WO2024051931A1 - Compositions de poudre de dispersion contenant un composé aminé - Google Patents

Compositions de poudre de dispersion contenant un composé aminé 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)
English (en)
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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/fr
Publication of WO2024051931A1 publication Critical patent/WO2024051931A1/fr

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Classifications

    • 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.

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne des compositions de poudre de dispersion pouvant être redispersées dans l'eau (compositions de poudre de dispersion) à base de copolymères de a) acétate de vinyle, b) éthylène, c) facultativement un ou plusieurs monomères auxiliaires, et d) facultativement un ou plusieurs monomères éthyléniquement insaturés supplémentaires. L'invention est caractérisée en ce qu'un ou plusieurs composés aminés (composés azotés) sélectionnés dans le groupe comprenant des polyoxyalkylène amines, polyéthylènes imines, polyamines aliphatiques, et des composés de la formule R-NR'H sont contenus, dans la formule R-NR'H, le groupe R représentant un groupe hydrocarboné linéaire ou ramifié et facultativement substitué ayant 1 à 20 atomes de carbone et R' est un atome d'hydrogène, un groupe NH2, ou un groupe carbonyle, à condition que les monomères auxiliaires c) soient choisis dans le groupe comprenant des acides mono- et dicarboxyliques éthyléniquement insaturés, nitriles d'acide carboxylique éthyléniquement insaturé, acrylamide (CH2CHCONH2), acides sulfoniques éthyléniquement insaturés, monomères à fonction silicium éthyléniquement insaturés, et acrylate ou méthacrylate d'hydroxyéthyle, d'hydroxypropyle ou d'hydroxybutyle ; les monomères éthyléniquement insaturés supplémentaires d) soient choisis dans le groupe comprenant de l'acrylate de méthyle, méthacrylate de méthyle, acrylate d'éthyle, méthacrylate d'éthyle, acrylate de propyle, méthacrylate de propyle, acrylate de n-butyle, méthacrylate de n-butyle, acrylate de 2-éthylhexyle, acrylate de norbornyle, aromatiques vinyliques et halogénures de vinyle ; et les compositions de poudre de dispersion pouvant être redispersées dans l'eau ne contiennent pas de composés contenant un groupe époxyde (composés époxyde).
PCT/EP2022/074769 2022-09-06 2022-09-06 Compositions de poudre de dispersion contenant un composé aminé WO2024051931A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
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US6063865A (en) 1997-07-31 2000-05-16 Wacker-Chemie Gmbh Crosslinkable powder composition which is redispersible in water
US6080806A (en) 1996-01-10 2000-06-27 Rhodia Chimie Water-redispersible powders of film-forming polymers prepared from ethylenically unsaturated monomers
EP1035175A2 (fr) * 1999-03-10 2000-09-13 Wacker-Chemie GmbH Concentrat de coagulation utilisable pour le préparation de masses aqueuses de platre et de revêtement de séchage rapide et ces masses
EP1216962A1 (fr) * 2000-12-21 2002-06-26 Consortium für elektrochemische Industrie GmbH Procédé pour éliminer les aldéhydes libres
US20100197831A1 (en) 2009-02-02 2010-08-05 Wacker Chemie Ag Crosslinkable polymer powder composition which is redispersible in water
WO2014108434A1 (fr) * 2013-01-08 2014-07-17 Henkel Ag & Co. Kgaa Liant résistant à l'eau à base d'alpha semi-hydrate de sulfate de calcium
US20170027544A1 (en) 2014-02-20 2017-02-02 Karlsruher Institut für Technologie Device for ultrasound-supported reflection and transmission tomography
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6080806A (en) 1996-01-10 2000-06-27 Rhodia Chimie Water-redispersible powders of film-forming polymers prepared from ethylenically unsaturated monomers
US6063865A (en) 1997-07-31 2000-05-16 Wacker-Chemie Gmbh Crosslinkable powder composition which is redispersible in water
EP1035175A2 (fr) * 1999-03-10 2000-09-13 Wacker-Chemie GmbH Concentrat de coagulation utilisable pour le préparation de masses aqueuses de platre et de revêtement de séchage rapide et ces masses
EP1216962A1 (fr) * 2000-12-21 2002-06-26 Consortium für elektrochemische Industrie GmbH Procédé pour éliminer les aldéhydes libres
US20100197831A1 (en) 2009-02-02 2010-08-05 Wacker Chemie Ag Crosslinkable polymer powder composition which is redispersible in water
WO2014108434A1 (fr) * 2013-01-08 2014-07-17 Henkel Ag & Co. Kgaa Liant résistant à l'eau à base d'alpha semi-hydrate de sulfate de calcium
US20170027544A1 (en) 2014-02-20 2017-02-02 Karlsruher Institut für Technologie Device for ultrasound-supported reflection and transmission tomography
US20220135784A1 (en) 2019-02-26 2022-05-05 Wacker Chemie Ag Crosslinkable polymer-powder compositions redispersible in water

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NACH FOX T. G., BULL. AM. PHYSICS SOC., vol. 1, no. 3, 1956, pages 123

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