Dispersion powder composition of amino-containing compound

Abstract

The present invention relates to a water redispersible powder composition based on a copolymer 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 by comprising one or more amino compounds (nitrogen compounds), the auxiliary monomer c) is selected from the group consisting of polyoxyalkylene amines, polyethyleneimine, aliphatic polyamines and compounds of formula R-NR 'H wherein in formula R-NR' H, the group R is a linear or branched, optionally substituted hydrocarbyl group having 1 to 20 carbon atoms and R 'is a hydrogen atom, an NH2 group or a carbonyl group, with the proviso that the auxiliary monomer c) is selected from ethylenically unsaturated monocarboxylic acids and dicarboxylic acids; an ethylenically unsaturated carboxylic acid nitrile; an acrylamide (CH2CHCONH2), an acrylamide (CH2CHCONH2); an ethylenically unsaturated sulfonic acid; an ethylenically unsaturated silicon functional monomer; and hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate or hydroxyethyl methylacrylate, hydroxypropyl methylacrylate or hydroxybutyl methylacrylate, the further ethylenically unsaturated monomer d) is selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatic compounds and vinyl halides; and the water-redispersible dispersible powder composition does not contain any compound with an epoxy group (epoxy compound).

Description

[0001] The present invention relates to water-redispersible dispersible powder compositions comprising amino compounds, to a process for their preparation and to their use in coating compositions or adhesives, in particular, for example, in the construction sector.

[0002] Water-redispersible polymer powders (dispersible powders) are usually obtained by drying aqueous polymer dispersions. Drying is usually carried out in the presence of a drying aid, which allows a shell of the drying aid to form around the polymer particles. During the drying process, the drying aid prevents the polymer particles from irreversibly sticking together during the production, storage, transportation and use of the drying aid. When the dispersible powder is dispersed in water, the drying aid matrix is ​​redissolved, resulting in the polymer particles being released again into the aqueous dispersion and present therein with the particle size distribution of the original dispersion.

[0003] Dispersible powders of this type are used in many construction chemical products, for example in coating compositions or adhesives, such as tile adhesives, caulking compounds, self-leveling compounds, thermal insulation composite systems or jointing mortars. Advantageously, the dispersible powders can be used in pre-prepared, storable dry mixtures, optionally with hydraulic binders such as cement, which mixtures are converted into ready-to-use products by adding water and mixing only shortly before use.

[0004] In order to improve their processing and performance properties, building material formulations are usually equipped with many additives, such as polymer powders, thickeners, plasticizers, retarders, accelerators, defoamers, air entraining agents and many other additives. The disadvantage of building material formulations modified in this way is that they can release low molecular weight, high volatility substances and other harmful substances, including ketones or alkanals, informally referred to as aldehydes, such as formaldehyde, acetaldehyde, propionaldehyde or higher homologues of alkanal group compounds. Such carbonyl compounds are usually reactive, and many are classified as carcinogens, which is why the emission of aldehyde and ketone compounds must be avoided as early as possible in the formulation stage. In addition, aldehydes or ketones can be released during the processing or use of building material products, and can endanger the health of users or consumers in construction sites, especially users in indoor spaces in private and commercial environments.

[0005] For commercial formulators of building material formulations, it is often simply impossible to determine which additive is responsible for the release of aldehydes or ketones. Methods for qualitative and quantitative determination of low-medium-volatility and low-molecular-weight chemicals are laborious and are not conventional analytical methods. As a further complicating factor, aldehyde or ketone impurities can be released from additives by chemical reactions only when the building material formulation is manufactured, and therefore the purification steps in the manufacturing process of the additives cannot completely solve the problem of aldehyde or ketone release. For example, aldehydes in fresh mortar with a high pH can be released by hydrolysis of residual monomer vinyl esters of long-chain carboxylic acids, which are not always completely removed by conventional methods such as stripping due to their low volatility. However, the dispersible powder itself does not usually constitute a significant source of aldehydes or ketones, because any aldehyde or ketone components formed or introduced during the preparation of the powder by emulsion polymerization, for example from initiators such as sodium formaldehyde sulfoxylate, are removed from the resulting dispersible powder composition at the latest during the drying of the polymer dispersion.

[0006] Against this background, it was an object of the present invention to provide measures which make it possible to reduce the aldehyde or ketone concentration in building material formulations during or after application.

[0007] Surprisingly, this object is essentially achieved by a water-redispersible dispersible powder composition based on a copolymer of a) vinyl acetate, b) ethylene, c) optionally an auxiliary monomer, and d) optionally other ethylenically unsaturated monomers, characterized in that

[0008] The presence of specific amino compounds, and

[0009] The auxiliary monomers c) and the further ethylenically unsaturated monomers d) are each selected from specific groups.

[0010] US6080806 recommends a dispersible powder composition of styrene-butadiene copolymer and amino acid for improving mechanical properties such as impact resistance, flexibility or bonding strength. US201727544 relates to an aqueous dispersion of a crosslinkable copolymer including lysine as a crosslinker and 1,3-dicarbonyl monomers and other monomers. US6063865A relates to a water-redispersible crosslinkable powder composition containing a) 30% to 95% by weight of a water-insoluble film-forming polymer of ethylenically unsaturated monomers, wherein 0.5% to 10% by weight of the monomers carry aldehyde, ketone, epoxy, isocyanate, carboxylic anhydride or aziridine groups, b) 5% to 70% by weight of a water-soluble film-forming polymer, and c) a compound having at least two functional groups from amine, hydrazide, hydroxylamine ester and aromatic or alkyl hydrazine or hydrazone series in the form of a salt. US20220135784 and US20100197831 relate to crosslinkable water-redispersible polymer powder compositions comprising a vinyl ester polymer and an epoxy compound and optionally a crosslinking curing agent having two or more amino groups.

[0011] The present invention provides a water-redispersible dispersible powder composition (dispersible powder composition) based on a copolymer 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

[0012] the presence of one or more amino compounds (nitrogen compounds) selected from the group consisting of polyoxyalkylene amines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H,

[0013] wherein, in the formula R-NR'H, the group R is a linear or branched, optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R' is a hydrogen atom, an NH2 group or a carbonyl group,

[0014] Provided that the auxiliary monomer c) is selected from ethylenically unsaturated monocarboxylic acids and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; acrylamide (CH2CHCONH2); ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate or hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate, and

[0015] The additional ethylenically unsaturated monomers d) are selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatic compounds and vinyl halides, and

[0016] The water-redispersible dispersible powder composition does not contain any compound carrying epoxy groups (epoxide compound).

[0017] The nitrogen compound preferably contains 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 all two amino groups.

[0018] The group R in the compound of the formula R-NR'H is preferably a straight-chain or branched, optionally substituted hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.

[0019] Preferred substituents in the radical R are acid, amide, amine, alcohol, alkylene oxide, thiol or thioether groups, for example methyl thioether groups, or aromatic or heteroaromatic groups, for example phenyl or imidazole groups. Preferred substituents in the R radical are amine or acid groups, for example sulfonic acid or preferably carboxylic acid groups. Preferably, the radical R carries at least two substituents, in particular two substituents.

[0020] The group R' is preferably a carbonyl group, more preferably a hydrogen atom. Nitrogen compounds having a carbonyl group as group R' are also known as amides. The carbonyl group preferably contains 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, most preferably 1 to 5 carbon atoms.

[0021] Preferred compounds of the formula R-NR'H are aliphatic or aromatic amines, especially amino acids.

[0022] Examples of aliphatic or aromatic amines are hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, tetraethylenepentamine, 1,2-propylenediamine, diproprenediamine, diethylaminopropylamine, phenylenediamine and isophoronediamine.

[0023] Natural amino acids are preferred, especially proteinogenic amino acids. The most preferred amino acids are glycine, aspartic acid, glutamic acid, and especially lysine.

[0024] The molecular weight MW of the nitrogen compound of formula R—NR′H is preferably ≤500 g / mol, more preferably ≤300 g / mol, most preferably ≤200 g / mol. The molecular weight MW of the nitrogen compound of formula R—NR′H is preferably ≥50 g / mol, more preferably ≥75 g / mol.

[0025] The polyoxyalkyleneamine is preferably a polyoxyalkylene with one or more amino groups, preferably 1 to 3 amino groups, more preferably 2 amino groups. The polyoxyalkylene units are preferably based on ethylene oxide (EO) groups, propylene oxide (PO) groups and / or butylene oxide groups. Ethylene oxide (EO) groups and / or propylene oxide (PO) groups are more preferred. The polyalkyleneoxy glycol preferably carries an amine group at one end of the chain or more preferably at both ends of the chain. The polyoxyalkyleneamine can be, for example, Jeffamine R Product name obtained.

[0026] The polyethyleneimine is preferably a polymer having a repeating structural unit -CH2-CH2-NH-. Such polyethyleneimine is available, for example, as Lupasol R Commercially available under the trade name HYDRAFLEX® from BASF SE.

[0027] Aliphatic polyamines are also generally known and can be found, for example, in the form of Anquamine R 、Epilink R and Epilox R The curing agent is commercially available under the trade name SUPERVISION®.

[0028] The molecular weight MW of the polyoxyalkyleneamines, polyethyleneimines and aliphatic polyamines is 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, most preferably ≤10 000 g / mol. The molecular weight MW of the polyoxyalkyleneamines, polyethyleneimines and aliphatic polyamines is preferably ≥200 g / mol, more preferably ≥300 g / mol, most preferably ≥400 g / mol.

[0029] The nitrogen compounds may also be present in salt form, for example in the form of their ammonium salts, for example with an acid group such as a carboxylic acid or a halide as counterion.

[0030] Preferred nitrogen compounds are polyoxyalkylene amines and compounds of the formula R-NR'H, especially amino acids.

[0031] The dispersible powder composition preferably contains 0.1 wt. % to 30 wt. %, more preferably 0.2 wt. % to 20 wt. %, even more preferably 0.3 wt. % to 15 wt. %, especially preferably 0.3 wt. % to 12 wt. %, most preferably 0.3 wt. % to 10 wt. %, and most preferably a total of 0.3 wt. % to 3 wt. % of nitrogen compound, based on the total weight of the dispersible powder composition.

[0032] 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.

[0033] The dispersible powder composition preferably contains 40 to 99 wt %, more preferably 50 to 95 wt %, and most preferably 70 to 90 wt % of the copolymer of the present invention, based on the total weight of the dispersible powder composition.

[0034] The extent to which the copolymer is based on vinyl acetate a) is preferably 50% to <100% by weight, more preferably 59.8% to 94% by weight and most preferably 68.5% to 90% by weight, based on the total weight of the copolymer.

[0035] The extent of the copolymers based on ethylene b) is preferably from >0 to 50% by weight, more preferably from 0.1 to 40% by weight, most preferably from 1 to 30% by weight, based on the total weight of the copolymers.

[0036] The auxiliary monomers c) are selected from the following group: 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 vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid; ethylenically unsaturated silicon-functional monomers, for example acryloxypropyltri(alkoxy)silane and methacryloxypropyltri(alkoxy)silane, vinyltrialkoxysilane and vinylmethyldialkoxysilane, in which methoxy, ethoxy and ethoxypropylene glycol ether groups can be present, for example, as alkoxy groups; and hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or hydroxyethyl, hydroxypropyl or hydroxybutyl methacrylate.

[0037] Particularly preferred auxiliary monomers c) are ethylenically unsaturated acids, for example acrylic acid, methacrylic acid and vinylsulfonic acid.

[0038] The auxiliary monomers c) are generally different from vinyl acetate a), ethylene b) and the optionally present further ethylenically unsaturated monomers d).

[0039] The extent of the copolymers based on auxiliary monomers c) is preferably 0% to 20% by weight, more preferably 0.1% to 10% by weight and most preferably 0.5% to 5% by weight, based on the total weight of the copolymers.

[0040] The further ethylenically unsaturated monomers d) are selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatic compounds (especially styrene and vinyltoluene) and vinyl halides (e.g. vinyl chloride). Particularly preferred are vinyl chloride, methyl methacrylate, n-butyl acrylate and styrene. Most preferred is vinyl chloride.

[0041] The further ethylenically unsaturated monomers d) are generally different from vinyl acetate a), ethylene b) and the optionally present auxiliary monomers c).

[0042] The degree of further ethylenically unsaturated monomers d) in the copolymers is preferably 0% to <50% by weight, more preferably 0.1% to 40% by weight and most preferably 1% to 30% by weight, based on the total weight of the copolymers.

[0043] The copolymer preferably consists of units of vinyl acetate a), ethylene b), optionally auxiliary monomers c), and optionally further ethylenically unsaturated monomers d). More preferably, the copolymer consists of units of vinyl acetate a), ethylene b), and optionally further ethylenically unsaturated monomers d).

[0044] The weight proportions of monomers and comonomers are selected to generally produce a glass transition temperature Tg of -50°C to +40°C, preferably -30°C to +35°C. The glass transition temperature Tg of a polymer can be determined in a known manner by differential scanning calorimetry (DSC). Tg can also be approximately predicted by the Fox equation. According to Fox TG, Bull. Am. Physics Soc. 1, 3, page 123 (1956): 1 / Tg=x1 / Tg1+x2 / Tg2+...+xn / Tgn, where xn is the mass fraction of monomer n (wt% / 100), and Tgn is the glass transition temperature of a homopolymer of monomer n in Kelvin. The Tg values ​​for homopolymers are listed in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975).

[0045] The copolymers are preferably prepared by an emulsion polymerization process. Emulsion polymerization is usually carried out in an aqueous medium. The polymerization temperature is usually from 40° C. to 110° C., preferably from 60° C. to 95° C. The copolymerization of gaseous comonomers such as ethylene, 1,3-butadiene or vinyl chloride can also be operated under pressure, usually between 5 and 100 bar.

[0046] Polymerization can usually be initiated using a redox initiator combination commonly used for emulsion polymerization. By metering the initiator, the monomer conversion can be controlled in the usual way. The initiator is usually metered in as a whole to ensure continuous polymerization. Examples of suitable oxidative initiators include sodium salts, potassium salts and ammonium salts of peroxodisulfuric acid, hydrogen peroxide, tert-butyl peroxide, tert-butyl hydroperoxide, potassium peroxydiphosphate, tert-butyl peroxypivalate, cumene hydroperoxide and azobisisobutyronitrile. Preferred sodium salts, potassium salts and ammonium salts of peroxodisulfuric acid and hydrogen peroxide. Based on the gross weight of the monomer, the mentioned initiator is usually used in an amount of 0.01% by weight to 2.0% by weight.

[0047] Examples of suitable reducing agents are alkali metal and ammonium sulfites and bisulfites, such as sodium sulfite, derivatives of hyposulfurous acid, such as zinc or alkali metal formaldehyde sulfoxylates, such as sodium formaldehyde bisulfoxylate (Bruggolite), and (iso)ascorbic acid. Sodium formaldehyde bisulfoxylate 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.

[0048] The oxidizing agents mentioned, in particular salts of peroxodisulphuric acid and hydrogen peroxide, can also be used alone as thermal initiators.

[0049] In the emulsion polymerization process, the material that serves as chain transfer agent can be used to control the molecular weight. When using chain transfer agent, they are usually used in an amount of 0.001% by weight to 5.0% by weight based on the monomer to be polymerized, and are metered in separately or in the form of a premix with the reaction components. Examples of such materials are n-dodecyl mercaptan, tert-dodecyl mercaptan, mercaptopropionic acid or its alkali metal salt, methyl mercaptopropionate, isopropanol, phosphonic acid or its derivatives, phosphinic acid or its derivatives, and acetaldehyde. Preferably, 2-mercaptopropionic acid or tert-dodecyl mercaptan is used.

[0050] For stability, protective colloids can be used, optionally in combination with emulsifiers. In the emulsion polymerization process, polymerization can also be carried out in the presence of an emulsifier. Based on the total weight of the monomers, the preferred amount of emulsifier is 1% by weight to 7% by weight. Examples of emulsifiers are anionic, cationic or nonionic emulsifiers, such as anionic surfactants, especially alkyl sulfates with a chain length of 8 to 18 carbon atoms, alkyl or alkyl aryl ether sulfates with 8 to 18 carbon atoms and up to 40 ethylene oxide or propylene oxide units in the hydrophobic group, alkyl or alkyl aryl sulfonates with 8 to 18 carbon atoms, esters and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants, such as alkyl polyglycol ethers or alkyl aryl polyglycol ethers with 8 to 40 ethylene oxide units.

[0051] The polymerization is particularly preferably carried out in the absence of emulsifiers. The aqueous dispersion and / or the polymer powder preferably do not contain any emulsifiers.

[0052] At the end of the polymerization, residual monomers can be removed by post-polymerization using known methods, for example by post-polymerization initiated by redox catalysts. Volatile residual monomers can also be removed by distillation, preferably under reduced pressure and optionally while passing or passing an inert entraining gas such as air, nitrogen or water vapor.

[0053] 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 stabilized protective colloids.

[0054] Examples of protective colloids are polyvinyl alcohol; polyvinyl acetals; polyvinyl pyrrolidone; water-soluble forms of polysaccharides, for example starch (amylose and amylopectin), cellulose and its carboxymethyl, methyl, hydroxyethyl and hydroxypropyl derivatives, dextrins and cyclodextrins; proteins, for example casein or caseinates, soy protein, gelatin; lignin sulfonates; synthetic polymers, for example poly(meth)acrylic acid, copolymers of (meth)acrylates with carboxyl-functional comonomer units, poly(meth)acrylamide, polyvinylsulfonic acid and water-soluble copolymers thereof; melamine-formaldehyde sulfonates, naphthalene-formaldehyde sulfonates, styrene-maleic acid copolymers and vinyl ether-maleic acid copolymers.

[0055] Partially or completely hydrolyzed polyvinyl alcohols with a degree of hydrolysis of preferably 80 to 100 mol % are preferred. Particularly preferred are partially hydrolyzed polyvinyl alcohols with a degree of hydrolysis of 80 to 95 mol %, in particular in 4 % aqueous solution. Viscosity 1 to 30 mPa·s (at 20°C) Most preferred are polyvinyl alcohols having a degree of hydrolysis of 85 to 94 mol%, in particular in a 4% aqueous solution. Viscosity 3 to 15 mPa·s (at 20°C) The protective colloids mentioned can be obtained by methods known to those skilled in the art. The protective colloid is preferably present in an amount of 1% to 30% by weight, more preferably 3% to 20% by weight, based on the total weight of the copolymer.

[0056] The solids content of the aqueous dispersion is preferably from 30% to 75% by weight, more preferably from 45% to 70% by weight.

[0057] The aqueous dispersion of the copolymer may itself be converted into the copolymer in the form of a water-redispersible powder in a conventional manner, for example in a manner analogous to that described further below for drying to prepare a dispersible powder composition.

[0058] The water-redispersible dispersible powder composition does not contain any compound having epoxy groups (epoxide compound). Epoxide compounds are detrimental in achieving the objects of the present invention.

[0059] Examples of epoxy compounds are epoxy resins. These are, for example, bisphenol A type epoxy compounds, i.e. condensation products of bisphenol A and epichlorohydrin or methyl epichlorohydrin. Other examples are epoxy resins based on bisphenol-F, which generally contain a mixture of bisglycidyloxyphenylmethane. Further examples include 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. Epoxy resins of this type are commercially available, for example under the name Epilox R Particularly preferably, no epoxy resins of the bisphenol A and bisphenol F types are present.

[0060] Other examples of epoxy compounds are bisglycidyloxyphenylmethane, butyl diglycidyl ether, vinylcyclohexane dioxide, dicyclopentadiene dioxide, 3,4-epoxy-6-methylcyclohexylmethyl and triglycidyl isocyanurate.

[0061] Epoxides also include free radical polymerizable epoxy compounds having at least two epoxy groups per molecule. Epoxides may be aliphatic, aliphatic or aromatic in nature.

[0062] The present invention also provides a method for preparing a water-redispersible dispersible powder composition (dispersible powder composition), characterized in that:

[0063] mixing a copolymer based on a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers, and d) optionally one or more further ethylenically unsaturated monomers with one or more amino compounds (nitrogen compounds), and

[0064] The amino compound (nitrogen compound) is selected from polyoxyalkylene amines, polyethylene imines, aliphatic polyamines and compounds of formula R-NR'H,

[0065] wherein, in the formula R-NR'H, the group R is a linear or branched, optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R' is a hydrogen atom, an NH2 group or a carbonyl group,

[0066] Provided that the auxiliary monomer c) is selected from ethylenically unsaturated monocarboxylic acids and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; acrylamide (CH2CHCONH2); ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate or hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate, and

[0067] The additional ethylenically unsaturated monomers d) are selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatic compounds and vinyl halides, and

[0068] No compound bearing an epoxy group (epoxide compound) is introduced into the water-redispersible dispersible powder composition.

[0069] The admixture of the nitrogen compound is usually carried out after the preparation of the copolymer by polymerization.

[0070] The mixing of the copolymer and the nitrogen compound can be carried out, for example, before, during or after the drying of the aqueous dispersion of the copolymer (polymer dispersion). Preferably, the addition of the nitrogen compound is carried out before the drying of the aqueous polymer dispersion. For this reason, preferably one or more nitrogen compounds are added to the aqueous polymer dispersion and the mixture thus obtained is then dried. Alternatively, one or more copolymers in the form of water-redispersible powders can be mixed with one or more nitrogen compounds.

[0071] Drying aids are usually added to the aqueous dispersion. Drying aids are usually 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 aids and protective colloids before the drying process is preferably 1% to 30% by weight, based on the solids content of the aqueous dispersion.

[0072] The aqueous dispersion can be dried, for example, by fluidized bed drying, freeze drying or spray drying. The dispersion is preferably spray dried. Spray drying is carried out in a standard spray drying system, by atomization through a one-, two- or multiphase nozzle or with a rotating disk. The outlet temperature selected is generally in the range of 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.

[0073] The viscosity of the feed to be atomized is adjusted via the solids content so that a value of <500 mPa·s (Brookfield viscosity at 20 rpm and 23° C.), preferably <250 mPa·s, is obtained. The solids content of the dispersion to be atomized is preferably 30% to 75% by weight, more preferably 45% to 70% by weight.

[0074] Contents of up to 1.5% by weight of defoamers, based on the copolymer, have proven to be advantageous in many cases. The defoamers are preferably added during the drying process.

[0075] In order to increase storage stability by improving adhesion stability, particularly in the case of copolymers with low glass transition temperature, one or more anti-blocking agents (anti-caking agents) can be provided to the polymer powder obtained. Preferably during or after drying, anti-blocking agents are added to the spray drying system during drying. Based on the gross weight of the polymer component, the preferred polymer powder comprises anti-blocking agents, particularly 1 wt % to 40 wt %. The example of anti-blocking agent is calcium carbonate or magnesium carbonate, talcum, gypsum, silicon dioxide, kaolin (such as metakaolin) and silicate, preferably with a particle size in the range of 10nm to 10 μm.

[0076] To improve the performance properties, further additives may be added, for example during the drying process.Examples of further ingredients present in the dispersible powder composition in the preferred embodiment are pigments, fillers, foam stabilizers, hydrophobic agents or cement plasticizers.

[0077] The dispersible powder composition, in particular the copolymer based on the monomers a), b), optionally c) and optionally d) according to the invention, preferably does not contain any reactive groups which are capable of reacting with the nitrogen compounds according to the invention, in particular with their amino groups, for example at a pH of 3 to 10 and / or at temperatures of up to 150° C. or, for example, during spray drying. This also contributes to making it easier to achieve the objects of the present invention.

[0078] The copolymers according to the invention based on monomers a), b), optionally c) and optionally d) preferably do not contain any monomer units substituted by aldehyde, ketone, epoxy, isocyanate, carboxylic anhydride or aziridine groups, in particular do not contain monomer units substituted by epoxy groups. Examples of monomers containing aldehyde and keto groups are acrolein, vinyl methyl ketone, allyl acetoacetate, vinyl acetoacetate, vinyl or allyl diacetoacetate, 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 are m- and p-isopropenyl-α,α-dimethylbenzyl isocyanate (TMI) and 2-methyl-2-isocyanatopropyl methacrylate, wherein the isocyanate groups of the monomers may also optionally be terminated, for example, with phenol, salicylate, ketoxime, caprolactam, dialkyl malonate, alkyl acetoacetate or 2,2-dimethyl-1,3-dioxane-4,6-dione. Examples of anhydride comonomers are allyl succinic anhydride and maleic anhydride. Particularly preferably, the copolymer does not contain any units of monomers selected from the group consisting of glycidyl (meth)acrylate, m- and p-isopropenyl-α,α-dimethylbenzyl isocyanate (TMI), allyl acetoacetate, acetoacetylated hydroxyethyl (meth)acrylate and acetoacetylated hydroxypropyl (meth)acrylate. Most preferably, the copolymer does not contain any glycidyl (meth)acrylate units.

[0079] The dispersible powder compositions are particularly suitable for use in construction chemical products. They can be used alone or in combination with conventional polymer dispersions or dispersible powders.

[0080] The present invention further provides a building material drying preparation based on

[0081] one or more hydraulic binders, such as cement (Portland cement, aluminate cement, pozzolanic cement, slag cement, magnesia cement, phosphate cement), gypsum and water glass;

[0082] one or more dispersible powder compositions of the present invention;

[0083] optionally one or more fillers, for example quartz sand, quartz powder, limestone powder, calcium carbonate, calcium magnesium carbonate (dolomite), chalk or white hydrated lime; and

[0084] Optionally one or more additives are present, for example crosslinkers, preservatives, film-forming aids, dispersants, foam stabilizers, plasticizers, flow improvers, flame retardants, dyes or biocides.

[0085] Dry formulations for building materials preferably contain 0.1 to 40% by weight, more preferably 0.3 to 25.0% by weight, most preferably 0.5 to 15% by weight, of the dispersible powder composition according to the invention, in each case based on the total weight of the dry formulation for building materials.

[0086] 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.

[0087] The dry building material formulation preferably comprises 1 to 90 wt. %, more preferably 5 to 45 wt. % and most preferably 10 to 35 wt. % of hydraulic binder, based on the total weight of the dry building material formulation.

[0088] The dry building material formulation preferably contains 10 to 99 wt. %, more preferably 30 to 90 wt. % and most preferably 50 to 85 wt. % of filler, based on the total weight of the dry building material formulation.

[0089] The building material formulation preferably contains 0.001 to 30 wt. %, more preferably 0.01 to 8 wt. %, most preferably 0.03 to 4 wt. % of additives, based on the dry weight of the building material formulation.

[0090] The aldehydes or ketones which may be present in the dry formulations of building materials 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.

[0091] Examples of aldehydes are hexanal, propionaldehyde, in particular formaldehyde and acetaldehyde. An example of a ketone is acetone.

[0092] Dry building material preparations containing aldehydes and ketones preferably contain a total of ≤1% by weight, more preferably ≤0.5% by weight, particularly preferably ≤0.1% by weight, most preferably ≤0.03% by weight and most preferably a total of ≤0.01% by weight of aldehydes and ketones, based on the total weight of the dry building material preparation.

[0093] The production of dry formulations for building materials can be carried out in a conventional manner in conventional apparatuses. The amount of water required for processing the dry formulations for building materials is usually added under mixing immediately before application.

[0094] 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 compositions. Examples of adhesives are adhesives for thermal and acoustic insulation panels, tile adhesives, joint mortars, and adhesives for bonding wood and wood-based materials. Examples of coating compositions are mortars, self-leveling and sealing compounds, mortars and plasters.

[0095] Surprisingly, the dispersible powder compositions according to the invention make it possible to reduce the concentration of aldehydes and ketones in building material formulations.

[0096] The following examples are provided to further illustrate the present invention.

[0097] Copolymer dispersion:

[0098] A polyvinyl alcohol-stabilized aqueous dispersion of vinyl acetate-ethylene-vinyl chloride copolymer having a glass transition temperature of 13° C. The polyvinyl alcohol has a degree of hydrolysis of 88 mol % and a relative humidity of 4 mPa·s. Viscosity (in 4% aqueous solution).

[0099] (Comparative) Preparation of dispersible powder compositions (DPP) of Examples 1-4:

[0100] The copolymer dispersion was optionally mixed with the nitrogen compound specified in Table 1 and dried in a conventional manner per se by spray drying at an inlet temperature of 130° C. and an outlet temperature of 80° C. to provide a dispersible powder composition. 5% by weight of kaolin and 10% by weight of calcium carbonate were added as anti-caking agents to the dispersible powder composition.

[0101] Table 1: Composition of dispersible powder composition:

[0102]

[0103]

[0104] a) Based on the polymer content of the dispersion (solids / solids).

[0105] (Comparative) Preparation of building material formulations of Examples 5-8:

[0106] The cement, filler, cellulose ether, calcium formate and corresponding dispersible powder composition specified in Table 2 were mixed.

[0107] Water was added to a content of 28% by weight, based on the total weight of solids.The resulting building material formulation was homogenized in a planetary mixer for a total of 10 minutes.

[0108] The building material formulation corresponds to a C2S1 grade tile adhesive with a polymer binder content of 8% and has the following composition:

[0109] Table 2: Composition of building material formulations:

[0110]

[0111] Aldehyde emission test:

[0112] The aldehyde emission was measured according to ISO 16000-3. For this purpose, the mortar samples were freshly mixed with 28% by weight of water in a laboratory mixer and spread evenly over 0.096 m 2 on a glass plate using a smooth spatula. 2 The target layer thickness is 3 mm. The corresponding samples are then immediately transferred to the VOC test chamber (manufacturer Volume = 240 L). The box 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 total period of 3 days, aldehyde emissions were collected by DNPH column and quantified by gas chromatography.

[0113] The results are listed in Table 3.

[0114] Plasters containing the powders according to the invention according to Examples 2 to 4 exhibit significantly reduced aldehyde emissions.

[0115] Table 3: Results of aldehyde emission testing of building material formulations:

Claims

1. A water-redispersible dispersible powder composition based on a copolymer 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 wherein there are one or more amino compounds selected from the group consisting of polyoxyalkylene amines, polyethyleneimines, aliphatic polyamines and compounds of formula R-NR'H, wherein, in the formula R-NR'H, the group R is a linear or branched, optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R' is a hydrogen atom, an NH2 group or a carbonyl group, Provided that the auxiliary monomer c) is selected from ethylenically unsaturated monocarboxylic acids and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; acrylamides; ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate or hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate, and The additional ethylenically unsaturated monomers d) are selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatic compounds and vinyl halides, and The water-redispersible dispersible powder composition does not contain any compound having an epoxy group.

2. The water-redispersible dispersible powder composition according to claim 1, characterized in that Each amino compound contains 1 to 50 amino groups.

3. The water-redispersible powder composition according to claim 1 or 2, characterized in that The radical R carries one or more substituents selected from the group consisting of acid, amide, amine, alcohol, alkylene oxide, thiol and thioether groups and aromatic or heteroaromatic groups.

4. The water-redispersible dispersible powder composition according to claims 1 to 3, characterized in that The one or more amino compounds are selected from the group consisting of hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, phenylenediamine, isophoronediamine and amino acids.

5. The water-redispersible dispersible powder composition according to claims 1 to 4, characterized in that The polyoxyalkyleneamines are based on units of ethylene oxide (EO), propylene oxide (PO) and / or butylene oxide and carry one or more amino groups, and the polyethyleneimines are based on -CH2-CH2-NH- structural units.

6. The water-redispersible dispersible powder composition according to claims 1 to 5, characterized in that The water-redispersible powder composition contains 0.1 wt% to 20 wt% of the amino compound based on the total weight of the water-redispersible powder composition.

7. The water-redispersible dispersible powder composition according to claims 1 to 6, characterized in that The water-redispersible powder composition contains 40 to 99 wt % of a copolymer of a) vinyl acetate, b) ethylene, c) optionally an auxiliary monomer, and d) optionally other ethylenically unsaturated monomers, based on the total weight of the water-redispersible powder composition.

8. The water-redispersible dispersible powder composition according to claims 1 to 7, characterized in that The water-redispersible dispersible powder composition does not contain any compound having an epoxy group selected from the group consisting of epoxy resins, aliphatic epoxy compounds, heterocyclic epoxy compounds, diglycidyloxyphenylmethane, butyl diglycidyl ether, vinylcyclohexane dioxide, dicyclopentadiene dioxide, 3,4-epoxy-6-methyl-cyclohexylmethyl, triglycidyl isocyanurate, and a free radical polymerizable epoxy compound having at least two epoxy groups per molecule.

9. A method for preparing a water-redispersible dispersible powder composition, characterized in that: mixing a copolymer based on a) vinyl acetate, b) ethylene, c) optionally one or more auxiliary monomers, and d) optionally one or more further ethylenically unsaturated monomers, with one or more amino compounds selected from the group consisting of polyoxyalkylene amines, polyethyleneimines, aliphatic polyamines and compounds of the formula R-NR'H, wherein, in the formula R-NR'H, the group R is a linear or branched, optionally substituted hydrocarbon group having 1 to 20 carbon atoms, and R' is a hydrogen atom, an NH2 group or a carbonyl group, Provided that the auxiliary monomer c) is selected from the group consisting of ethylenically unsaturated monocarboxylic acids and dicarboxylic acids; ethylenically unsaturated carboxylic acid nitriles; acrylamides; ethylenically unsaturated sulfonic acids; ethylenically unsaturated silicon-functional monomers; and hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate or hydroxyethyl methacrylate, hydroxypropyl methacrylate or hydroxybutyl methacrylate, and The additional ethylenically unsaturated monomers d) are selected from the group consisting of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, norbornyl acrylate, vinyl aromatic compounds and vinyl halides, and No compound bearing an epoxy group is introduced into the water-redispersible dispersible powder composition.

10. The method for preparing a water-redispersible dispersible powder composition according to claim 9, characterized in that: The copolymer based on a) vinyl acetate, b) ethylene, c) optionally auxiliary monomers, and d) optionally further ethylenically unsaturated monomers is dried in the form of an aqueous dispersion and mixed with the amino compound before, during or after drying; or A copolymer based on a) vinyl acetate, b) ethylene, c) optionally auxiliary monomers, and d) optionally further ethylenically unsaturated monomers in the form of a water-redispersible powder is mixed with the amino compound.

11. A dry formulation for building materials based on one or more hydraulic binders, one or more water-redispersible dispersible powder compositions according to claims 1 to 8, optionally one or more fillers, and optionally one or more additives.

12. The dry building material preparation according to claim 11, characterized in that: The amino compounds are present in the dry building material formulations in an amount of >0% to 1.0% by weight, based on the total weight of the dry building material formulations.

13. Use of the dry formulation of building materials according to claim 11 or 12 for producing reinforcing compounds for thermal insulation composite systems, or for producing adhesives or coating compositions.

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