry formulations containing aldehydes and ketones contain in total preferably < 1 wt.%, more preferably < 0.5 wt.%, particularly preferably < 0.1 wt.%, most preferably < 0.03 wt.% and most preferably < 0.01 wt.% of aldehydes and ketones, based on the total weight of the building material dry formulations.

[0075] The dry formulations can be produced in a conventional manner using conventional equipment. The amount of water required to process the dry formulations is usually added while mixing immediately before application.

[0076] The dry building material formulations are suitable, for example, for the production of reinforcing compounds for external thermal insulation composite systems, or for the production of adhesives or coatings. Examples of adhesives include adhesives for thermal insulation boards and soundproofing panels, tile adhesives, joint mortar, and adhesives for bonding wood and wood-based materials. Examples of coatings include mortar, leveling and sealing compounds, screeds, and plasters.

[0077] Surprisingly, the dispersion powder compositions according to the invention can be used to reduce the aldehyde or ketone concentration in building material formulations.

[0078] The following examples serve to further illustrate the invention.

[0079] Copolymer dispersion:

[0080] 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).

[0081] Preparation of the dispersion powder compositions (DPP) of (Comparative) Examples 1-4: The copolymer dispersion was optionally mixed with a nitrogen compound, as indicated in Table 1, and spray-dried in a conventional manner at an inlet temperature of 130°C and an outlet temperature of 80°C, thereby obtaining a dispersion powder composition. 5 wt.% kaolin and 10 wt.% calcium carbonate were added to the dispersion powder composition as an anti-caking agent.

[0082] Table 1: Composition of the dispersion powder compositions: a) based on the polymer content of the dispersion (solid / solid).

[0083] Production of building material formulations of

[0084] (Comparison) Examples 5~8:

[0085] Cement, filler, cellulose ether and calcium formate and the respective dispersion powder composition according to the information in Table 2 were mixed.

[0086] The mixture was mixed with 28% water by weight, based on the total weight of the solids. The resulting building material formulation was homogenized for a total of 10 minutes in a planetary mixer.

[0087] The building material formulations correspond to a tile adhesive of class C2S1 with 8% polymer binder and are constructed as follows: Table 2 : Composition of the building material formulations :

[0088] Testing of aldehyde emissions:

[0089] Aldehyde emissions were measured in accordance with ISO 16000-3. For this purpose, the mortar sample was freshly mixed with 28 wt.% water in a laboratory mixer and spread evenly on a glass plate over an area of ​​0.096 m 2 distributed. 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% with an air exchange rate of 2 L / min. Over a period of 3 days, the aldehyde emissions were collected via a DNPH column and quantitatively determined by gas chromatography.

[0090] The results of the testing are summarized in Table 3 .

[0091] Mortars containing the powders of Examples 2 to 4 according to the invention exhibited significantly reduced aldehyde emissions. Table 3: Results of testing the aldehyde emissions of the building material formulations:

Claims

Patent claims:

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 are present, where in the formula R-NR 'H the radical R stands for a linear or branched, optionally substituted hydrocarbon radical having 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 carrying epoxy groups.; 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 radicals. 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 polyoxyalkyleneamines 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-. 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, 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 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 carrying 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-methylcyclohexylmethyl, triglycidyl isocyanurate and radically polymerizable epoxy compounds having at least two epoxy groups per molecule. Process for the preparation of 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, where in the formula R-NR 'H the radical R stands for a linear or branched, optionally substituted hydrocarbon radical having 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 carbonitriles; 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 no compounds bearing epoxy groups are introduced into the water-redispersible dispersion powder compositions. Process for the preparation of 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 amino compounds are added before, during or after drying; or 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. Dry building material 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. Dry building material formulations according to claim 11, characterized in that > ​​0 to 1.0 wt . -% amino compounds are present, based on the total weight of the dry building material formulations. Use of the dry building material formulations of claim 11 or 12 for producing reinforcing compounds for thermal insulation composite systems or for producing adhesives or coating agents.

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